Polymerization catalysts

Details Polymerization catalysts Polymerization catalysts

2000-11-01

2004-01-27

Harlan, Robert Deshon (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S172000, C502S155000, C502S167000, C556S013000, C556S051000, C556S136000, C556S138000, C546S020000

Reexamination Certificate

active

06683141

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.
Patent Application WO98/27124 discloses 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). In J. Chem. Soc. (A), 1970, 2964-2966, oxovanadium (IV) complexes of the general formula VO[2,6-bis-(1-(phenylimino)ethyl)pyridine]X
2
where X is Cl or Br are disclosed, but no polymerisation utility is mentioned.
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 fuirther 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 homopolymners 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.
The present invention provides a transition metal complex having the Formula A
wherein M is a transition metal, lanthanide or actinide; X represents an atom or group covalently or ionically bonded to the transition metal M; b is the valency of the atom or group X; Z
1
is N or P; Z
2
is N, P, N
−
, P
−
or NR
5
; Z
3
is one of N P, O, S, NHR
3
, NR
3
R
4
, OH, OR
3
, SH, SR
3
, PHR
3
, PR
3
R
4
, (NR
3
)
−
, O
−
, S
−
, (PR
3
)
−
, P(R
3
R
4
)O, NR
3
or PR
3
, subject to the proviso that the ligand joined to M via Z
1
, Z
2
and Z
3
is monoanionic or neutral, and that when neutral it is not a pyridyl diimine ligand; T is the oxidation state of the transition metal M when both Z
2
and Z
3
are neutral, and 1 less than the oxidation state of M when one of Z
2
or Z
3
is anionic; A and B are independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and may together with Z
2
form part of a heterocyclic substituent; B may be joined to Z
3
by either a single or a double bond; R
1
to R
5
are each independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and any two or more of R
1
to R
5
when hydrocarbyl may be joined together to form a ring; L is a solvate molecule, and n is from 0 to 5.
In a preferred embodiment either Z
2
or Z
3
is N
−
and is joined to M by a covalent bond.
Preferably M is Ti[II], Ti[III], Ti[IV], Fe[II], Fe[III], Co[II], Co[III], Ni[II], Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Ta[II], Ta[III], Ta[IV], Rh[II], Rh[III], Y[II], Y[(III], Sc[II], Sc[III], Ru[II], Ru[III], Ru[IV], Pd[II], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], Nb[IV] or Nb[V].
Preferably the complex of the invention comprises the skeletal unit shown in Formula B
wherein M is Ti[II], Ti[III], TI[IV], Fe[II], Fe[III], Co[II], Co[III], Ni[II], Cr[II], Cr[III], Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III], Ru[IV], Pd[II], Zr[II], Zr[III], Zr[IV], Hf[II], Hf[III], Hf[IV], V[II], V[III], V[IV], Nb[II], Nb[III], or Nb[IV]; X represents an atom or group covalently or ionically bonded to the transition metal M; b is the valency of the atom or group X; Z
1
is N or P; Z
3
is one of NHR
3
, NR
3
R
4
, OH, OR
3
, SH, SR
3
, PHR
3
, PR
3
R
4
, (NR
3
)
−
, O
−
, S
−
, (PR
3
)
−
or P(R
3
R
4
)O; T is the oxidation state of the transition metal M when Z
3
is neutral, and 1 less than the oxidation state of M when Z
3
is anionic; Q is joined to Z
3
by a single bond and is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, preferably —C(R
9
)(R
10
)—; R
1
to R
10
are each independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and when hydrocarbyl any two or more of R
1
to R
10
may be joined together to form a ring; L is a solvate molecule, and n is from 0 to 5, preferably 0.
In a preferred embodiment R
2
is preferably represented by the structure
and R
3
by the structure
wherein R
19
to R
28
are each independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, and when hydrocarbyl any two or more thereof may be joined to

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