Water‐soluble starch derivatives containing quarternary ammonium groups of high degree of substitution are prepared by reacting starch with 2,3‐epoxypropyltrimethylammonium chloride in different reaction media. The reaction was carried out in aqueous sodium hydroxide under dissolution of the product, in dimethyl sulfoxide homogeneously, and completely heterogeneously in ethanol/water. The DS values of up to 1.1 in an one‐step synthesis of the samples can be controlled by adjusting the molar ratio of cationization agent to anhydroglucose unit and are only slightly dependent on the amylose content of the starting starch material. A two‐step reaction yields products of a DS of up to 1.5. The structure of the cationic starch derivatives was confirmed by means of elemental analysis, FTIR‐ and NMR spectroscopy as well as GC‐MS.

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By means of photoinitiated SH-En-polyaddition of 2-ethylidene-6-hepten-5-olide (d-lactone) and 2,29-(ethylenedioxy)diethanethiol or 1,3-bis(3-mercaptopropyl)-1,1,3,3-tetramethyldisiloxane, it was possible for the first time to form a high-molecular linear polymer with an intact lactone structure. Under these conditions, the reactivity does not depend on the carbon-carbon double bond structure. With pentaerythritoltetrakis(3-mercaptopropionate) as a crosslinking agent, networks are formed; the structure of the comonomers and the proportionate composition of the monomers modify the polymer properties. These novel polymers have been fully characterized.ZUSAMMENFASSUNG: Durch photoinduzierte SH-En-Polyaddition mit 2,29-(Ethylendioxy)diethanthiol bzw. 1,3-Bis(3-mercaptopropyl)-1,1,3,3-tetramethyldisiloxane war es erstmalig möglich, das 2-Ethyliden-6hepten-5-olid (d-Lacton) unter Erhalt der Lactonstruktur in hochmolekulare lineare Polymere zu überführen. Strukturell bedingte Reaktivitätsunterschiede der beiden Doppelbindungen konnten unter diesen Bedingungen nicht beobachtet werden. Mit Pentaerythrit-tetrakis(3-mercaptopropionat) als Vernetzer werden Netzwerkstrukturen aufgebaut, deren Eigenschaften durch die Struktur der Comonomeren und deren anteilsmäßige Zusammensetzung modifiziert werden können. Diese neuen Polymeren wurden umfassend charakterisiert.

By means of photoinitiated SH‐En‐polyaddition of 2‐ethylidene‐6‐hepten‐5‐olide (δ‐lactone) and 2,2'‐(ethylenedioxy)diethanethiol or 1,3‐bis(3‐mercaptopropyl)‐1,1,3,3‐tetramethyldisiloxane, it was possible for the first time to form a high‐molecular linear polymer with an intact lactone structure. Under these conditions, the reactivity does not depend on the carbon‐carbon double bond structure. With pentaerythritol‐tetrakis(3‐mercaptopropionate) as a crosslinking agent, networks are formed; the structure of the comonomers and the proportionate composition of the monomers modify the polymer properties. These novel polymers have been fully characterized.

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