Preparation of polymerisation catalysts

Details Preparation of polymerisation catalysts Preparation of polymerisation catalysts

2000-09-26

2003-04-15

Berch, Mark L. (Department: 1624)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S010000

Reexamination Certificate

active

06548672

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to a novel process for preparing transition metal compounds used as polymerisation catalysts.
The use of certain transition metal compounds to polymerise 1-olefins, for example, ethylene, 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. In recent years the use of certain metallocene catalysts (for example biscyclopentadienylzirconiumdichloride activated with alumoxane) has provided catalysts with potentially high activity and capable of providing an improved distribution of the comonomer units. Most recently, WO98/27124 has disclosed that ethylene may be polymerised by contacting it with certain iron or cobalt complexes of selected 2,6-(pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines); and our own copending application WO 99/12981 has disclosed novel nitrogen-containing transition metal compounds comprising the skeletal unit depicted in Formula B:
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
6
and R
7
are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R
1
-R
7
are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents.
The above transition-metal complexes are disclosed as being made by first forming the ligand (eg Examples 1 to 6 of WO 98/27124) and then separately reacting the ligand with the desired metal salt such as FeCl
2
or CoCl
2
(eg Examples 7 to 17 of WO 98/27124) to form the complex. This route is also exemplified in WO 99/12981, for example in the synthesis of 2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl
2
(Formula D below), where the reaction scheme is shown as follows:
Hitherto, it has been considered necessary to complete the reaction between Intermediates B and C to form Intermediate A (the ligand), and to isolate Intermediate A from Intermediates B and C prior to reacting with the transition metal compound to form the transition metal complex compound (Formula B). However we have now discovered that this two step process can in fact be performed as a single stage reaction, using, for example, a single reaction vessel. This provides substantial process and economic advantages.
SUMMARY OF THE INVENTION
Accordingly a first aspect of the present invention provides a process for producing a transition metal complex of the formula
wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II], Mn[III], Mn[IV], Ru[II], Ru[II] 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
6
and R
7
are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R
1
-R
7
are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents;
comprising reacting together in a single stage reaction components comprising (1) precursors capable of forming Ligand B
and (2) a compound of the formula M[T]-(T/b)X.
The reaction is preferably carried out in a single reaction vessel.
In the process of the present invention, the final product is obtained directly in a single stage reaction, without the need for any additional process steps: however at a molecular level the reaction may of course still proceed through more than one step.
DETAILED DESCRIPTION OF THE INVENTION
Preferred transition metal complexes to be made by the process of the present invention comprise the skeletal unit depicted in Formula Z:
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
to R
4
, R
6
and R
19
to R
28
are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; when any two or more of R
1
to R
4
, R
6
and R
19
to R
28
are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents; with the proviso that at least one of R
19
, R
20
, R
21
and R
22
is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl when neither of the ring systems P and Q forms part of a polyaromatic fused-ring system. In this particular aspect of the present invention, in the case that neither of the ring systems P and Q forms part of a polyaromatic ring system, it is preferred that at least one of R
19
and R
20
, and at least one of R
21
and R
22
is selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and most preferably each of R
19
, R
20
, R
21
and R
22
is selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl. The atom or group represented by X is preferably halide, sulphate, nitrate, thiolate, thiocarboxylate, BF
4
−
, PF
6
−
, hydride, hydrocarbyloxide, carboxylate, hydrocarbyl, substituted hydrocarbyl and heterohydrocarbyl. Examples of such atoms or groups are chloride, bromide, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, tosylate, triflate, formate, acetate, phenoxide and benzoate.
Subject to the foregoing provisos regarding R
19
, R
20
, R
21
and R
22
in Formula Z, R
1
to R
4
, R
6
and R
19
to R
28
in the compounds depicted in Formulae B and Z of the present invention are preferably independently selected from hydrogen and C
1
to C
8
hydrocarbyl, for example, methyl, ethyl, n-propyl, n-butyl, n-hexyl, and n-octyl. In Formula B, R
5
and R
7
are preferably independently selected from substituted or unsubstituted alicyclic, heterocyclic or aromatic groups, for example, phenyl, 1-naphthyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl, 2,6-dimethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2-t-butylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl, 2,6-trifluoromethylphenyl, 4-bromo-2,6-dimethylphenyl, 3,5 dichloro2,6-diethylphenyl, and 2,6,bis(2,6-dimethylphenyl)phenyl, cyclohexyl and pyridinyl.
The ring systems P and Q in Formula Z are preferably independently 2,6-hydrocarbylphenyl or fused-ring polyaromatic, for example, 1-naphthyl, 2-naphthyl, 1-phenanthrenyl and 8-quinolinyl.
A further aspect of the present invention provides process for producing a transition metal complex having the Formula T:
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 ato

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