Synthesis of reactive poly(norbornene): Ring‐opening metathesis polymerization of norbornene monomer bearing cyclic dithiocarbonate moiety

Abstract

A norbornene monomer bearing cyclic dithiocarbonate moiety (NB‐DTC) was successfully synthesized from the corresponding precursor having epoxy moiety by its reaction with carbon disulfide. NB‐DTC underwent the ring‐opening metathesis polymerization (ROMP) catalyzed by a ruthenium carbene complex to give the corresponding poly(norbornene). The dithiocarbonate moiety incorporated into the side chain of the obtained poly(norbornene) reacted with amine to afford the corresponding thiourethane moiety with thiol group, which underwent oxidative S‐S coupling and/or addition reaction to the C‐C double bond in the main chain, leading to formation of a cross‐linked polymer. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.

Protected thiol strategies in macromolecular design

“…Although disulfide formation is undoubtedly a useful reaction, a major drawback is that the oxidation of thiols can occur (quite easily) at inappropriate timings, leading to unwanted sideproducts. Quite some examples exist in which the synthesis of polythiols is intended, but the final end-product is isolated as an insoluble cross-linked polymer network [61]. A correct use of protecting group strategies is therefore required to overcome these problems.…”

“…More recently, the research group investigated the synthesis of a norbornene monomer bearing a cyclic dithiocarbonate moiety (NB-DTC; see Scheme 46) [61], intended for the synthesis of reactive poly(norbornene).…”

Synthesis and radical polymerization of styrene‐based monomer having a five‐membered cyclic dithiocarbonate structure

“…Among various sulfur‐derived functional groups, cyclic dithiocarbonate15–18 have attracted much attention because they exhibit low dielectric constants, high refractive indices, high metal coordination abilities, and specific reactivities toward amines. Our research group has already studied the synthesis of polymers having the five‐membered cyclic dithiocarbonate structures, and revealed their unique properties 10, 11, 13. However, styrenic polymers having five‐membered dithiocarbonate groups have not been synthesized so far.…”

“…INTRODUCTION Sulfur-containing materials have been widely applied for optical materials, 1À3 metal absorbents, [4][5][6][7] and reactive polymers [8][9][10][11][12][13][14] owing to their high refractive indices, high metal coordination ability, and specific reactivity. Among various sulfur-derived functional groups, cyclic dithiocarbonate [15][16][17][18] have attracted much attention because they exhibit low dielectric constants, high refractive indices, high metal coordination abilities, and specific reactivities toward amines.…”

“…Our research group has already studied the synthesis of polymers having the five-membered cyclic dithiocarbonate structures, and revealed their unique properties. 10,11,13 However, styrenic polymers having five-membered dithiocarbonate groups have not been synthesized so far.…”