Accession Number : ADA310761

Title :   Functionalization of Reactive Polymers by Metalation with Superbases followed by Reaction with Electrophiles.

Descriptive Note : Technical rept.,

Corporate Author : CORNELL UNIV ITHACA NY BAKER LAB

Personal Author(s) : Frechet, Jean M. ; Steinke, Joachim H. ; Haque, Shah A. ; Wynne, Kenneth J.

PDF Url : ADA310761

Report Date : 30 JUN 1996

Pagination or Media Count : 32

Abstract : In order to test novel routes for the functionalization of polyolefins, hydrocarbon-soluble superbases have been used for the selective metalation of a copolymer of isobutylene and p- methylstyrene. The metalation reaction directed at the benzylic p-methyl position is followed by (1)H NMR spectrometry after quenching with an electrophile. Superbases obtained by the procedure of Lochmann involving the reaction of butyl lithium with a heavier alkali alkoxide have a reactivity that increases with the size of the metal cation. Best results are obtained using a superbase derived from s-BuLi and cesium l-(-)-menthoxide in the ratio of 1:3. Complete metalation of all the benzylic p-methyl groups is possible if an excess of superbase is used. This method of functionalization developed for solutions of the poly(isobutylene-co-p-methylstyrene) rubbers may also be applicable to introduce functional groups onto surfaces.

Descriptors :   *POLYMERS, *REACTIVITIES, *BASES(CHEMISTRY), *OLEFIN POLYMERS, *METALATION, TEST AND EVALUATION, METALS, CATIONS, METHYL RADICALS, MOLECULES, STYRENES, SPECTROMETRY, CESIUM, QUENCHING, LITHIUM, ELECTRONS, HYDROCARBONS, BENZYL RADICALS, POLYETHYLENE PLASTICS, ALKALI METALS, BUTYL RUBBER.

Subject Categories : Polymer Chemistry
      Inorganic Chemistry
      Organic Chemistry
      Elastomers and Rubber
      Atomic and Molecular Physics and Spectroscopy

Distribution Statement : APPROVED FOR PUBLIC RELEASE