Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
1999-04-28
2001-12-25
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S123000, C502S125000, C502S102000, C502S156000, C502S172000, C526S141000, C526S142000, C526S147000, C526S161000, C526S164000, C556S050000, C556S051000, C556S449000
Reexamination Certificate
active
06333292
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 triethylaluminiur, is fundamental to many commercial processes for manufacturing polyolefins. Over the last twenty or thirty years, advances in the technology have lead 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 usefull for making articles where inherent rigidity is required. Copolymerisation of ethylene with higher 1-olefins (eg 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-olefins 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.
An object of the present invention is to provide a novel catalyst suitable for polymerising olefins, and especially for polymerising ethylene alone or for copolymerising ethylene with higher 1-olefins. A further object of the invention is to provide an improved process for the polymerisation of olefins, especially of ethylene and C
2-20
linear or branched &agr;-olefins, or the copolymerisation of ethylene with higher 1-olefins to provide homopolymers and copolymers having controllable molecular weights. For example, using the catalyst of the present invention there can be made a wide variety of polyolefins such as, for example, liquid polyolefins, resinous or tacky polyolefins, solid polyolefins suitable for making flexible film and solid polyolefins having high stiffness.
In its broadest aspect the present invention provides a nitrogen-containing transition metal complex compound comprising the skeletal unit depicted in Formula (I)
Formula (I)
wherein O is oxygen, N is nitrogen, Q represents a divalent organic group or a group based on a Group 14 atom; R
1
is hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; M is scandium yttrium, or a Group IV or Group V metal or a lanthanide or actinide; T is the oxidation state of M and is II or greater; X represents a monodentate atom or group covalently or ionically bonded to M; L is a mono- or bidentate molecule datively bound to M, and n is from 0 to 5. Q may be datively coordinated to the metal M.
Preferred metals are those of Group IV, or scandium or yttrium. More preferred are Ti(IV), Ti(III), Ti(II), Zr(IV), Zr(III), Zr(II), Hf(IV), Hf(III), Hf(II), Sc(III) and Y(III).
L is preferably an ether, alcohol, amine, ester, phosphine, alkene, alkyne or arene, and in particular may be a diene.
In a preferred embodiment, the present invention provides a compound comprising the skeletal unit depicted in Formula A:
Formula A
wherein O is oxygen, N is nitrogen, Q represents a divalent organic group or a group based on a Group 14 atom, M is titanium(IV), zirconium(IV) or hafnium(IV), R
1
is hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and each X represents a monodentate atom or group covalently or ionically bonded to M. It is preferred that n is zero.
The divalent bridging group Q can be, for example, the simple divalent group CR
2
or a polyalkylene chain (CR
2
)
q
, a silane bridge (SiR
2
)
m
, or a polyalkylene-silane bridge (CR
2
)
p
(SiR
2
)
m
, wherein the R groups can be, for example, independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heterocarbyl and substituted heterocarbyl, m is one or more, p is one or more and q is two or more. Two or more of the R groups may connect together, for example, to form a carbocyclic or heterocyclic ring system within the bridging group Q. Specific examples of Q include methylene, dimethylmethylene, ethylene, propylene, dimethylpropylene, 1,1-dimethyl-3,3-dimethylpropylene or butylene; dimethylsilyl, methylphenylsilyl, tetramethyldisiloxane, 1,1,4,4-tetramethyldisilylethylene and dimethylgermanyl; or Q may be phenyl.
In the complex compound depicted in Formula A of the present invention the bridging group Q preferably comprises a saturated or unsaturated ring system, for example, a benzene, cyclohexene, cyclohexane, pyrazole, pyridine, piperidine, pyrazine, pyrimidine, or a thiazole ring system, or a polynuclear homocyclic or heterocyclic system such as, for example, naphthalene, quinoline or imidazole. For example, such a ring system may be a substituent on the divalent bridging group, or may be the bridging group itself or a part thereof. Thus for example, Q may comprise a benzene ring system. Such a benzene ring
Gibson Vernon Charles
Kimberley Brian Stephen
BP Chemicals Limited
Choi Ling-Siu
Finnegan, Henderson Farabow, Garrett and Dunner L.L.P.
Wu David W.
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