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

Abstract

3-Ethylidene-6-vinyltetrahydro-2H-pyran-2-one, a divinyl δ-lactone derived from CO 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. The networks have sharp and uniform glass transitions and show good thermal stability with T from 287 to 332 °C. Mechanical properties of the networks can be adjusted by the cross-link density; 6.18 MPa of tensile strength, 574% break elongation and 1.84 of tan δ at maximum are reached. Metal complexation makes the networks tougher due to additional cross-links. The highly homogeneous networks are transparent with average 90% transmittance of visible light, and of decent refractive indices around 1.55. Swelling-induced twist shape transformation and visible QR code under UV light is realized by pattern of the network.

Combination of Ethylene, 1,3-Butadiene, and Carbon Dioxide into Ester-Functionalized Polyethylenes via Palladium-Catalyzed Coupling and Insertion Polymerization

“…Recently, we were also interested in the catalytic coupling reaction of CO 2 and BD and the chemistry of EVL monomer containing a six-membered ring and two types of vinyl groups. We for the first time developed a highly reactive trivinyl methacrylate-type monomer III (see Scheme ) derived from EVL and then described its chemoselective RAFT polymerizations to obtain well-defined polymers with linear and hyperbranched topologies. , At the same time, our interests also focused on the field of late-transition-metal (especially Ni and Pd) catalyzed copolymerization of olefin and polar monomers to prepare high-valued functionalized polyolefins. − Because the copolymerization reaction for two of E, BD, and CO 2 remains highly challenging as above-mentioned, the copolymerization for three of E, BD, and CO 2 together is more elusive. In this contribution, intrigued by these previous advances, we first used the strategy of synthesizing EVL by the Pd-catalyzed C–C coupling reaction of CO 2 and BD, which further facilely reacted with methanol and subsequently with acryloyl chloride to yield the desired monomer II with three different reactive vinyl groups (acrylate, allyl ester, and 1,2-disubstituted acrylate).…”

Degradable Polymer Structures from Carbon Dioxide and Butadiene

“…Inoue and Musco discovered coupling CO 2 and BD with a phosphine-ligated palladium catalyst produces the unsaturated disubstituted delta-valerolactone 2-ethyliden-6-hepten-5-olide ( 1 : EVL, Scheme a). − Behr further demonstrated the synthesis of 1 in a continuous reactor. − The homopolymerization of 1 was first described by Nozaki and co-workers to yield a poly­(acrylate) structure ( 2 , Scheme b) with high glass transition temperatures ( T g s) up to 192 °C. − Postpolymerization modification of the polylactone 2 results in reversible hydrolysis and aminolysis . In addition to radical homopolymerization, the copolymerizations of EVL ( 1 ) with dithiols, ethylene, or methacroyl moieties produce polysulfide, polyolefin, and polyacrylate repeating units, respectively.…”

“…29−31 Postpolymerization modification of the polylactone 2 results in reversible hydrolysis and aminolysis. 30 In addition to radical homopolymerization, the copolymerizations of EVL (1) with dithiols, 32 ethylene, 33 or methacroyl moieties 34 produce polysulfide, polyolefin, and polyacrylate repeating units, respectively.…”

Ring-Opening Polymerization of CO2-Based Disubstituted δ-Valerolactone toward Sustainable Functional Polyesters

“…2,3 Stepgrowth polymerization of EVL with di-and trithiol through thiol−ene click reaction, resulting in linear polymers or polymer networks, is another strategy to utilize EVL. 4,5 The cyclic ester bond keeps intact in the above polymerizations. The EVL ring is indeed possible to open by an alcoholysis reaction, and the product can further react with acrylic or methacrylic chloride.…”

“…Free-radical polymerizations of EVL were reported by Nozaki using 1,1′-azobis­(cyclohexane-1-carbonitrile) as the initiator and ZnCl 2 as the additive. A reversible polymer modification involving structural changes of the polymer chains was then developed based on the bicyclic structures of the obtained copolymer of butadiene and CO 2 . , Step-growth polymerization of EVL with di- and trithiol through thiol–ene click reaction, resulting in linear polymers or polymer networks, is another strategy to utilize EVL. , The cyclic ester bond keeps intact in the above polymerizations. The EVL ring is indeed possible to open by an alcoholysis reaction, and the product can further react with acrylic or methacrylic chloride.…”