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
2000-08-03
2004-04-06
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S117000, C502S155000, C502S167000, C526S134000, C526S160000, C526S165000, C526S943000
Reexamination Certificate
active
06716786
ABSTRACT:
BACKGROUND INFORMATION
The present invention relates to catalyst compositions that are particularly adapted for use in the polymerization of olefins and other addition polymerizable monomers under slurry, high pressure or gas phase polymerization conditions. More particularly, the present invention relates to catalyst compositions comprising a support material, a metal complex catalyst, and an activator compound comprising an anion containing at least two Lewis basic sites that are coordinated to Lewis acids.
It is previously known in the art to activate Ziegler-Natta Polymerization catalysts, particularly such catalysts comprising Group 3-10 metal complexes containing delocalized &pgr;-bonded ligand groups, by the use of Bronsted acid salts capable of transferring a proton to form a cationic derivative or other catalytically active derivative of such Group 3-10 metal complex Preferred Bronsted acid salts are such compounds containing a cation/anion pair that is capable of rendering the Group 3-10 metal complex catalytically active. Suitable activators comprise fluorinated arylborate anions, such as tetrakis(pentafluorophenyl)borate. Additional suitable anions include sterically shielded diboron anions of the formula:
wherein:
R is a hydrogen, alkyl, fluoroalkyl, aryl, or fluoroaryl, Ar
F
is fluoroaryl, and X
1
is either hydrogen or halide, disclosed in U.S. Pat. No. 5,447,895. Additional examples include carborane compounds such as are disclosed and claimed in U.S. Pat. No. 5,407,884.
Examples of preferred charge separated (cation/anion pair) activators are ammonium, sulfonium, or phosphonium salts capable of transferring a hydrogen ion, disclosed in U.S. Pat. Nos. 5,198,401, 5,132,380, 5,470,927 and 5,153,157, as well as oxidizing salts such as ferrocenium, silver or lead salts, disclosed in U.S. Pat. Nos. 5,189,192 and 5,321,106 and strongly Lewis acidic salts such as carbonium or silylium salts, disclosed in U.S. Pat. Nos. 5,350,723 and 5,625,087.
Further suitable activators for the above metal complexes include strong Lewis acids including tris(perfluorophenyl)borane and tris(perfluorobiphenyl)borane. The former composition has been previously disclosed for the above stated end use in EP-A-520,732, whereas the latter composition is similarly disclosed by Marks, et al., in
J. Am. Chem. Soc
., 118, 12451-12452 (1996). Catalyst activator compounds comprising an anion containing at least two Lewis basic sites which are coordinated to Lewis acids and their use in the polymerization of unsaturated compounds by means of any suitable process including a slurry or gas phase polymerization are disclosed in U. S. provisional application No. 60/75329, and in U.S. Ser. No. 09/251664, filed Feb. 17, 1999.
SUMMARY OF THE INVENTION
According to the present invention there are now provided supported catalyst compositions for use in an addition polymerization comprising:
A) an inert support;
B) a Group 3-10 or Lanthanide metal complex; and
C) an activator compound capable of causing the metal complex B) to form an active polymerization catalyst, said compound corresponding to the formula:
(A*
+a
)
b
(Z*J*
j
)
−c
d
, (I)
wherein:
A* is a cation of charge +a,
Z* is an anion group of from 1 to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites;
J* independently each occurrence is a Lewis acid coordinated to at least one Lewis base site of Z*, and optionally two or more such J* groups may be joined together in a moiety having multiple Lewis acidic functionality,
j is a number from 2 to 12 and
a, b, c, and d are integers from 1 to 3, with the proviso that a×b is equal to c×d.
Additionally according to the present invention there is provided a process for polymerization of one or more addition polymerizable monomers, especially ethylenically unsaturated monomers, most preferably, C
2-20,000
&agr;-olefins, comprising contacting the same, optionally in the presence of an inert aliphatic, alicyclic or aromatic hydrocarbon, with the above catalyst composition under continuous or semi-continuous solution, high pressure, slurry, bulk or gas phase polymerization conditions.
