Zwitterionic catalyst activator

Details Zwitterionic catalyst activator Zwitterionic catalyst activator

1999-12-06

2002-02-05

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...

C502S103000, C502S117000, C502S155000, C502S202000, C526S159000, C526S160000, C526S163000, C526S198000, C526S172000, C556S007000, C556S087000, C556S402000, C556S170000, C556S172000, C564S008000, C564S281000, C564S282000, C568S001000, C568S002000, C568S008000

Reexamination Certificate

active

06344529

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 zwitterionic compound able to activate the metal complex to cause addition polymerization. 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 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, preferably tetrakis(pentafluorophenyl)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 (trisperfluorophenyl)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 in the activation of various metal complexes under a variety of reaction conditions. In particular, the previously known activators comprising a Bronsted acid salt capable of transferring a proton to a ligand of the metal complex, generally simultaneously produce a neutral by-product such as an amine or phosphine compound. Such byproducts are often difficult to remove from the resulting catalyst composition and can adversely affect the catalytic performance of the resulting catalyst composition. 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 zwitterionic compounds, corresponding to the formula:
wherein:
L
+
is a protonated derivative of an element of Group 15 of the Periodic Table of the Elements, additionally bearing two hydrocarbyl substituents of from 1 to 50 carbons each. or a positively charged derivative of an element of Group 14 of the Periodic Table of the Elements, said Group 14 element being substituted with three hydrocarbyl substituents of from 1 to 50 carbons each;
R
1
is a divalent linking group of from 1 to 40 non-hydrogen atoms;
R
2
independently each occurrence is a ligand group of from 1 to 50 nonhydrogen atoms with the proviso that in a sufficient number of occurrences to balance charge in the compound, R
2
is L
+
—R
1
—;
R
4
is a bridging hydride or halide group or a divalent linking group of from 1 to 40 non-hydrogen atoms;
M
1
is boron, aluminum or gallium;
Ar
f
independently each occurrence is a monovalent, fluorinated organic group containing from 6 to 100 non-hydrogen atoms;
Y is a Group 15 element; and
Z is a Group 14 element.
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 zwitterionic 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 zwitterionic boron compounds are uniquely capable of forming active catalyst compositions from neutral Group 3-10 metal complexes without generating separate Lewis base byproducts able to coordinate to the resulting active metal species. As a result the compounds possess improved catalyst activation properties. 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.
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.
The compounds of the invention are further characterized in the following manner. Examples of preferred zwitterionic boron compounds according to the present invention correspond to the formula: HL′
+
—R
1
—B
−
(Ar
f
)
3
, wherein:
R
1
is a hydrocarbylene group or a halo-, alkoxy-, N,N-dihydrocarbylamino-, silyl-, or germyl-substituted hydrocarbylene group, said R
1
having from 2 to 40 atoms not counting hydrogen atoms;
L′ is dihydrocarbyl substituted nitrogen or phosphorus group, having from 1 to 50 carbons in each hydrocarbyl group; and
Ar
f
independently each occurrence is a monovalent, fluorinated organic group containing from 6 to 100 atoms not counting hydrogen atoms.
Highly preferred are zwitterionic compounds corresponding to the formula:
HN
+
(R
5
)
2
—R
1
—B
−
(Ar
f
)
3
,
wherein:
R
1
is a C
1-40
alkylene group or a C
6-40
arylene group;
R
5
independently each occurrence is a C
1-50
hydrocarbyl group; and
Ar
f
each occurrence is perfluorophenyl, perfluoronaphthyl or perfluorobiphenyl.
Generally, solubility of the compounds of the invention in aliphatic compounds is increased by incorporation of one or more oleophilic R
5
groups such as long chain alkyl groups; long chain alkenyl groups; or halo-, alkoxy-, amino-, silyl-, or germyl-substituted long chain alkyl groups or long chain alkenyl groups. By the term “long chain” are meant groups having from 10 to 50 non-hydrogen atoms in such group, preferably in a non-branched form. It is understood that the catalyst activator may comprise a mixture of R
5
groups of differing lengths. For example, one suitable activator (wherein L is nitrogen) may be derived from the commercially available long chain amine comprising a mixture of two C
14
, C
16
or C
18
alkyl groups and one methyl group. Such amines are available from Witco Corp., under the trade name Kemamine™ T9701, and from Akzo-Nobel under the trade name Armeen™ M2HT.
Most highly preferred zwitterionic compounds for use herein are:
wherein R
5
is methyl, phenyl or a mixture of C
14-18
alkyl.
The present

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