Catalyst for polymerization of norbornene

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...

Reexamination Certificate

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C526S098000, C526S100000, C526S108000, C526S135000, C526S139000, C526S141000, C526S143000, C526S145000, C526S147000, C526S172000, C526S279000, C502S102000, C502S162000, C502S167000, C502S169000, C502S170000, C502S172000

Reexamination Certificate

active

07122611

ABSTRACT:
This invention is based upon the discovery that a catalyst system which is comprised of (a) palladium or a palladium compound and (b) a fluorinated alcohol is effective for polymerizing norbornene-functional monomers into polynorbornene-functional polymers. It has been further discovered that this catalyst system is more effective in polymerizing certain norbornene-functional monomers that are difficult to polymerize, such as norbornene ester monomers, than prior art catalyst systems. The activity of the catalyst systems of this invention can be further improved with respect to polymerizing some monomers by including a Lewis acid and/or a ligand, such as a phosphine or a carbene, in the system. In any case, the catalyst systems of this invention offer the advantage of being soluble in a wide variety of solvents, relatively inexpensive, and capable of polymerizing many norbornene-functional monomers that are difficult to polymerize with conventional catalyst systems. The subject invention more specifically discloses a catalyst system that is especially useful for the polymerization of norbornene-functional monomers which is comprised of (a) palladium or a palladium compound and (b) a fluorinated alcohol. The present invention also reveals a process for synthesizing a norbornene-functional polymer which comprised polymerizing a norbornene-functional monomer in a solvent in the presence of a catalyst system which is comprised of (a) palladium or a palladium compound and (b) a member selected from the group consisting of fluorinated alcohols, fluorinated acids, and ionic liquids, wherein the catalyst system is void of alkyl aluminum compounds.

REFERENCES:
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Magna et al, The importance of Imidazolium Substituents in the Use of Imidazolium-Based Room-Temperature Ionic Liquids as Solvents for Palladium-Catalyzed Telomerization of Butadiene with Methanol, Organometallics 2003, 22, 4418-4425.
Selvakumar, et al., New Palladium Carbene Catalyst for the Heck Reaction of Aryl Chlorides in Ionic Liquids, Organic Letters 2002, 4(18), 3031-3033.
Okubo, et al., Heck reaction in a non-aqueous ionic liquid using silica-supported palladium complex catalysts, Tetrahedron Letters 43 (2002) 7115-7118.
Calo'. et al., Heck Reaction Catalyzed by Nanosized Palladium on Chitosan in Ionic Liquids, Organometallics 2004, 23, 5154-5158 (Web Publication Date: Sep. 18, 2004).

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