The free radical polymerization controlled by 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) was carried out in a water/oil suspension at 120–135°C. Suspension polymerization is a polymerization reaction with high conversion and allows high‐molecular‐weight polymers to be synthesized. The polymerization was started by a styrene macroinitiator. The block length is determined by the level of conversion and the initial macroinitiator concentration. A kinetic model is introduced which predicts a drastic reduction of polymerization time (at ca. 90% conversion a reduction from ca. 20 h to 5–3 h) and improved polydispersity through selective addition of initiator. The agreements between the simulated results and the experimental findings are surprisingly good. From model calculation, the percentage and molar mass distributions of the dead polymers can also be derived.

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Radical polymerization of styrene and mixtures of styrene and 4‐vinylpyridine was performed in the presence of 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) producing polymers with controlled molecular weights and molecular weight distributions. The living nature of these polymers was confirmed by using them as macroinitiators in the block copolymerization of styrene and butyl acrylate. The thermal properties of the synthesized statistical diblock copolymers measured by differential scanning calorimetry indicated that a phase‐separated morphology was exhibited in most of the block copolymers. The results were confirmed by transmission electron microscopy (TEM) and small angle X‐ray scattering (SAXS) showing microphase‐separated morphology as is known for homo A‐B diblock polymers. SAXS of a block copolymer synthesized from S/V 70:30 macroinitiators (03) with one detected Tg.magnified imageSAXS of a block copolymer synthesized from S/V 70:30 macroinitiators (03) with one detected Tg.

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