Metal Oxide Catalyzed Oxidation of Polymeric Aromatic Ketone With Molecular Oxygen Towards the Synthesis of Poly(4- vinylphenol)

摘要

Poly(4-vinylphenol) (PVPh) and PVPh based polymers are extremely versatile specialty polymers. They are useful in a number of applications such as designing light emitting materials, curing agents for epoxy resins, polymeric adsorbents for the removal of organic matter from aqueous waste, in the formulation of fire-retardant blends, in the preparation of membranes with selective permeability, as radical scavengers, as polymeric antioxidants and as supports for solid-phase and combinatorial synthesis. They are expensive compared to novolac based polymers used in photoresist application, but are the best available materials, currently, for deep UV development -3 In recent times, there has been considerable interest in this laboratory towards the chemical modification of polymers for different applications -10 In the past we have reported the direct introduction of several functional groups by chemical transformation of polystyrene (PS) by polymer modification chemistry towards the synthesis of photoresist material PVPh The in situ generation of active species capable of catalytic action such as peracids has derived lots of interest in the recent years both for small organic molecules and polymers , 11 In the present preprint we report about the oxidation of poly(styrene-co-4- acetylstyrene) (ACPS) prepared from PS by chemical modification. Perbenzoic acid generated in situ using metal oxide, benzaldehyde and molecular oxygen is used for the chemical transformation to poly(4- acetoxystyrene) (APS). The hydrolysis of APS using hydrazine hydrate gives PVPh in dioxane The polymer modications reactions are shown in Scheme.