Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-12-11
2002-12-03
Powers, Fiona T. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C548S469000, C548S490000, C548S563000, C548S577000, C548S950000, C564S289000, C568S009000
Reexamination Certificate
active
06489480
ABSTRACT:
TECHNICAL FIELD
This invention relates to ionic catalyst systems, especially to polymerization processes using ionic catalyst systems; to precursors for ionic catalyst systems comprising Group-15-containing cations and noncoordinating anions; and to methods of use of Group-15-element-containing cations.
BACKGROUND
The term “noncoordinating anion” (NCA) is now accepted terminology in the field of olefin and vinyl monomer polymerization, both by coordination or insertion polymerization and carbocationic polymerization. See, for example, EP 0 277 004, U.S. Pat. No. 5,198,401, Baird, Michael C., et al., J. Am. Chem. Soc. 1994, 116, 6435-6436, U.S. Pat. No. 5,312,881, U.S. Pat. No. 5,668,234, and WO 98/03558. The noncoordinating anions are described to function as electronic stabilizing counterions for essentially cationic metallocene complexes that are active for polymerization. The term noncoordinating anion as used here applies both to truly noncoordinating anions and anions that at most, coordinate so weakly that they are labile enough to allow for olefinic or acetylenic monomer insertion. These noncoordinating anions can be effectively introduced into a polymerization medium, separate from the organometallic catalyst compound or premixed with the catalyst prior to adding it to the polymerization medium, as Bronsted acid salts containing charge-balancing countercations.
Both U.S. Pat. No. 5,198,401 and WO 97/35893 specifically address nitrogen-containing Bronsted acid cations that are capable of abstracting a leaving (labile) group on neutral, organometallic transition-metal catalyst precursor compounds by donating a proton to such labile groups, thus rendering the catalyst precursor compounds cationic and providing a compatible, counterbalancing noncoordinating anion. U.S. Pat. No. 5,198,401 describes catalyst activator compounds represented by the formula [(L′—H)
+
]
d
[(M′)
m+
Q
1
Q
2
. . . Q
n
]
d−
where L′ is a neutral base, H is a hydrogen atom and [(M′)
m+
Q
1
Q
2
. . . Q
n
] is a metal or metalloid atom connected to a variety of ligands, preferably where M is boron and two or more of Q
n
are aromatic radicals, such as phenyl, napthyl and anthracenyl, each preferably fluorinated. L′ is illustrated with various trialkyl-substituted ammonium complexes and N,N-dialkylanilinium complexes. WO 97/35893 describes cocatalyst activator compounds represented by the formula [L*—H]
+
[BQ′
4
]
−
where L* includes nitrogen-containing neutral Lewis bases, B is +3 boron, and Q′ is a fluorinated C
1-20
hydrocarbyl group, preferably a fluorinated aryl group. The cocatalyst compounds are said to be rendered soluble in aliphatic solvents by incorporation of aliphatic groups, such as long chain alkyl or substituted-alkyl groups, into the Bronsted acid [L*—H]
+
. Bis(hydrogenated-tallow-alkyl)methylammonium and di(dicosyl)methyl-ammonium salts are exemplified.
In view of the above there is a continuing need for cocatalyst activation compounds both to improve industrial economics and to provide alternative synthesis and preparation methods of these cocatalyst compounds. In particular, the catalyst activation reaction by the above nitrogen-containing cocatalyst compounds can result in neutral amine compounds, L, by loss of the hydronium atom, H
+
, in the activating protonation reaction. These L compounds are Lewis bases that may interact with the strong Lewis acid, organometallic catalyst cations, and may in some cases adversely interfere with overall polymerization kinetics. See in particular, EP 0 426 637, where the use of carbenium, oxonium, and sulphonium cations are taught for replacement of Lewis base amines with the suggestion that catalyst poisons and undesirable residual amines can thus be avoided.
