Polymerization catalyst

Details Polymerization catalyst Polymerization catalyst

2000-10-18

2002-10-15

Wu, David W. (Department: 1713)

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

Catalyst or precursor therefor

Organic compound containing

C502S152000, C502S167000, C502S117000, C502S104000, C526S115000, C526S116000, C526S160000, C526S161000, C526S172000

Reexamination Certificate

active

06465386

ABSTRACT:

The present invention relates to novel transition metal compounds and to their use 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. 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 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.).
Commodity polyethylenes are commercially produced in a variety of different types and grades. Homopolymerisation of ethylene with transition metal based catalysts leads to the production of so-called “high density” grades of polyethylene. These polymers have relatively high stiffness and are useful for making articles where inherent rigidity is required. Copolymerisation of ethylene with higher 1-olfins (e.g. butene, hexene or octene) is employed commercially to provide a wide variety of copolymers differing in density and in other important physical properties. Particularly important copolymers made by copolymerising ethylene with higher 1-olefins using transition metal based catalysts are the copolymers having a density in the range of 0.91 to 0.93. These copolymers which are generally referred to in the art as “linear low density polyethylene” are in many respects similar to the so called “low density” polyethylene produced by the high pressure free radical catalysed polymerisation of ethylene. Such polymers and copolymers are used extensively in the manufacture of flexible blown film.
An important feature of the microstructure of the copolymers of ethylene and higher 1-olfins is the manner in which polymerised comonomer units are distributed along the “backbone” chain of polymerised ethylene units. The conventional Ziegler-Natta catalysts have tended to produce copolymers wherein the polymerised comonomer units are clumped together along the chain. To achieve especially desirable film properties from such copolymers the comonomer units in each copolymer molecule are preferably not clumped together, but are well spaced along the length of each linear polyethylene chain. 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. 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.
WO99/02472 and Small, et al, J.Am.Chem. Soc, vol 120, pp 7143-4 (1998) disclose that ethylene may be polymerised to form &agr;-olefins by contacting it with iron complexes of selected 2,6-pyridinecarboxaldehydebis (imines) and 2,6-diacylpyridinebis(imines). Copending applications WO99/46302 and WO99/50318 both disclose polymerisation catalysts comprising such complexes in combination a further catalyst which may for example be a Ziegler Natta catalyst, a Phillips type (chromium oxide) catalyst, a metallocene catalyst, a monocyclopentadienyl constrained geometry type catalyst or a bidentate &agr;-diimine late transition metal catalyst. As an example of the above-mentioned iron complexes, WO99/50318 discloses such complexes in combination with certain metallocene or monocyclopentadienyl constrained geometry type catalysts, of which the specific combinations of 2,6-diacetylpyridinebis(2-methylanil)FeCl
2
with each of the following four compounds have a priority date earlier than that of the present invention:
1,1-Dimethylsilyl(1-tetramethylcyclopentadienyl)(1-t-butylamino)titanium dichloride,
Propane-2,2-[(cyclopentadienyl)(1-fluorenyl)]zirconium dichloride,
Butane-2,3-(2,6-dimethylphenyl-1-imino)nickel dibromide, and
2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl
2
.
An object of the present invention is to provide a novel catalyst system suitable for polymerising monomers, for example, olefins, and especially for polymerising ethylene alone to form polyethylene varying from HDPE to LLDPE. 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 with higher 1-olefins to provide homopolymers and copolymers having controllable molecular weights. A particular object of the invention is to produce LLDPE by the polymerisation of ethylene alone.
We have discovered a novel catalyst system one component of which is capable of producing &agr;-olefins in situ, and a second component of which copolymerises the &agr;-olefins with ethylene to form polyethylene containing short chain branching.
By “&agr;-olefin” in this specification is meant a compound of the formula H(CH
2
CH
2
)
n
CH═CH
2
where n is an integer from 1 to 20. The term “&agr;-olefins” encompasses mixtures of such compounds, which may additionally include compounds where n is greater than 20.
Accordingly the present invention provides in one aspect a polymerisation catalyst comprising
(1) a catalyst comprising a compound of the 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
to R
5
and R
23
to R
28
are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; R
19
is an optionally substituted primary, secondary or tertiary hydrocarbyl or heterohydrocarbyl group;
when R
19
is an optionally substituted primary hydrocarbyl or heterohydrocarbyl group, one of R
20
to R
22
is hydrogen and the others are each independently hydrogen, halogen or an optionally substituted primary hydrocarbyl or heterohydrocarbyl group;
when R
19
is an optionally substituted secondary hydrocarbyl or heterohydrocarbyl group, two of R
20
to R
22
are hydrogen and the other is hydrogen, halogen or an optionally substituted primary or secondary hydrocarbyl or heterohydrocarbyl group;
when R
19
is an optio

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