Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-01-15
2003-06-03
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S091000, C526S093000, C526S123100, C526S124100, C526S141000, C526S147000, C526S169100, C526S171000, C526S172000, C502S117000, C502S155000
Reexamination Certificate
active
06573345
ABSTRACT:
The present invention is directed to organometallic catalysts and catalyst compositions useful in the oligomerization or polymerization of alpha-olefins alone or in combination with functionalized olefins, certain bidentate ligand compounds useful in providing the subject catalysts, processes of forming the bidentate ligand compounds and catalysts therefrom, processes of forming olefin oligomers and polymers utilizing the subject catalysts, and catalyst compositions and the oligomers and polymers formed therefrom.
The polyolefin industry has relied on various catalyst and initiator systems. The polymerization of ethylene and other non-polar 1-olefins has been commonly accomplished using organometallic Ziegler-Natta coordination-type catalysts, chromium catalysts, other early transition metal catalysts as well as free-radical type initiators. Although the array of catalysts available provides different approaches to the manufacture of polyolefins with differing physical and mechanical properties, these catalysts are highly susceptible to a range of substances which poison or deactivate the catalyst's activity. It is well known that even trace amounts of oxygen, carbon monoxide, acetylene or water causes deactivation. Further, catalyst deactivation is caused by organic compounds having oxygen donor groups such as ethers, esters, alcohols, or ketones. Industrial application of these organometallic catalysts requires careful and elaborate measures to assure the absence of such poisons. Because these catalysts are easily poisoned, they tend to form low molecular weight materials, can not be used to provide copolymerization of ethylene with an oxygenated functional monomer, such as an ester, acid or ether functionalized olefin, and generally may produce highly branched polymer products.
More recently, olefin polymerizaton catalysts have been developed which are less oxophilic than the early transition metal counterparts. For example, U.S. Pat. Nos. 4,310,716; 4,382,153; 4,293,727; 4,301,318; and 4,293,502 each disclose late transition metal (e.g. Ni) complexes which provide low molecular weight oligomers of ethylene. Further, polymerization of ethylene has been successfully shown using complexes based on phosphorus ylide ligands in U.S. Pat. No. 4,537,982 as well as in U.S. Pat. Nos. 4,698,403; 4,716,205; and 4,906,754. These nickel based catalysts formed from P-O bidentate ligands have been shown to provide high activity in the oligomerization and polymerization of ethylene. Still more recently, L. K. Johnson et al in J. Am. Chem. Soc. 1995 117, 6414, reported the formation and use of Pd(II) and Ni(II) based cationic complexes formed from diimine ligands to provide high molecular weight polyolefins. Finally, WO 96/23010 describes a process for the polymerization of olefins using a variety of transition metal complexes of certain diimine bidentate ligands. In many cases the polymerization provided highly branched polyolefins and were not shown to be useful in providing functionalized copolymer products. Further, in those instances where functionalized copolymers were formed, it was shown that the functional groups reside exclusively at the end of chain branches.
Certain processes and cationic nickel (II) catalyst compositions have been described also by L. K. Johnson et al in WO 97/02298. These cationic complexes are described as active for the polymerization of ethylene and other olefins. They require use of an acid of a non-coordinating mono-anion, or some combination of compounds that will generate such acid, in order for the catalyst composition to be rendered active towards olefin polymerization. The present neutral complexes, as well as the use of a Lewis base is not suggested by Johnson et al.
Löfgren et al, in Macromolecules 1997, 30, 171-175 describe polymerization of ethylene by cationic zirconium salen bis-chloride complexes with or without a Lewis base (tetrahydrofuran). They show that the catalyst composition exhibits only low levels of activity. There are many references to the deleterious effect of Lewis base toward late transition metal catalyst compositions as well as single-site catalyst compositions of the metallocene type. For example, EP 94/304642 and EP 94/630910 disclose that Lewis base, such as dialkyl ether, substantially terminates olefin polymerization by a single-site catalyst composition composed of a metallocene compound and partially hydrolyzed aluminum alkyl compound (aluminoxane). Additionally, U.S. Pat. No. 5,571,881 and WO 95/14048 indicate that an unsaturated Lewis base, e.g., vinyl ether, either reacts with the cationic late transition metal catalysts to destroy their activity or causes reduction of the resultant polymer molecular weight. It is highly desired to provide a catalyst for the oligomerization and polymerization of olefins, in particular ethylene, which provides a substantially linear (low degree of branching) product. It is also highly desired to provide a nonionic catalyst which can provide the linear polymer product. It is still further desired to provide a nonionic catalyst which is capable of providing a product of high molecular weight which is substantially linear and, optionally, which is capable of promoting copolymerization of olefin and functionalized olefin monomer units.
Finally, it is desired to provide a catalyst composition composed of a non-ionic catalyst in combination with an adjunct agent and/or a Lewis base which is capable of providing a product of high molecular weight which is substantially linear and, optionally, which is capable of promoting copolymerization of olefin and functionalized olefin monomer units.
SUMMARY OF THE INVENTION
The present invention is directed to certain late transition metal pyrrolaldimine chelates as olefin oligomerization or polymerization catalysts, to the bidentate ligand compounds of substituted pyrrolaldimine which are precursors for said catalysts, to catalyst compositions composed of said pyrrolaldimine chelates in combination with an adjunct agent and/or a Lewis base, the methods of forming said precursor compounds and said catalysts, and the method of polymerizing olefin monomers, especially ethylene, as well as copolymerization of olefin and functionalized olefin monomers. Each of the above elements of the present invention is fully described herein below.
DETAILED DESCRIPTION
The present invention provides a process for polymerizing olefin monomers, in particular ethylene, in the presence of catalysts taken from the selected family of pyrrolaldimine late transition metal chelates and to catalyst compositions composed of said pyrrolaldimine chelates in combination with an adjunct agent and/or a Lewis base, to produce olefin oligomers or polyolefins which can be either substantially linear and have a weight average molecular weight of at least 150.
It has been presently found that certain pyrrolaldimine late transition metal chelates can provide catalyst systems for the oligomerization or homopolymerization of ethylene and copolymerization of ethylene and functionalized olefins to provide substantially linear polymer products. The catalyst of the present invention can be represented by the following
wherein
R
1
represents a hydrogen atom, C
1
-C
11
alkyl (preferably C
1
-C
5
and most preferably tert-butyl); aryl, such as phenyl, biphenyl, terphenyl, naphthyl, anthracyl, phenanthracyl and the like; substituted aryl wherein the substitution group is selected from C
1
-C
6
alkyl, perfluoroalkyl, nitro, sulfonate, or halo group; arylalkyl, such as toluyl and the like; halo, such as chloro, bromo, and the like; nitro group; sulfonate group or siloxyl (—OSiA
3
where A is selected from phenyl or C
1
-C
4
alkyl such as isopropyl or butyl and the like); or a hydrocarbyl terminated oxyhydrocarbylene group, —(BO)
z
R
7
, wherein each B independently represents a C
1
-C
4
(preferably C
2
-C
3
) alkylene group or an arylene group (preferably phenyl, especially the B group adjacent to the base structure to which R
1
is bonded); R
7
represents a C
1
-C
11
(preferably a C
1
-
Bansleben Donald Albert
Friedrich Stefan K.
Grubbs Robert Howard
Li Robert Tan
Wang Chunming
Cryovac Inc.
Rabago R.
Wu David W.
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