PREPARATION OF FUNCTIONALIZED POLYMERS UTILIZNG A SOLUBLE HIGHLY REACTIVE FORM OF CALCIUM

Authors

• Reuben D. Rieke, Lincoln, NE

Document Type

Article

Date of this Version

1993

Citation

Patent Number: 5,211,886

Comments

Appl. No.: 739,294

Abstract

Calcium-substituted polymeric reagents are provided. These reagents can be prepared via the oxidative addition of a soluble highly reactive calcium species to organic and inorganic polymers containing alkyl, aryl, or alkylaryl pendent groups substituted with halide atoms, cyanide molecules, 1,3-dienes, or any conjugated poly unsaturated system. Preferably, the polymer is a cross linked p-bromopolystyrene, p-chloropolystyrene, p fluoropolystyrene, or chloromethylated polystyrene. Preferably, the soluble highly reactive calcium species is prepared from the reduction of Ca(II) salts with an alkali metal arene, such as lithium biphenylide. These calcium-substituted polymeric reagents react with a variety of electrophiles to yield functionalized polymers. Reaction with Cu(I) salts yields calcium-sub stituted polymeric cuprate reagents, which can react, for example, with acid chlorides to form ketones, alkyl halides containing functionality, and undergo 1,4-conjugate addition with af-unsaturated ketones, aldehydes, esters, and amides. Bifunctionalization of the polymer can be achieved by the addition of highly reactive calcium to a functionalized polymer containing a halogen. Polymers can be cross-coupled with dyes, UV stabilizers, biologically active substrates, molecules that impart specifically desired characteristics, among other desirable functional groups.