Polymerization catalyst

Details Polymerization catalyst Polymerization catalyst

2000-10-30

2002-10-08

Wu, David W. (Department: 1713)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S167000, C526S064000, C526S075000, C526S115000, C526S116000, C526S161000, C526S171000, C526S172000, C526S901000, C526S905000

Reexamination Certificate

active

06461994

ABSTRACT:

The present invention relates to transition metal complex compounds, to polymerisation catalysts based thereon and to their use in the polymerisation and copolymerisation of olefins.
The use of certain transition metal compounds to polymerise 1-olefins, for example, ethylene or propylene, is well established in the prior art. The use of Ziegler-Natta catalysts, for example, those catalysts produced by activating titanium halides with organometallic compounds such as triethylaluminium, is fundamental to many commercial processes for manufacturing polyolefins. Over the last twenty or thirty years, advances in the technology have led to the development of Ziegler-Natta catalysts which have such high activities that olefin polymers and copolymers containing very low concentrations of residual catalyst can be produced directly in commercial polymerisation processes. The quantities of residual catalyst remaining in the produced polymer are so small as to render unnecessary their separation and removal for most commercial applications. Such processes can be operated by polymerising the monomers in the gas phase, or in solution or in suspension in a liquid hydrocarbon diluent. Polymerisation of the monomers can be carried out in the gas phase (the “gas phase process”), for example by fluidising under polymerisation conditions a bed comprising the target polyolefin powder and particles of the desired catalyst using a fluidising gas stream comprising the gaseous monomer. In the so-called “solution process” the (co)polymerisation is conducted by introducing the monomer into a solution or suspension of the catalyst in a liquid hydrocarbon diluent under conditions of temperature and pressure such that the produced polyolefin forms as a solution in the hydrocarbon diluent. In the “slurry process” the temperature, pressure and choice of diluent are such that the produced polymer forms as a suspension in the liquid hydrocarbon diluent. These processes are generally operated at relatively low pressures (for example 10-50 bar) and low temperature (for example 50 to 150° C.).
In recent years the use of certain metallocene catalysts (for example biscyclopentadienylzirconiumdichloride activated with alumoxane) has provided catalysts with potentially high activity. However, metallocene catalysts of this type suffer from a number of disadvantages, for example, high sensitivity to impurities when used with commercially available monomers, diluents and process gas streams, the need to use large quantities of expensive alumoxanes to achieve high activity, and difficulties in putting the catalyst on to a suitable support.
WO 99/12981 discloses that ethylene and other 1-olefins may be polymerised by contacting it with certain late transition metal complexes of selected 2,6-pyridinecarboxaldehydebis (imines) and 2,6-diacylpyridinebis (imines).
An object of the present invention is to provide a novel catalyst suitable for polymerising and oligomerising monomers, for example, olefins such as &agr;-olefins containing from 2 to 20 carbon atoms, and especially for polymerising ethylene alone, propylene alone, or for copolymerising ethylene or propylene with other 1-olefins such as C
2-20
&agr;-olefins. A further object of the invention is to provide an improved process for the polymerisation of olefins, especially of ethylene alone or the copolymerisation of ethylene or propylene with higher 1-olefins to provide homopolymers and copolymers having controllable molecular weights. For example, using the catalysts of the present invention there can be made a wide variety of products such as, for example, liquid polyolefins, oligomers, linear &agr;-olefins, branched &agr;-olefins, resinous or tacky polyolefins, solid polyolefins suitable for making flexible film and solid polyolefins having high stiffness.
SUMMARY OF THE INVENTION
The present invention provides a nitrogen containing transition metal complex having the following Formula (I)
wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atom or group covalently or ionically bonded to the transition metal M; T is the oxidation state of the transition metal M and b is the valency of the atom or group X; R
1
, R
2
, R
3
, R
4
, R
5
, R
19
, R
20
, R
21
, R
22
, R
23
, R
25
, R
26
and R
28
are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; when any two or more of R
1
R
2
, R
3
, R
4
and R
5
and are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents;
characterised in that R
24
and R
27
are either both halogen or at least one of them has two or more carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
R
1
, R
2
, R
3
, R
4
, R
5
, R
19
, R
20
, R
21
, R
22
, R
23
, R
25
, R
26
and R
28
are preferably independently selected from hydrogen and C
1
to C
8
hydrocarbyl, for example, methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, phenyl and benzyl.
When R
24
and R
27
are both halogen, they may independently be fluorine, chlorine, bromine or iodine, and are preferably both fluorine.
In the case where at least one of R
24
and R
27
contains two carbon atoms, they preferably have from 2 to 10 carbon atoms, more preferably from 4 to 8 carbon atoms. If desired one, but not both, of the groups R
24
and R
27
can be selected from hydrogen or methyl. However, it is preferred that both R
24
and R
27
contain from 2 to 10 carbon atoms, most preferably from 4 to 8 carbon atoms. R
24
and R
27
are preferably independently selected from ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert.-butyl, n-pentyl, neopentyl, n-hexyl, 4-methylpentyl, n-octyl, phenyl and benzyl. Most preferably in this case R
24
and R
27
are both tertiary butyl.
Alternatively, one of R
24
and R
27
contains at least two carbon atoms and the other is halogen, preferably fluoro.
Preferably at least one of R
19
, R
20
, R
21
and R
22
is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. More preferably at least one of R
19
and R
20
, and at least one of R
21
and R
22
, is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. Most preferably R
19
, R
20
, R
21
and R
22
are all independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. R
19
, R
20
, R
21
and R
22
are preferably independently selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert.-butyl, n-pentyl, neopentyl, n-hexyl, 4-methylpentyl, n-octyl, phenyl and benzyl. However in the case when R
24
and R
27
are both halogen, it is preferred that one of R
21
and R
22
and also one of R
19
and R
20
is hydrogen.
Preferably R
23
, R
25
, R
26
and R
28
are all hydrogen.
In the nitrogen-containing complex of the present invention the transition metal M is preferably Fe(II), Fe(III) or Co(II).
Each of the nitrogen atoms N
1
, N
2
and N
3
is coordinated to the transition metal M by a “dative” bond, ie a bond formed by donation of a lone pair of electrons from the nitrogen atom. The remaining bonds on each nitrogen atom are covalent bonds formed by electron sharing between the nitrogen atoms and the organic ligand as shown in the defined formula for the transition metal complex illustrated above.
The atom or group represented by X in the compounds of Formula (I) can be, for example, selected from halide, sulphate, nitrate, thiolate, thiocarboxylate, BF
4
−
; PF
6
−
, hydride, hydrocarbyloxide, carboxylate, hydrocarbyl, substituted hydrocarbyl and heterohydrocarbyl, or &bgr;-diketonates. Examples of such atoms or groups are chloride, bromide, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, tosylate, triflate, fomate, acetate, p

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