Catalyst System
A catalyst system suitable for the polymerisation of olefins, said system comprising (a) a transition metal compound or lanthanide metal compound (b) a cocatalyst and (c) at least one porous support material characterised in that the porous support material has been pretreated with a halogen-containing organometallic compound, in particularly with a fluorine-containing organometallic compound. The catalyst system is particularly suitable for the preparation of polymers having broad molecular weight distributions from the polymerisation of olefins in the presence of a single site catalyst.
1 . A catalyst system suitable for the polymerisation of olefins, said system comprising
(a) a transition metal compound or lanthanide metal compound
(b) a cocatalyst and
(c) at least one porous support material
characterised in that the porous support material has been pretreated with a halogen-containing organometallic compound.
2 . A catalyst system according to claim 1 wherein the halogen-containing organometallic compound comprises elements of Groups 1, 2, 13, 14, 15, 16 or 17 of the Periodic Table.
3 . A catalyst system according to claim 2 wherein the element is a Group 13 element.
4 . A catalyst system according to claim 1 wherein the halogen-containing organometallic compound is a fluorine-containing organometallic compound.
5 . A catalyst system according to claim 4 wherein the fluorine-containing organometallic compound has the formula
A1R x F y
wherein x and y may be either 1 or 2 and R is an organic moiety.
6 . A catalyst system according to claim 5 wherein the R groups may be the same or different and are linear or branched alkyl groups having from 1-20 carbon atoms.
7 . A catalyst system according to claim 5 wherein the fluorine-containing organometallic compound is diethylaluminium fluoride, dimethylaluminium fluoride (DMAF) or diisobutyl aluminium fluoride.
8 . A catalyst system according to claim 1 wherein the porous support material is silica.
9 . A catalyst system according to claim 1 comprising (a) a first porous support material pretreated with a halogen-containing organometallic compound and (b) a second porous support material.
10 . A catalysts system according to claim 9 wherein the second porous support material has been pretreated with a trialkylaluminium compound.
11 . A catalyst system according to claim 1 wherein the transition metal compound is a metallocene complex.
12 . A catalyst system according to claim 10 wherein the metallocene is a monocyclopentadienyl metallocene complex.
13 . A catalyst system according to claim 11 wherein the metallocene complex has the general formula:
wherein:—
R′ each occurrence is independently selected from 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 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.
14 . A catalyst system according to claim 12 wherein the metal is titanium.
15 . A catalyst system according to claim 1 wherein the cocatalyst is represented by the formula:
(L*-H) + d (A d- )
wherein
L* is a neutral Lewis base
(L*-H) + d is a Bronsted acid
A d is a non-coordinating compatible anion having a charge of d − , and d is an integer from 1 to 3.
16 . A catalyst system suitable for the polymerisation of olefins, said system comprising
(a) a transition metal compound or lanthanide metal compound,
(b) a non-aluminium containing cocatalyst and
(c) at least one porous support material
characterised in that the porous support material has been pretreated with a halogen-containing compound.
17 . A catalyst system according to claim 15 wherein the halogen-containing compound is a halogen-containing organometallic compound.
18 . A catalyst system according to claim 15 wherein the halogen-containing compounds are fluorine-containing compounds.
19 . A catalyst system suitable for the polymerization of olefins, said system comprising
(a) a metallocene complex,
(b) a cocatalyst,
(c) a polymerisable monomer, and
(d) at least one porous support material
characterised in that the porous support material has been pretreated with a halogen-containing organometallic compound.
20 . A catalyst system according to claim 18 wherein the halogen-containing organometallic compound is a fluorine-containing organometallic compound.
21 . A catalyst system according to claim 18 wherein the polymerisable monomer is 1-hexene.
22 . A process for the polymerisation of olefin monomers selected from (a) ethylene, (b) propylene (c) mixtures of ethylene and propylene and (d) mixtures of (a), (b) or (c) with one or more other alpha-olefins, said process performed in the presence of a supported polymerisation catalyst system prepared as claimed in claim 1 .
23 . A process for the polymerisation of ethylene or the copolymerisation of ethylene and α-olefins having from 3 to 10 carbon atoms, said process performed under polymerisation conditions in the present of a supported catalyst system prepared according to claim 1 .
24 . A process according to claim 21 wherein the α-olefins are chosen from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.
25 . A process according to claim 21 performed in the gas phase.
26 . A method for the preparation of polymers having a molecular weight distribution >4, said method comprising polymerisation in a single reactor in the presence of a single site catalyst system, said system comprising
(a) a transition metal compound,
(b) a cocatalyst,
(c) a first porous support material pretreated with a halogen-containing compound, and
(d) a second porous support material.
27 . A method according to claim 25 wherein the polymers have a molecular weight distribution >5.
28 . A method according to claim 25 wherein the polymers have a molecular weight distribution >6.
29 . A method according to claim 25 wherein the second porous support material has been pretreated an organometallic compound.
30 . A method according to claim 28 wherein the organometallic compound is a trialkylaluminium compound.
31 . A method according to claim 25 wherein the halogen-containing compound is a fluorine-containing compound.
32 . A method according to claim 25 wherein the transition metal compound is a metallocene complex.