Dataset Information

Degradable Alternating Copolymers by Radical Copolymerization of 2-Methylen-1,3-dioxepane and Crotonate Esters.

ABSTRACT: Producing backbone degradable copolymers via free-radical copolymerization is a promising, yet challenging method to develop more sustainable materials for many applications. In this work, we present the copolymerization of 2-methylen-1,3-dioxepane (MDO) with crotonic acid derivative esters. MDO can copolymerize by radical ring-opening polymerization incorporating degradable ester moieties in the polymer backbone, although this can often be difficult due to the very unfavorable reactivity ratios. Crotonic acid derivatives, on the other hand, can be easily produced completely from biomass but are typically very difficult to (co)polymerize due to low propagation rates and very unfavorable reactivity ratios. Herein, we present the surprisingly easy copolymerization between MDO and butyl crotonate (BCr), which shows the ability to form alternating copolymers. The alternating nature of the copolymer was characterized by MALDI-TOF and supported by the reactivity ratios calculated experimentally (r_MDO = 0.105 and r_BCr = 0.017). The alternating nature of the copolymers favored the degradability that could be achieved under basic conditions (in 2 h, all chains have molar masses smaller than 2 kg/mol). Last, the work was expanded to other crotonate monomers to expand the portfolio and show the potential of this copolymer family.

SUBMITTER: Barquero A

PROVIDER: S-EPMC10956490 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature

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Degradable Alternating Copolymers by Radical Copolymerization of 2-Methylen-1,3-dioxepane and Crotonate Esters.

Barquero Aitor A Zanoni Arianna A Gabirondo Elena E González de San Román Estibaliz E Hamzehlou Shaghayegh S Ximenis Marta M Moscatelli Davide D Sardon Haritz H Leiza Jose Ramon JR

ACS macro letters 20240308 3

Producing backbone degradable copolymers via free-radical copolymerization is a promising, yet challenging method to develop more sustainable materials for many applications. In this work, we present the copolymerization of 2-methylen-1,3-dioxepane (MDO) with crotonic acid derivative esters. MDO can copolymerize by radical ring-opening polymerization incorporating degradable ester moieties in the polymer backbone, although this can often be difficult due to the very unfavorable reactivity ratios ...[more]

PMID: 38457274

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Project description:The radical (co)polymerization of long-chain α-olefins (C4+) to produce high molecular weight (Mw) polymers is of great importance. However, this process is currently faced with significant challenges due to the presence of less reactive allylic radicals during radical (co)polymerization, leading to oligomers or polymers with extremely low Mw (less than 1 × 104 g mol-1). Using copolymerization of 1-octene with methyl acrylate (MA) as a proof-of-concept for addressing this challenge, we present a feasible method for synthesizing high Mw α-olefin copolymers via scandium trifluoromethanesulfonate (Sc(OTf)3)-mediated radical copolymerization. In this case, copolymers of 1-octene and MA (poly(1-octene-alt-MA)) with a Mw exceeding 3 × 104 g mol-1 were successfully synthesized in the presence of Sc(OTf)3. Meanwhile, the presence of alternating 1-octene-MA sequential structures was observed. To further enhance the Mw of poly(1-octene-alt-MA), a difunctional comonomer, 1,7-octadiene, was introduced to copolymerize with 1-octene and MA. The results indicate that the incorporation of difunctional comonomer leads to a significant increase in the Mw of the copolymers synthesized. The addition of 1 mol% of 1,7-octadiene resulted in a copolymer with a remarkably high Mw of up to 13.45 × 104 g mol-1 while still maintaining a high degree of the alternating 1-octene-MA sequence (41%). The influence of polymerization parameters on the molecular weight were also investigated. Increasing the monomer concentration, reducing the dosage of initiator, and lowering the polymerization temperature have been found to be advantageous in enhancing the molecular weight. This approach has also been successfully applied to the synthesis of high molecular weight alternating copolymers of other long-chain α-olefins, including 1-hexene, 1-decene and 1-tetradecane, with methyl acrylate. In summary, this study provides a feasible method for converting "less activated" α-olefins into high Mw olefin copolymers. This approach holds significant potential for the production of value-added polyolefins, thus offering promising prospects for future applications.

Dataset Information

Degradable Alternating Copolymers by Radical Copolymerization of 2-Methylen-1,3-dioxepane and Crotonate Esters.

Publications

Degradable Alternating Copolymers by Radical Copolymerization of 2-Methylen-1,3-dioxepane and Crotonate Esters.

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