Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1998-08-10
2000-08-22
Wu, David W.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526160, 526161, 526172, 5263486, 526943, 556 8, 556 53, 502104, 502152, 502202, C08F 444, C07F 502
Patent
active
061074217
DESCRIPTION:
BRIEF SUMMARY
This invention relates to metal complexes and to addition polymerization catalysts formed therefrom that have improved catalytic performance. More particularly the present invention relates to an addition polymerization catalyst composition comprising a Group 3, 4, or Lanthanide metal complex containing a boratabenzene group or divalent derivative thereof bonded via its delocalized .pi. electrons to the metal (also referred to as a boracyclohexadienyl group). In addition, the present invention relates to certain of the foregoing complexes possessing a novel bridged structure. Finally, the invention relates to a method of using the foregoing catalyst compositions in an addition polymerization process for polymerizing addition polymerizable monomers.
In EP-A-416,815 there are disclosed certain constrained geometry metal complexes and catalysts derived by reacting the metal complex with activating cocatalysts. Supported derivatives of such catalysts were prepared by contacting them with a support such as alumina, silica or MgCl.sub.2. In U.S. Pat. No. 5,064,802 (EP-A-418,044) there are disclosed certain further catalysts formed by reacting metal complexes with ion forming activating cocatalysts that are salts of Bronsted acids containing a noncoordinating compatible anion. The reference discloses the fact that such complexes are usefully employed as catalysts in addition polymerizations. In EP-A-520,732 an alternative technique for preparing cationic constrained geometry catalysts using borane activators is disclosed.
In U.S. Pat. No. 4,892,851 there are disclosed biscyclopentadienyl Group 4 metal complexes, especially complexes of zirconium or hafnium that are usefully employed with alumoxane activating cocatalysts for use in addition polymerizations, especially the polymerization of aliphatic .alpha.-olefins. In a series of patents, W. Spaelick has disclosed certain ring substituted stereorigid bisindenyl complexes and their use as olefin polymerization catalysts. The bridging group of such complexes generically includes silicon, germanium or tin containing divalent groups containing hydride, halogen, C.sub.1-10 alkyl, C.sub.1-10 fluoroalkyl, C.sub.6-10 aryl, C.sub.6-10 fluoroaryl, C.sub.1-10 alkoxy, C.sub.2-10 alkenyl, C.sub.7-40 aralkyl, C.sub.8-40 aralkenyl or C.sub.7-40 alkylaryl groups or ring forming combinations thereof. Such disclosure may be found in U.S. Pat. No. 5,243,001, U.S. Pat. No. 5,145,819, U.S. Pat. No. 5,304,614, U.S. Pat. No. 5,350,817, among others.
Boratabenzenes are anionic ligands which are boron containing six membered ring systems. They are previously known in the art having been described by A. Ashe, et al., J. Am. Chem. Soc., 93,1804-1805 (1971). They may be prepared by reaction of 1,1-diorgano-1-stannacyclohexa-2,5-diene and a borontrihalide followed by substitution with a hydrocarbyl, amino, silyl or germyl group. Such ligand groups correspond to the formula: ##STR1## wherein J is selected from the group consisting of hydrogen, hydrocarbyl, dihydrocarbylamino, silyl, germyl, halohydrocarbyl, or halocarbyl, said J having up to 20 non-hydrogen atoms.
It would be desirable if there were provided an improved catalyst system based on the foregoing boratabenzene groups as well as an improved addition polymerization process utilizing such catalyst systems.
As a result of investigations carried out by the present inventors there have now been discovered new and improved Group 3, 4, or Lanthanide metal complexes corresponding to the formula: ##STR2## or a dimer, solvated adduct, chelated derivative or mixture thereof, wherein:
Y is a divalent derivative of a boratabenzene group or a hydrocarbyl-, dihydrocarbylamino-, silyl- or germyl-substituted boratabenzene group containing up to 50 nonhydrogen atoms that is bonded via its delocalized .pi.-electrons to M;
L is Y or a hydrocarbadiyl group that is bound to M by means of its delocalized .pi.-electrons, or L is a monovalent or divalent amido group, said L group containing up to 50 nonhydrogen atoms;
M is a metal of Group 3, 4 or the Lant
REFERENCES:
patent: 5554775 (1996-09-01), Krishnamurti et al.
Bazan, et al. Aminoboratabenzene Derivatives of Zirconium: A New Class of Olefin Polymerization Catalysts, JACS 1996, 118, 2291-2292, Mar. 1996.
Al-Ahmad Saleem A.
Ashe, III Arthur J.
Devore David D.
Fang Xinggao
Timmers Francis J.
Harlan R.
The Dow Chemical Company
The Regents of the University of Michigan
Wu David W.
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