Supported polymerisation catalysts
View Patent ↗Supported catalyst system for the polymerization of olefins, having at least two different monocyclopentadienyl transition metal compounds, one or more activators including an ionic compound having (i) a cation and (ii) an anion having up to 100 non-hydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen, and one or more support materials. The supported “mixed or dual site” catalyst systems having different monocyclopentadienyl catalysts when activated by specific ionic activators lead to catalyst systems showing an improved balance of properties which may be used to prepare LLDPE polymers having broad melt flow ratios.
1. A supported catalyst system for the polymerisation of olefins, said catalyst system comprising:
(a) at least two different monocyclopentadienyl transition metal compounds, having the formula
(i) (Cp)mM(PI)nLq
wherein Cp is a ligand from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl and substituted fluorenyl,
M is a Group 4 metal selected from hafnium, titanium or zirconium,
PI is a phosphinimine ligand,
L is an activatable ligand,
m is 1 and n is 1 or 2, q is 1 or 2, and
m+n+q equals the valence of said metal
or
(ii)
wherein:—
R′ each occurrence is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R′ having up to 20 nonhydrogen atoms, and optionally, two R′ groups (where 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;
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 the group consisting of 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* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system,
(b) one or more activators comprising an ionic compound comprising (i) a cation and (ii) an anion having up to 100 non-hydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen, and
(c) one or more support materials.
2. A catalyst system according to claim 1 wherein the phosphinimine ligands are defined by the formula:
R 3 P═N—
wherein each R is independently selected from the group consisting of a hydrogen atom, a halogen atom, a C 1-20 hydrocarbyl radical, a C 1-8 alkoxy radical,
a C 6-10 aryl or aryloxy radical, an amido radical, a silyl radical and a germanyl radical.
3. A catalyst system according to claim 1 wherein the monocyclopentadienyl transition metal compounds are titanium compounds.
4. A catalyst system according to claim 1 wherein the monocyclopentadienyl transition metal compounds are present in an equimolar ratio.
5. A catalyst system according to claim 1 wherein the activator is an alkylammonium(trispentafluorophenyl)(4-hydroxyphenyl)borate.
6. A catalyst system according to claim 1 wherein each monocyclopentadienyl transition metal compound are supported on the same support material.
7. A catalyst system according claim 1 wherein each monocyclopentadienyl transition metal compound are supported on a separate support material.
8. A catalyst system according to claim 1 comprising a physical mixture of
(a) a first monocyclopentadienyl transition metal compound, an activator comprising an ionic compound comprising (i) a cation and (ii) an anion having up to 100 non-hydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen and a support material, and
(b) a second monocyclopentadienyl transition metal compound, an activator comprising an ionic compound comprising (i) a cation and (ii) an anion having up to 100 non-hydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen and a support material.
9. A catalyst system according to claim 1 wherein the support material is silica.
10. A method for the preparation of a supported catalyst system for the polymerisation of olefins as claimed in claim 1 , said method comprising the following steps:
(i) addition of an activator comprising an ionic compound comprising (a) a cation and (b) an anion having up to 100 non-hydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen to a support material,
(ii) addition of a first monocyclopentadienyl transition metal compound, and
(iii) addition of a second monocyclopentadienyl transition metal compound.