Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-06-04
2004-04-27
Harlan, Robert (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S161000, C526S171000, C526S172000, C526S901000, C502S152000, C502S155000
Reexamination Certificate
active
06727329
ABSTRACT:
BACKGROUND INFORMATION
The present invention relates to compounds that are useful as catalyst components. More particularly the present invention relates to such compounds that are particularly adapted for use in the coordination polymerization of unsaturated compounds comprising an anion containing at least two Lewis basic sites derived from certain inorganic or organic Bronsted acids, which are coordinated to Lewis acids. Such compounds are particularly advantageous for use in forming supported polymerization catalysts wherein at least the catalyst activator is chemically attached to a substrate material.
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:
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 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).
In WO99/42467, WO01/23442 and WO02/08303 expanded ionic catalyst activators are disclosed that are well suited for use as olefin polymerization activators.
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 especially under a variety of reaction conditions. Accordingly, it would be desirable if there were provided compounds that could be employed in solution, slurry, gas phase or high pressure polymerizations and under homogeneous or heterogeneous process conditions having improved activation properties.
SUMMARY OF THE INVENTION
According to the present invention there are now provided compounds useful as catalyst activators corresponding to the formula: (A*
+a
)
b
(Z*
J
*
j
)
−c
d
, wherein:
A* is a proton or a cation of from 1 to 80 atoms, preferably 1 to 60 atoms, not counting hydrogen atoms, said A* having a charge +a,
Z* is an anion group of from 1 to 50 atoms, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites, said Z* being the conjugate base of an inorganic Bronsted acid or a carbonyl- or non-cyclic, imino-group containing organic Bronsted acid;
J* independently each occurrence is a Lewis acid of from 1 to 80 atoms, preferably 1 to 60 atoms, not counting hydrogen atoms, 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 1 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.
The foregoing compounds may be utilized in combination with one or more Group 3-10 or Lanthanide metal complexes to form catalyst compositions for polymerization of addition polymerizable monomers, especially ethylenically unsaturated monomers, most preferably, C
2-20,000
&agr;-olefins. Additionally, the compounds may be utilized to form latent activators, that is, compounds that may themselves not cause a metal complex to become catalytically active due, for example, to the presence of a reactive group such as a hydroxyl group, but which may be converted to an active compound by, for example, in-situ reaction of the hydroxyl group with a Lewis acid, especially an aluminum hydrocarbyl compound, or an alkali metal halide or ammonium halide salt. Moreover, such compounds may be deposited onto solid supports, such as by impregnation, surface deposition, physisorption or chemical reaction with the support, reactive functionality of the support, or chemical modifiers associated with the support, to form heterogeneous catalyst components for use in preparing heterogeneous catalyst compositions for use in polymerization of the foregoing monomers.
Thus, in one embodiment of the invention, the foregoing compounds containing hydroxyl or other reactive functionality are used to form supported catalyst components by reaction of the hydroxyl group thereof with reactive functionality of a support material, or by conversion of the dialkylaluminumoxyhydrocarbyl, trihydrocarbylsiloxyhydrocarbyl or hydrocarbyloxyhydrocarbyl group to a reactive functionality and reaction thereof with reactive functionality of a support material. The resulting supported catalyst components are highly resistant to loss of activator compound in a liquid reaction medium such as occurs in a slurry polymerization. One or more Group 3-10 or Lanthanide metal complexes, preferably a Group 4 metal complex, and additional additives, modifiers and adjuvants may be added to the catalyst component, either before, after or simultaneous with addition of the cocatalyst of the present invention, to form the fully formulated catalyst composition. Accordingly, in one embodiment of the invention the foregoing structures can be created on a surface containing chemically or physically bonded anionic groups, Z*.
Another embodiment of the invention is a composition of matter comprising the admixture or reaction product, optionally in an inert diluent, of an inorganic Bronsted acid or a carbonyl- or non-cyclic, imino-group-containing organic Bronsted acid; from one to twelve moles per mole of Bronsted acid of a Lewis acid having from 1 to 80, preferably 1 to 60 atoms, not counting hydrogen atoms; optionally a Lewis base of from 1 to 80, preferably 1 to 60 atoms, not counting hydrogen, preferably an amine or phosphine containing Lewis base; and further optionally an organoaluminum compound, preferably an alumoxane, especially methylalumoxane or modified methylalumoxane.
Additionally according to the present invention there is provided a catalyst composition for polymerization of an ethylenically unsaturated, polymerizable monomer comprising, in combination, the above described activator compound or composition of matter, a Group 3-10 metal complex that is capable of activation to form an addition polymerization catalyst, or the reaction product of such combination, and optionally a support.
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 catalyst compositions or supported catalyst compositions.
The foregoing compounds are uniquely adapted for use in activation of a variety of metal complexes, especially Group 4 metal complexes, under standard and a typical olefin polymerization c
Dow Global Technology Inc.
Harlan Robert
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