New crystalline polymers: poly(2,5‐dialkyl‐1,4‐phenylene oxide)s

New heat‐reversibly crystalline poly‐(alkylated phenylene oxide)s are described. the oxidative polymerization of 2,5‐dimethylphenol catalyzed by (1,4,7‐triisopropyl‐1,4,7‐triazacyclononane) copper dichloride produced poly(2,5‐dimethyl‐1,4‐phenylene oxide), which showed heat‐reversible crystallinity with a high melting point at ca. 300°C, although the isomeric polymer, poly(2,6‐dimethyl‐1,4‐phenylene oxide), never recrystallizes once melted. The polymerization of 2,5‐diethylphenol and 2,5‐dipropylphenol gave the polymers consisting of 1,4‐phenylene oxide units; the latter polymer possessed heat‐reversible crystallinity, however, the former one did not.     

A new crosslinkable polyphenol from a renewable resource

Cardanol, a major component obtained by thermal treatment of cashew nut shell liquid, is a phenol derivative mainly having a C15 unsaturated hydrocarbon chain with 1–3 double bonds at the m‐position. We polymerized cardanol using an Fe‐salen complex as the catalyst to give a soluble polyphenol containing the unsaturated alkyl group in the side chain. The polymer was subjected to hardening by a cobalt naphthenate catalyst or thermal treatment, yielding crosslinked film with high gloss surface.     

Preparation of monodisperse polymer particles from 4-vinylpyridine

Dispersion polymerization of 4-vinylpyridine was performed by using polystyrene-block-polybutadiene as stabilizer in a mixture of N,N-dimethylformamide (DMF) and toluene to produce polymer particles. The weight ratio of the solvents affects the particle size and dispersity. In the range of DMF content from 5 to 20 wt.-%, uniform particles of a diameter of ca. 1 μm were obtained. The present system was expanded to the preparation of monodisperse particles of poly[(4-vinylpyridine)-co-(methacrylic acid)].     

Enzymatic synthesis of a soluble polyphenol derivative from 4,4′-biphenyldiol

Enzymatic oxidative polymerization of 4,4′-biphenyldiol was performed in an aqueous organic solvent using horseradish peroxidase as catalyst. In the polymerization using a mixture of 1,4-dioxane and phosphate buffer (pH 7.0) (80:20 vol-%) as solvent, the monomer was quantitatively consumed to give powdery polymeric materials in a high yield. The resulting polymer is soluble in polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, and acetone. The molecular weight of the methylated product is 7.3 × 10³. The polymer exhibits high thermal stability under nitrogen.     

First Diazosulfonate Homopolymer by Enzymatic Polymerization

The polymerization behavior of phenolic azosulfonates and triazene by means of enzymatic polymerization using horseradish peroxidase was studied. While for the latter one, only oligomerization was observed, sodium 4‐hydroxybenzenediazosulfonate was successfully homopolymerized. The obtained polymer had an average molecular weight of M _n = 3 000 with a polydispersity index of 1.51. This is the first example of a homopolymer bearing an azosulfonate function in every monomer unit.