Chemoselective Polymerization Research Articles

Selectivity in anionic and cationic ring‐opening polymerizations of tetramethyl‐1‐(3′‐trifluoromethylphenyl)‐1‐phenylcyclotrisiloxane and tetramethyl‐1‐[3′,5′‐bis(trifluoromethyl)phenyl]‐1‐phenylcyclotrisiloxane

AbstractAnionic and cationic ring‐opening polymerizations of two novel cyclotrisiloxanes, tetramethyl‐1‐(3′‐trifluoromethylphenyl)‐1‐phenylcyclotrisiloxane (I) and tetramethyl‐1‐[3′,5′‐bis(trifluoromethyl)phenyl]‐1‐phenylcyclotrisiloxane (II), are reported. Anionic ring‐opening polymerization of I or II leads to copolymers with highly regular microstructures. Copolymers obtained by cationic polymerizations of I or II, initiated by triflic acid, have less regular microstructures characteristic of chemoselective polymerization processes. The composition and microstructure of copolymers have been characterized by 1H and 29Si‐NMR, the molecular weight distributions by GPC, and the thermal properties by DSC and TGA. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5235–5243, 2004

Synthesis of new crosslinkable polymers by chemoselective polymerizations of 2-(1-aziridinyl)ethyl methacrylate

Synthesis of new crosslinkable polymers by chemoselective polymerizations of 2-(1-aziridinyl)ethyl methacrylate

Regio- and chemo-selective polymerization of phenols catalyzed by oxidoreductase enzyme and its model complexes

Oxidative polymerizations of phenol derivatives have been performed using an oxidoreductase enzyme and its model complexes as catalyst to produce new functional polymers. Soluble polyphenols were synthesized using peroxidase catalyst in an aqueous methanol. Enzymatic polymerization of syringic acid involved elimination of carbon dioxide and hydrogen from the monomer to give poly(1,4-oxyphenylene) (PPO). Tyrosinase-model complexes catalyzed highly regioselective oxidative polymerization of a 2,6-unsubstituted phenol, 4-phenoxyphenol, to produce unsubstituted PPO showing crystallinity with a melting point. Chemoselective polymerization of phenols having an unsaturated group took place through peroxidase catalysis, yielding crosslinkable polyphenols.

Chemoselective Ring-Opening Polymerization of a Lactone Having exo-Methylene Group with Lipase Catalysis

Chemoselective Ring-Opening Polymerization of a Lactone Having <i>e</i><i>xo</i>-Methylene Group with Lipase Catalysis

Chemoselective Oxidative Polymerization of m-Ethynylphenol by Peroxidase Catalyst to a New Reactive Polyphenol

Enzymatic oxidative polymerization of m-ethynylphenol possessing two reactive groups, phenol and acetylene moieties, was carried out in aqueous methanol under air. Horseradish peroxidase and hydrogen peroxide were used as catalyst and oxidizing agent, respectively. (1)H NMR and IR analysis showed that only the phenolic moiety was polymerized to produce the polymer having the ethynyl group in the side chain. The reaction of the monomer using a copper/amine catalyst, a conventional catalyst for oxidative coupling, exclusively produced a diacetylene derivative. From these data, it was found that the peroxidase catalysis induced the chemoselective polymerization of the monomer. The resulting polymer was converted to carbonized polymer in a much higher yield than enzymatically synthesized poly(m-cresol) and is expected to have potential applications as a reactive starting polymer.

Chemoselective Polymerization of a Phenol Derivative Having a Methacryl Group by Peroxidase Catalyst

It is found that the phenolic moiety is selectively reacted in the horseradish-catalyzed polymerization of 2-(4-hydroxyphenyl)ethyl methacrylate. The polymer was thermally cross-linked at a relatively low temperature. The resulting polymer posssessed a methacryloyl group in the side chain and hence, is expected to have various applications as a highly reactive polymer