Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts

Abstract

Described are certain mono(cyclopentadienyl) Group IV B metal compounds, catalyst systems comprising such mono(cyclopentadienyl) metal compounds and an activator, and to a process using such catalyst systems for the production of polyolefins, particularly ethylene-α-olefin copolymers having a high molecular weight and high level of α-olefin incorporation.

We claim:  
     
       1. A compound of the formula:                    
       wherein: 
       M is Zr, Hf or Ti;  
       (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with from zero to four substituent groups R, “x” is 0, 1, 2, 3, or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C 1 -C 20  hydrocarbyl radicals, substituted C 1 -C 20  hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, and alkoxy radical, C 1 -C 20  hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group IV A of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C 5 H 4-x R x ) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C 4 -C 20  ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;  
       R′ is a radical selected from C 1 C 3 -C 20  aliphatic and alicyclic hydrocarbyl radicals wherein one or more hydrogen atoms may be replaced by radicals selected from halogen, amido, phosphido, alkoxy or any other radical containing a Lewis acidic or basic functionality, with the proviso that R′ is convalently bonded to the nitrogen atom through a 1° or 2° carbon atom;  
       each Q may be independently an univalent anionic ligand, or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand with the proviso that where any Q is a hydrocarbyl such Q is not a substituted or unsubstituted cyclopentadienyl radical;  
       T is a covalent bridging group containing a Group IV A or V A element;  
       L is a neutral Lewis base; and  
       “w” is a number from 0 to 3.  
     
     
       2. A compound of the formula:                    
       wherein: 
       M represents Ti, Hf or Zr;  
       (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with from zero to four substituent groups R, “x” is 0, 1, 2, 3, or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C 1 -C 20  hydrocarbyl radicals, substituted C 1 -C 20  hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, and alkoxy radical, C 1 -C 20  hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group IV A of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C 5 H 4-x R x ) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C 4 -C 20  ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;  
       each of R 1  and R 2  are independently selected from C 1 -C 20  hydrocarboyl radicals;  
       each Q is independently selected from halide, hydride, substituted or unsubstituted C 1 -C 20  hydrocarbyl radical, alkoxide, aryloxide, amide and phosphide radicals with the proviso that Q is not a substituted or unsubstituted cyclopentadienyl radical;  
       R′ is selected from C 1 C 3     -C 20  aliphatic and alicyclic hydrocarbyl radicals with the proviso that R′ is covalently bonded to the nitrogen atom through a 1° or 2° carbon atom;  
       L is a neutral Lewis base; and  
       “w” is a number from 0 to 3.  
     
     
       3. The compound of  claim 2  wherein M is Ti. 
     
     
       4. The compound of  claim 2  where: 
       M is Ti; and  
       R 1  and R 2  are each independently selected from alkyl and aryl radicals having from 1 to 20 carbon atoms.  
     
     
       5. The compound of  claim 2  wherein R′ is alicyclic. 
     
     
       6. A compound of the formula:                    
       M is Zr, Hr or Ti in its highest formal oxidation state (+4, d o  complex);  
       (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with from zero to four substituent groups R, “x” is 0, 1, 2, 3, or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C 1 -C 20  hydrocarbyl radicals, substituted C 1 -C 20  hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, and alkoxy radical, C 1 -C 20  hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group IV of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals; alkoxy radicals, alkylborido radicals or any other radical containing Lewis acidic or basic functionality; or (C 5 H 4-x R x ) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C 4 -C 20  ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;  
       R′ is a radical selected from C 1 C 3 -C 20  aliphatic and alicyclic hydrocarbyl radicals wherein one or more hydrogen atoms may be replaced by radicals selected from halogen, amido phosphido, alkoxy or any other radical containing a Lewis acidic or basic functionality, with the proviso that R′ is covalently bonded to the nitrogen atom through a 1° or 2° carbon atom;  
       each Q may be independently an univalent anionic ligand selected from a halide, hydride, or substituted or unsubstituted C 1 -C 20  hydrocarbyl, alkoxide, aryloxide, amide, phosphide, or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand with the proviso that where any Q is a hydrocarbyl such Q is not a substituted or unsubstituted cyclopentadienyl radical,;  
       “w” is a number from 0 to 3;  
       T is selected from radicals of the formula (CR 3 R 4 ) wherein R 3  and R 4  are independently selected from hydrogen and C 1 -C 20  hydrocarbyl radicals; and  
       y is 1 or 2.  
     
     
       7. The compound of  claim 6  wherein M is Ti. 
     
     
       8. The compound of  claim 6  wherein: 
       M is Ti and  
       R 3  and R 4  are selected from hydrogen, C 1 -C 6  alkyl radicals and C 6 -C 12  aryl radicals.  
     
     
       9. A compound of the formula:                    
       wherein R 1  and R 2  are each independently a hydrocarbyl radical, each Q and Q′ is independently a halide or a C 1 -C 20  hydrocarbyl radical, R′ is an aliphatic or alicyclic hydrocarbyl radical having from 1   3 to 20 carbon atoms and R′ is covalently bonded to the nitrogen atom through a 1° or 2° carbon atom, L is a neutral Lewis base where “w” denotes a number from 0 to 3 and each R is, independently a C 1 -C 4  hydrocarbyl radical or hydrogen, x is 0, 1, 2, 3 or 4, or two adjacent R groups may join to form a C 4 -C 10  ring. 
     
     
       10. The compound of  claim 9 , having the formula:                    
       wherein R 1  and R 2  are each independently a hydrocarbyl radical, each Q and Q′ is independently a halide or alkyl radical, R′ is an aliphatic or alicyclic hydrocarbyl radical of from 1   3 to 20 carbon atoms and R′ is covalently bonded to the nitrogen atom through a 1° or 2° carbon atom, and L is a neutral Lewis base where “w” denotes a number from 0 to 3.