Synthesis of polymers with an intact lactone ring structure in the main chain

Abstract

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.

Use of carbon dioxide as feedstock for chemicals and fuels: homogeneous and heterogeneous catalysis

“…308 Despite many efforts it has not been possible to achieve synthesis of optically pure isomers of the lactone. 309 Attempts have been made to find industrial use of the lactone as comonomer 310 or by converting it into an acyclic monomer with specific properties as plasticizer. 2-ethylheptanoic acid has been prepared in high yield by hydrogenation and ring opening 311 or by hydroformylation and amination.…”

Preparation and application of air-stable P,N-bidentate ligands for the selective synthesis of δ-lactone via the palladium-catalyzed telomerization of 1,3-butadiene with carbon dioxide

“…As shown in Table 2, Pd catalyst precursors significantly influenced the selective formation of 2. Using Pd(acac) 2 , which was also employed in section 2.3.1, yielded 43% of product 2 with 66% selectivity (entry 1). Pd(OAc) 2 showed inferior efficiency and yielded 30% of product 2 with 50% selectivity (entry 2).…”

Synthesis and Properties of Networks Based on Thiol‐ene Chemistry Using a CO2‐Based δ‐Lactone

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found with direct or indirect approaches, because it exhibits rather poor polymerizability toward conventional methods. [17][18][19] The first successful polymerization of EVL was carried out through optimized radical polymerization with additives by Nozaki and coworkers. [17] The resultant polymers had high molecular weights up to 8.5 × 10 4 g mol −1 and high T g resulting from rigid backbone structure, which made them promising engineer plastics.

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“…[18] Dinjus reported the coupling reaction of EVL with dithiols to yield polymers, but only very preliminary results were obtained. [19] Still, there are very limited reports concerning the synthesis of polymers from EVL.Thiol-ene click chemistry has developed into a mature and diverse field of study in the past two decades. The reaction has advantages like fast kinetics, high conversion, good selectivity, and lack of byproduct.…”

“…[32] According to previous research, these two vinyl groups have minor difference in reactivity toward thiol-ene click reaction without detailed discussion. [19] Hereby, we carried out a photoinitiated thiol-ene click reaction to Thiol-ene Networks -6-vinyltetrahydro-2H-pyran-2-one, a divinyl δ-lactone derived from CO 2 and 1,3-butadiene, is used for the synthesis of networks with various compositions through the thiol-ene click reaction with di-and tri-thiol compounds. Thermal, mechanical, and optical properties of the networks are characterized.…”