Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
2000-10-17
2003-01-28
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S103000, C502S117000, C502S155000, C502S168000, C502S216000, C502S219000, C502S220000, C502S222000, C502S223000, C526S161000, C526S172000
Reexamination Certificate
active
06511934
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a family of novel catalyst precursor compounds and compositions for the polymerization of olefins, including homopolymers of ethylene, propylene and other alpha-olefins and/or alpha olefin-dienes, as well as copolymers of alpha olefins, cyclic olefins and/or alpha olefin-dienes. In particular, the present invention provides catalyst precursor compounds and catalyst compositions which have good resistance to catalyst poisons, which can provide acceptable activity without the use of more expensive co-catalysts such as methyl alumoxane (MAO) or modified methyl alumoxane (MMAO), and which offer the possibility of polar comonomer incorporation into growing polymer chains.
BACKGROUND OF THE INVENTION
Numerous catalyst precursor compounds have been developed for use in forming catalyst compositions for polymerization of olefins to produce polyolefins. For example, a number of late transition metal complexes have been known to be effective as catalysts, e.g., for oligomerization of ethylene. Brookhart et al. have disclosed that late metals such as Ni, Pd, Fe and Co, when constrained in an appropriate ligand environment, are effective catalysts for the polymerization of ethylene (see e.g.,
J. Am. Chem. Soc.
1996, 118, 267-268 and
J. Am. Chem. Soc.
1995, 117, 6414-6415). According to Brookhart et al, the ability of the late metal Ni and Pd catalysts to polymerize rather than oligomerize ethylene is due to the steric bulk of the ligand, which prevents olefin approach at the axial sites, thus avoiding chain transfer to olefin. Brookhart et al. assert that the potential advantages offered by these catalysts include the incorporation of functionalized comonomers and the use of less expensive co-catalysts, i.e., diethyl aluminum chloride.
Despite these and other efforts, there remains an ongoing need for catalyst precursor compounds and compositions which enable various olefin polymerization reactions to be performed more efficiently, e.g., at a lower cost with acceptable yield and activity. There is also an ongoing need for such catalyst precursor compounds which offer the possibility of polar comonomer incorporation into growing polymer chains. The catalyst compounds of the present invention, as well as catalyst compositions which contain the catalyst compounds of the present invention, and olefin polymerization reactions which employ the catalyst compounds of the present invention, as described below, satisfy these needs. The present invention provides a family of catalysts which are robust late transition metal complexes containing bulky, neutral, sulfur-containing ligands.
SUMMARY OF THE INVENTION
The present invention provides catalyst precursor compounds for use in olefin polymerization reactions. According to the present invention, there are provided sterically bulky bidentate and tridentate, neutral sulfur-containing ligands, and transition metal complexes of such ligands. The ligands of the present invention contain at least two neutral sulfur-containing linkages. In addition to coordinating to two (and in some cases three) sulfur-containing ligands, the metal centers are also coordinated to two monoanionic groups, e.g., chlorides or methyls.
The catalyst precursor compounds of the present invention, when used in polymerization of olefins, provide acceptable activity and other properties.
The catalyst precursor compounds of the present invention include those having a formula selected from among:
wherein:
E is O, S, N or P;
M is a transition metal;
R
1
and R
2
are each independently selected from among halogen, alkoxide, aryloxide, amide, phosphide, hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid, or R
1
and R
2
are joined to form a ring structure;
R
3
and R
4
are each independently selected from among hydrogen, halogen, alkoxide, aryloxide, amide, phosphide, hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid, or R
3
and R
4
are joined to form a ring structure;
T
1
and T
2
are each independently C, N, or P;
T
3
and T
4
are each independently C, N, P or Si, except that where E is S, T
3
and T
4
are both C;
T
5
and T
6
are each independently C, N, or P;
n is 2, 3 or 4, depending on the oxidation number of M and the valency or valencies of each group X;
each group X is independently selected from among halogen, alkoxide, aryloxide, amide, phosphide, hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl-substituted organometalloid, or two X groups are joined to form a ring structure;
----
is a single or double bond; and
each J is independently a CH
2
group (as in Compound 5, below) or a covalent bond (i.e., directly bonding one of the depicted S atoms with either T
1
or T
2
, as in Compounds 1 and 4, below).
In addition, the present invention is directed to ligand compounds which can readily be reacted to provide a catalyst precursor of the present invention as defined above, such ligand compounds including compounds having a formula selected from among:
wherein E, R
1
, R
2
, R
3
, R
4
, T
1
, T
2
, T
3
, T
4
and
----
have the same definitions as set forth above.
In formulas 1-4 above, preferred groups for R
1
and/or R
2
include 2,4,6-triisopropylphenyl and 2,4,6-trimethylphenyl.
In formulas 1 and 3 above, R
3
and R
4
are preferably joined so as to form, together with T
1
and T
2
, a six-membered ring, most preferably a phenyl group.
In formulas 2 and 4 above, R
3
and R
4
are preferably joined so as to form, together with T
1
, E and T
2
, a six-membered ring, most preferably a pyridyl group.
In formulas 2 and 4 above, E is preferably O or N.
In formulas 1-4 above, M is preferably selected from among Ni, Pd, Co, Fe, Pt, Rh, Ir, Ru and Os. Most preferably, M is either Ni or Pd.
In formulas 1-4 above, the or each X is preferably halogen, or alkyl, most preferably Cl or methyl.
The present invention also provides a method of forming a catalyst precursor compound as defined above, in which a ligand compound as defined above is employed as a reactant.
The present invention also provides a catalyst composition comprising a catalyst precursor compound according to the present invention and an activating co-catalyst, as disclosed below.
The present invention also provides a catalyst system comprising a catalyst precursor according to the present invention and an activating co-catalyst, in which the catalyst precursor and the activating co-catalyst are introduced to a reaction system at different locations.
The present invention further provides a process for producing an olefin polymer, which comprises contacting at least one olefin monomer under polymerization conditions with a catalyst precursor compound, a catalyst composition and/or a catalyst system as described above. As described below, a wide variety of olefin polymers can be produced according to the present invention, with a preferred olefin polymer being polyethylene, preferably of relatively high molecular weight, typically in the range of from 10,000 to 10,000,000, although the present invention is not limited to any particular molecular weight.
The present invention further provides olefin polymers, such as ethylene polymers, produced by a process as described in the preceding paragraph, and products, e.g., blown and cast films including clarity and shrink applications, extrusion coatings, wire and cable insulation and jacketing, crosslinked power cable insulation, molded articles made by injection molding, blow molding or rotational molding, extrusions of pipe, tubing, profiles and sheeting, and insulating and semiconductive jacketing and/or shields, etc., made from such olefin polymers.
DETAILED DESCRIPTION OF THE INVENTION
In this specification, the term “olefinically unsaturated hydrocarbons” is often represented for convenience by
Bielak John Joseph
Cook Jessica Ann
Rabago R.
Union Carbide Chemicals & Plastics Technology Corporation
LandOfFree
Transition metal precursors containing sulfur ligands, and... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Transition metal precursors containing sulfur ligands, and..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Transition metal precursors containing sulfur ligands, and... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3055734