Titanium (II) or zirconium (II) complexes and addition polymerization catalysts therefrom

Claim 2

A catalyst composition comprising a metal complex which is catalytically activated by combination with an activating cocatalyst or by use of an activating technique, said complex containing one and only one cyclic delocalized, anionic, Π-bonded group, and corresponding to the formula: ##STR10## wherein: M is titanium or zirconium in the +2 formal oxidation state; L is a group containing a cyclic, delocalized, anionic, Π-system through which the group is bound to M, and which group is also bound to Z; Z is a moiety bound to M via a σ-bond, comprising an element selected from the group consisting of boron and the members of Group 14 of the Periodic Table of the Elements, and also comprising an element selected from the group consisting of nitrogen, phosphorus, sulfur and oxygen, said moiety having up to 60 non-hydrogen atoms; and X is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more groups selected from hydrocarbyl or trimethylsilyl groups, said X having up to 40 carbon atoms and forming a Π-complex with M.

Claim 3

A composition according to claim 1 wherein the complex corresponds to the formula: ##STR11## wherein: Z, M and X are as defined in claim 1, and Cp is a C 5 H 4 group bound to Z and bound in an η 5 bonding mode to M or is such an η 5 bound group substituted with from one to four substituents independently selected from hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said substituent having up to 20 nonhydrogen atoms, and optionally, two such substituents (except cyano or halo) together cause Cp to have a fused ring structure.

Claim 4

A composition according to claim 1 wherein the complex corresponds to the formula: ##STR12## wherein R' each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, cyano, halo and combinations thereof, said R' having up to 20 non-hydrogen atoms, and optionally two R' groups (when R' is not hydrogen, halo or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure; X is a neutral η 4 -bonded diene group having up to 30 non-hydrogen atoms, which forms a Π-complex with M; Y is --O--, --S--, --NR*--, --PR*--; M is titanium or zirconium in the +2 formal oxidation state; and Z* is SiR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*═CR*, CR* 2 SiR* 2 , or GeR* 2 ; wherein: R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 10 non-hydrogen atoms, and optionally, two R* groups from Z*, or an R* group from Z* and an R* group from Y (when R* is not hydrogen) form a ring system.

Claim 5

A composition according to claim 1 wherein the complex corresponds to the formula: ##STR13## wherein: M is titanium in the +2 formal oxidation state; X is s-trans-η 4 -1,4-diphenyl-1,3-butadiene; s-trans-η 4 -3-methyl-1,3-pentadiene; s-trans-η 4 -1,4-dibenzyl-1,3-butadiene; s-trans-η 4 -2,4-hexadiene; s-trans-η 4 -1,3-pentadiene; s-trans-η 4 -1,4-ditolyl-1,3-butadiene; s-trans-η 4 -1,4-bis(trimethylsilyl)-1,3-butadiene; s-cis-η 4 -1,4-diphenyl-1,3-butadiene; s-cis-η 4 -3-methyl-1,3-pentadiene; s-cis-η 4 -1,4-dibenzyl-1,3-butadiene; s-cis-η 4 -2,4-hexadiene; s-cis-η 4 -1,3-pentadiene; s-cis-η 4 -1,4-ditolyl-1,3-butadiene; or s-cis-η 4 -1,4-bis(trimethylsilyl)-1,3-butadiene, said s-cis isomers forming a Π-bound diene complex; R' each occurrence is independently selected from the group consisting of hydrogen, silyl, hydrocarbyl and combinations thereof said R' having up to 10 carbon or silicon atoms, and optionally two such R' groups (when R' is not hydrogen) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure; R" is C 1-10 hydrocarbyl; R'" independently each occurrence is hydrogen or C 1-10 hydrocarbyl; E is independently each occurrence silicon or carbon; and m is or 2.

Claim 6

A composition according to claim 4 wherein the metal complex is (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) s-trans-η 4 -3-methyl-1,3-pentadiene; (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)-dimethylsilanetitanium(II) s-trans-η 4 -1,3-pentadiene; (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)-dimethylsilanetitanium(II) s-trans-η 4 -2,4-hexadiene; (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) s-trans-η 4 -1,4-bis(trimethylsilyl)-1,3-butadiene; (tertbutylamido)-(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) s-trans-η 4 -trans, trans-1,4-diphenyl-1,3-butadiene; (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) s-cis-η 4 -3-methyl-1,3-pentadiene; (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)-dimethylsilanetitanium(II) s-cis-η 4 -1,3-pentadiene; (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)-dimethylsilanetitanium(II) s-cis-η 4 -2,4-hexadiene; (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) s-cis-η 4 -1,4-bis(trimethylsilyl)-1,3-butadiene; or (tert-butylamido)-(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) s-cis-η 4 -trans, trans-1,4-diphenyl-1,3-butadiene.

Claim 7

A composition according to claim 1 wherein the activating cocatalyst is selected from the group consisting of polymeric or oligomeric alumoxanes; strong Lewis acids; nonpolymeric, inert, compatible, noncoordinating, ion forming compounds; and combinations thereof.

Claim 8

A composition according to claim 6 wherein the activating cocatalyst comprises methylalumoxane, triisobutyl aluminum modified methylalumoxane, or diisobutylalumoxane.

Claim 9

A composition according to claim 6 wherein the activating cocatalyst comprises both an oligomeric or polymeric alumoxane compound and a tri(hydrocarbyl)aluminum compound having from 1 to 10 carbons in each hydrocarbyl group.

Claim 10

A composition according to claim 6 wherein the activating cocatalyst comprises a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating, inert anion.

Claim 11

A composition according to claim 9 wherein the activating cocatalyst is represented by the formula: (L*--H).sub.d.sup.+ (A.sup.d-) wherein: L* is a neutral Lewis base; (L*--H) + is a Bronsted acid; A d- is a noncoordinating, compatible anion having a charge of d-, and d is an integer from 1 to 3.

Claim 12

A composition according to claim 10 wherein the inert, compatible, noncoordinating anion is tetrakis(pentafluorophenyl)borate.

Claim 13

A composition according to claim 6 wherein the activating cocatalyst comprises both: 1) a salt of a cation which is a Bronsted acid capable of donating a proton and a noncoordinating, inert anion, and 2) a tri(hydrocarbyl)aluminum compound having from 1 to 10 carbons in each hydrocarbyl group.

Claim 14

A composition according to claim 6 wherein the activating cocatalyst comprises a hydrocarbyl substituted Group 13 compound having from 1 to 10 carbons in each hydrocarbyl group, or a halogenated derivative thereof.

Claim 15

A composition according to claim 13 wherein the activating cocatalyst comprises tris(pentafluorophenyl)borane.

Claim 16

A composition according to claim 1 wherein the metal complex is activated by bulk electrolysis of the metal complex in the presence of a supporting electrolyte comprising a noncoordinating, inert anion.