Use of Alcohol as Initiator for Reversible Chain Transfer Catalyzed Polymerization

Abstract

A novel initiation system, using a hydroxyl group as an initiating moiety, was developed for reversible chain transfer catalyzed polymerization (RTCP), a living radical polymerization. The hydroxyl (alcohol) group was reacted with an iodinating agent and a monomer (M), giving a dormant species RO–M–I (I = iodine). It was prepared in the polymerization medium (monomer) and used in the polymerization without the purification, leading to a one‐pot RTCP from a hydroxyl group (an alcohol).

Regio‐ and Diastereo‐Selective Biomimetic Synthesis of (±)‐ϵ‐Viniferin by NIS and Resveratrol

“…NIS could act as the radical promoter on an hydroxyl group. In fact, alcohols are known to be oxidized by NIS to form the hypoiodites (RO‐I) [16] . The oxygen–iodine bond of RO–I is thermally or photochemically cleaved to generate the alkoxy and the iodine radicals.…”

“…In fact, alcohols are known to be oxidized by NIS to form the hypoiodites (RO-I). [16] The oxygen-iodine bond of RO-I is thermally or photochemically cleaved to generate the alkoxy and the iodine radicals. Therefore the likely radical mechanism for dimerization process can start with the formation of a radical moiety on the para-phenol of iodinated resveratrol 9 which is stabilized by resonance forms A, B, C and D. The CÀ C coupling between C and D generated compound 10 (scheme 2).…”

Reversible complexation mediated polymerization (RCMP) starting with a complex of iodine with organic salt and thermal initiators

“…Recently, Goto et al developed two new families of RDRPs employing iodine as capping agent (X) and an organic compound as catalyst. One method is referred as reversible chain transfer catalyzed polymerization (RTCP), in which different iodides, including tin (Sn) [12,13], germanium (Ge) [12,13], phosphorus (P) [14,15], nitrogen (N) [16,17], oxygen (O) [18,19] and carbon (C) [20] centered iodides were used as organic catalysts. These catalysts (deactivators) could react with Polymer• formed by conventional initiator to generate the dormant species, Polymer-I, and the activator of Polymer-I at the same time.…”

H‐Phosphonic Acid Derivatives as Catalysts for Reversible Chain Transfer Catalyzed Polymerization (RTCP) at Ambient and High Pressure

“…[2] An RTCP system consists of monomer, an alkyl iodide (source of X ¼ iodine and initiator of the living process), a conventional radical initiator (source of P ), and a non-transition-metal catalyst or its precursor. Currently used catalysts include tin (Sn), [2,3] germanium (Ge), [2,3] phosphorus (P), [2][3][4] nitrogen (N), [3][4][5][6] oxygen (O), [7,8] and carbon (C) [8] -centered compounds. Without a catalyst, the system corresponds to an iodine transfer polymerization (ITP), [9] which is based on a degenerative chain transfer (DT).…”