The foregoing supported catalyst compositions are uniquely adapted for use under slurry polymerization conditions and uniquely produce polymers of high bulk density with low reactor fouling. In addition, the foregoing compositions and processes are highly desirable for use in the gas phase polymerization of olefins, particularly ethylene or propylene and combinations of ethylene with a C
3-8
&agr;-olefin.
DETAILED DESCRIPTION OF THE INVENTION
All references herein to elements belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1995. Also any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. When mentioned herein, the teachings of any patent, patent application or publication are hereby incorporated by reference.
The activator compound of formula (I), component C), is further characterized in the following manner. A*
+a
is desirably chosen to provide overall neutrality to the compound and to not interfere with subsequent catalytic activity. Moreover, the cation may participate in the formation of the active catalyst species, desirably through a proton transfer, oxidation, or ligand abstraction mechanism, or a combination thereof.
Examples of suitable cations include ammonium, sulfonium, phosphonium, oxonium, carbonium, and silylium cations, preferably those containing up to 80 atoms not counting hydrogen, as well as ferrocenium, Ag
+
, Pb
+2
, or similar oxidizing cations. In a preferred embodiment, a, b, c and d are all equal to one.
Z* can be any anionic moiety containing two or more Lewis basic sites. Preferably, the Lewis base sites are on different atoms of a polyatomic anionic moiety. Desirably, such Lewis basic sites are relatively sterically accessible to the Lewis acid, J*. Preferably the Lewis basic sites are on nitrogen or carbon atoms. Examples of suitable Z* anions include cyanide, azide, amide and substituted amide, amidinide and substituted amidinide, dicyanamide, imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, substituted benzimidazolide, tricyanomethide, tetracycanoborate, puride, squarate, 1,2,3-triazolide, substituted 1,2,3-triazolide, 1,2,4-triazolide, substituted 1,2,4-triazolide, 4,5-benzi-1,2,3-triazolide, substituted 4,5-benzi-1,2,3-triazolide, pyrimidinide, substituted pyrimidinide, tetraimidazoylborate and substituted tetraimidazoylborate anions, wherein each substituent, if present, is a halo, hydrocarbyl, halohydrocarbyl, silyl, (including mono-, di- and tri(hydrocarbyl)silyl), silylhydrocarbyl, or halocarbyl group of up to 20 atoms not counting hydrogen, or two such substituents together form a saturated or unsaturated ring system.
Specific examples of Z* groups include: imidazolide, 2-nonadecylimidazolide, 2-undecylimidazolide, 2-tridecylimidazolide, 2-pentadecylimidazolide, 2-heptadecylimidazolide, 2-nonadecylimidazolide, 4,5-difluoroimidazolide, 4,5-dichloroimidazolide, 4,5-dibromoimidazolide, 4,5-bis(heptadecyl)imidazolide, 4,5-bis(undecyl)imidazolide, imidazolinide, 2-nonadecylimidazolinide, 2-undecylimidazolinide, 2-tridecylimidazolinide, 2-pentadecylimidazolinide, 2-heptadecylimidazolinide, 2-nonadecylimidazolinide, 4,5-difluoroimidazolinide, 4,5-dichloroimidazolinide, 4,5-dibromoimidazolinide, 4,5-bis(heptadecyl)imidazolinide, 4,5-bis(undecyl)imidazolinide, didecylamide, piperidinide, 4,4-dimethylimidazolinide, tetra-5-pyrimidinylborate, pyrimidinide, 2-undecylbenzimidazolide, 5,6-dichlorobenzimidazolide, 4,5-dicyanoimidazolide, and 5,6-dimethylbenzimidazolide anions.
Preferred Z* groups for the formation of the supported catalysts of the present invention are imidazolide, 2-undecylimidazolide, 1,2,3-triazolide, substituted 1,2,3-triazolide, 1,2,4-tria
Campbell, Jr. Richard E.
Devore David D.
Jacobsen Grant B.
LaPointe Robert E.
Neithamer David R.
Bell Mark L.
Jenkens & Gilchrist
Pasterczyk J.
The Dow Chemical Company
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