Random Terpolymer of Carbon Dioxide, Butadiene and Epoxides: Synthesis, Functionalization and Degradability

Abstract

Comprehensive SummaryThe utilization of carbon dioxide (CO2) as a C1 feedstock is consistently attractive, especially in the preparation of sustainable polymeric materials. In this contribution, a terpolymer of CO2, 1,3‐butadiene (BD) and epoxide is synthesized by scandium triflate catalyzed cationic ring‐opening copolymerization of α‐ethylidene‐δ‐vinyl‐δ‐valerolactone (EVL), an intermediate derived from CO2 and BD, with epoxides. The obtained terpolymer with a CO2 content of 22 mol% has a number‐average molecular weight (Mn) up to 7.8 kg/mol and a dispersity (Đ) of 2.4. The reactivity ratios of EVL and cyclohexene oxide (CHO) are determined as 0.01 and 1.07, respectively, suggesting random characteristic of the terpolymer. The preserved C=C double bonds from BD allow for the further modification of the terpolymer by photoinitiated crosslinking. The yielded networks are fluorescent and degradable. This method offers enhanced versatility to the synthesis and additional functionalization of CO2‐based polymers.

Ring-Opening Copolymerizations of a CO2-derived δ-Valerolactone with ε-Caprolactone and L-Lactide

“…However, there have been a few recent copolymer syntheses with EVP (Figure 1), which were developed because EVP is reticent to homopolymerize. [29][30][31][32] The Ni group has reported the use of b-butyrolactone (Figure 1, reaction A), 29 ε-CL (Figure 1, reaction B), 30 and cyclohexene oxide (Figure 1, reaction C) 31 as comonomers for the ROP of EVP to synthesize random copolymers; similarly, the Tang group has used propylene oxide (Figure 1, reaction D). 32 In all cases, low molar mass polymers with high dispersities were obtained, especially at high feed ratios of EVP.…”

Ring-Opening Copolymerizations of a CO2-Derived δ-Valerolactone with ε-Caprolactone and l-Lactide

“…No EtVP-based copolymers have been reported to date. However, there have been a few recent copolymer syntheses with EVP. − For example, the Nozaki group reported radical alkene copolymerization of EVP with various commodity monomers. , ROCOP of EVP has also been explored since EVP is reticent to homopolymerize (Figure , left). − The Ni group has reported the use of β-butyrolactone (Figure , reaction A), ε-CL (Figure , reaction B), and cyclohexene oxide (Figure , reaction C) as comonomers for the ROP of EVP to synthesize random copolymers; similarly, the Tang group has used propylene oxide (Figure , reaction D) . In all cases, low-molar-mass polymers with high dispersities were obtained, especially at high feed ratios of EVP.…”

Polyester Platform with High Refractive Indices and Closed-Loop Recyclability from CO2, 1,3-Butadiene, and Thiols

“…At the same time, our group developed a new terpolymer of CO 2 , butadiene, and epoxides via the direct cationic ROCOP of EVL, with epoxides catalyzed by scandium triflate. 23 However, the above-mentioned strategies to activate the EVL remove the functional unsaturated bonds irreversibly, except the cationic ROCOP.…”

“…α-Ethylidene-δ-vinyl-δ-valerolactone (EVL, a.k.a. 3-ethylidene-6-vinyltetrahydro-2 H -pyran-2-one, EVP, Figures S1 and S2), an unsaturated disubstituted δ-valerolactone derived from CO 2 and 1,3-butadiene, has emerged as a charming intermediate to bypass the thermodynamic stability of CO 2 . − Ring-opening polymerization (ROP) of EVL or its derivatives is a desirable method to construct chemically recyclable polyesters with multifunctional groups, high CO 2 content, and inexpensive feedstocks. ,− Landmark progress has been achieved since the first reported cationic ROP of EVL with β-butyrolactone (Scheme A) . Eagan and co-workers exploited a pioneering yet uncontrollable polymerization of EVL catalyzed by an organic base, revealing that the 1,4-conjugate addition of EVL is crucial to opening the ring .…”

“…Lin’s group synthesized the same hydrogenated EVL derivatives contemporaneously and employed phosphazene bases and alkali-metal alkoxides as the catalysts to produce polymers with M n values up to 613.8 kg·mol –1 . , Our group reported a one-pot–one-step “scrambling polymerization” of EVL, with ε-caprolactone producing polyesters with various topologies, where the ROP of EVL was accessible exclusively after the in situ trimerization of conjugated double bonds. , Recently, Tang et al reported the anionic ring-opening copolymerization (ROCOP) of EVL with epoxides via an in situ generated EVL dimer intermediate using a chronicum salen complex catalyst, yielding polyester- co -polyethers containing EVL dimer repeating units. At the same time, our group developed a new terpolymer of CO 2 , butadiene, and epoxides via the direct cationic ROCOP of EVL, with epoxides catalyzed by scandium triflate . However, the above-mentioned strategies to activate the EVL remove the functional unsaturated bonds irreversibly, except the cationic ROCOP.…”