BRIEF SUMMARY
Embodiments of this invention address a process for preparing polyolefins from one or more olefinic monomers in which the olefins are combined with the reaction product of i) an organometallic catalyst compound and ii) a cocatalyst complex comprising a fluoroaryl-ligand-substituted secondary amine or phosphine and a Group-13-based noncoordinating or weakly coordinating anion. The invention cocatalysts provide residual amine or phosphine compounds with reduced basicity relative to those of the prior art, as well as noncoordinating or weakly coordinating anions for organometallic catalyst complexes that exhibit surprisingly high polymerization activities.
The term noncoordinating anion as used here applies both to truly noncoordinating anions and coordinating anions that are less coordinating than olefinic or acetylenic monomers. These noncoordinating anions can be effectively added to a polymerization medium or premixed with an organometallic catalyst compound before adding it to the polymerization medium, as Bronsted acid salts containing the invention charge-balancing countercations.
DETAILED DESCRIPTION
The invention provides a process for olefin polymerization in which Group-13 cocatalyst complexes and transition metal organometallic catalyst precursor compounds can be combined to form active olefin polymerization catalysts. After activation or essentially concurrent with activation, the catalyst is exposed to suitable monomer that has accessible olefinic, vinylic or acetylenic unsaturation.
Using the general formula [L—H]
+
[A]
−
, where [A]
−
is any anion suitable for olefin polymerization, the Lewis base compounds, L, of the invention are typically based on fluorinated amine compounds meeting the general formula R′
i
ArF—ER
2
where ArF is a fluoroaryl ligand, E is nitrogen or phosphorous, and each R is independently a C
1
-C
20
linear or branched hydrocarbyl or hydrocarbylsilyl substituent. Additionally, the two R's may connect to form a substituted or unsubstituted, halogenated or non-halogenated, C
2
-C
20
cycloaliphatic, C
2
-C
10
hyrodcarbyl or C
2
-C
10
hydrocarbylsilyl. R′ is a C
1
-C
20
hydrocarbyl or halogenated hydrocarbyl. Suitable fluoroaryl substituents on the nitrogen atom can be substituted or unsubstituted phenyl, or biphenyl. The substitutions can be on ring carbon atoms, or the ring carbon atom itself can be substituted, yielding a hetero-aromatic ring. Some embodiments use a perfluorinated aromatic ring. The R′ substituent may be a linear or branched, fluorinated or unfluorinated alkyl or alkenyl substituent. Some embodiments are based on the following fluoroaryl-ligand-substituted amines, ArF—NR
2
, where the fluoroaryl ligand, ArF, may be a fluoro- or perfluoro-substituted aryl. R represents substituted or unsubstituted, alkyl or cycloalkyl groups as defined above, which may be selected independently. Some embodiments employ the following cyclic secondary amines: N-pentafluorophenylpyrrolidine, N-para-nonafluorobiphenylpyrolidine, N-tridecafluoroterphenylpyrolidine, N-pentafluorophenylpyrrole, N-paranonafluorobiphenylpyrrole, N-tridecafluoroterphenylpyrrole, N-pentafluorophenylpiperidine, N-paranonafluorobiphenylpiperidine, N-tridecafluoroterphenylpiperidine, N-pentafluorophenylindoline, N-paranonafluorobiphenylindoline, N-tridecafluoroterphenylindoline, N-pentafluorophenylindole, N-paranonafluorobiphenylindole, N-tridecafluoroterphenylindole, N-pentafluorophenyazetidine, N-paranonafluorobiphenylazetidine, N-tridecafluoroterphenylazetidine, N-pentafluorophenyaziridine, N-paranonafluorobiphenylaziridine, and N-tridecafluoroterphenylaziridine.
Effective, invention Group-13 cocatalyst complexes are, in some embodiments, derived from an ionic salt comprising a 4-coordinate, Group-13 anionic complex, represented as:
[L—H]
+
[(M′)Q
1
Q
2
. . . Q
n
]
−
,
where [L—H]
+
is defined above, M is one or more Group-13 metal or metalloid, including boron or aluminum. Each Q is a ligand effective for providing electronic or steric effects rendering [(M′)Q
1
Q
2
. . . Q
n
&
ExxonMobil Chemical Patents Inc.
Powers Fiona T.
Runyan Charles E.
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