Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Boron or compound containing same
Reexamination Certificate
2000-05-12
2003-10-21
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Boron or compound containing same
C502S150000, C502S203000, C526S134000, C526S160000, C556S007000, C556S008000, C556S009000, C568S006000
Reexamination Certificate
active
06635597
ABSTRACT:
The present invention relates to a compound that is useful as a catalyst activator. More particularly the present invention relates to such compounds that are particularly adapted for use in the addition polymerization of unsaturated compounds in combination with a Group 3-10 metal complex, said activator comprising at least one perfluoronaphthyl substituted boron compound. Such an activator is particularly advantageous for use in a polymerization process wherein catalyst, catalyst activator, and at least one polymerizable monomer are combined under polymerization conditions to form a polymeric product.
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 of such Group 3-10 metal complex. Preferred Bronsted acid salts are such compounds containing a cation/anion pair that are capable of rendering the Group-3-10 metal complex catalytically active. Suitable activators comprise fluorinated arylborate anions, preferably tetrakis(pentafluoro-phenyl)borate anions. Additional suitable anions include sterically shielded diboron anions corresponding to the formula:
wherein:
S is 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 protonated ammonium, sulfonium, or phosphonium salts capable of transferring a hydrogen ion, disclosed in U.S. Pat. No. 5,198,401, U.S. Pat. No. 5,132,380, U.S. Pat. No. 5,470,927, and U.S. Pat. No. 5,153,157, as well as oxidizing salts such as carbonium, ferrocenium and silyilium salts, disclosed in U.S. Pat. No. 5,350,723, U.S. Pat. No. 5,189,192 and U.S. Pat. No. 5,626,087.
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).
Despite the satisfactory performance of the foregoing catalyst activators under a variety of polymerization conditions, there is still a need for improved cocatalysts for use activation of various metal complexes under a variety of reaction conditions. Accordingly, it would be desirable if there were provided catalyst activators that could be employed in solution, slurry, gas phase or high pressure polymerizations and under homogeneous or heterogeneous process conditions having improved activation properties.
According to the present invention there is now provided Group 13 containing compounds in neutral (Lewis acid) or charge separated (cation/anion pair) form, corresponding to the formula:
(R
1
)
r
—B(Ar
f
)
m
wherein:
B is boron;
R
1
independently each occurrence is a monovalent, anionic ligand group, with the proviso that for cationic compounds, one R
1
additionally comprises a dissociated cation moiety;
Ar
f
independently each occurrence is a monovalent, fluorinated organic group containing from 10 to 100 non-hydrogen atoms,
r is 0, 1, 2 or 3, and
m is 1, 2 or 3;
with the proviso that the sum of r and m is 3 or 4, and if r+m=3, then B is neutral and if r+m=4, then B is negatively charged, said charge being balanced by a cation component of one R
1
.
Additionally according to the present invention there is provided a catalyst composition capable of polymerizing an ethylenically unsaturated, polymerizable monomer comprising, in combination, a Group 3-13 metal complex and the above described Group 13 compound, or the reaction product resulting from such combination.
Additionally according to the present invention there is provided a process for polymerization of one or more ethylenically unsaturated, polymerizable monomers comprising contacting the same, optionally in the presence of an inert aliphatic, alicyclic or aromatic hydrocarbon, with the above described catalyst composition.
The foregoing Group 13 compounds are uniquely capable of forming monomeric and dimeric cationic metal complexes from neutral metallocene complexes under certain operating conditions. They are also uniquely adapted for use in activation of a variety of metal complexes, especially Group 4 metal complexes, under standard and atypical polymerization conditions, and give improved yields of resulting olefin polymer.
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, in reference to a cation portion of any compound herein, it is stated that a ligand group comprises such cation, it is to be understood that the cation is not chemically or physically incorporated in said ligand, or necessarily chemically attached thereto, in as much as the cation may freely dissociate from the anion portion of the compound. Rather, such ligand group is said to “comprise” the cation in order to properly account for the correct number of cations as dictated by considerations of charge balance.
The compounds of the invention are further characterized in the following manner. Preferred examples of suitable neutral Lewis acids according to the present invention correspond to the formula:
(R
1
)
r
—B(Ar
f
)
m
wherein:
R
1
independently each occurrence is a monovalent, anionic ligand group containing from 1 to 1000 non-hydrogen atoms;
r is 0, 1 or 2, and
the sum of r and m is 3.
More preferably, in the foregoing formula, R
1
is a C
1-40
hydrocarbyl ligand, halohydrocarbyl or halocarbyl group.
Further preferred examples of the foregoing Lewis acid compounds are pentafluorophenylbis(pertluoronaphthyl)borane and tris(perfluoronaphthyl)borane.
Examples of preferred charge separated activating compounds according to the present invention correspond to the formula:
(R
1
)
r
—B(C
10
F
7
)
m
wherein:
R
1
each occurrence is a C
1-1000
hydrocarbyl, halohydrocarbyl, or halocarbyl group, and one R
1
additionally comprises a cation which is a protonated cation of a Bronsted acid, ferrocenium, a carbonium cation, a silylium cation, Ag
+
, or the cationic derivative of a Group 3-10 metal complex catalyst;
r is 1, 2 or 3;
m is 1, 2, or 3; and
the sum of r and m is 4.
More preferably, in the foregoing formula, R
1
is a C
1-40
hydrocarbyl ligand, halohydrocarbyl or halocarbyl group, and in one occurrence additionally comprises a tri(C
1-40
hydrocarbyl)ammonium cation;
Most highly preferred examples of the foregoing charge separated catalyst activators are L
+
B
−
(C
6
F
5
)
3
(C
10
F
7
), L
+
B
−
(C
6
F
5
)
2
(C
10
F
7
)
2
, L
+
B
−
(C
6
F
5
)
1
(C
10
F
7
)
3
, and L
+
B
−
(C
10
F
7
)
4
,
wherein L
+
is a cation of a Bronsted acid, ferrocenium, a carbonium cation, a silylium cation, Ag
+
, or the cationic derivative of a Group 3-10 metal complex catalyst.
More preferably L
+
is an ammonium cation of the formula HN
+
R
3
, wherein R is C
1-50
hydrocarbyl. Most preferably, one or two R groups are C
14-50
aliphatic groups, and the remaining R group(s) is (are) C
1-4
aliphatic.
The skilled artisan will appreciate that upon activation of a metal complex to a catalytically active state by the present compounds, to the extent a cationic derivative thereof is formed, the foregoing charge separated compounds may include therein the cationic derivative of such metal complex in place of the foregoing Bronsted acid, ferrocenium, carbonium, silylium, or Ag
+
cations. For the preferred c
Chen You-Xian
Li Liting
Marks Tobin J.
McAdon Mark H.
Nickias Peter N.
Northwestern University
Rabago R.
Wu David W.
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