Unzipping and scrambling <scp>reaction‐induced</scp> sequence control of copolymer chains via temperature changes during cationic <scp>ring‐opening</scp> copolymerization of cyclic acetals and cyclic esters

Higuchi, Motoki; Kanazawa, Arihiro; Aoshima, Sadahito

doi:10.1002/pol.20210197

Cited by 7 publications

(7 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since poly 1 is completely amorphous (Figure E), the crystalline regions in poly( 1 - co - 3 ) are likely derived from CL homosequences, further supporting a gradient microstructure. DSC analysis of poly( 1 - co - 3 ) with up to 25% incorporation of 1 also revealed an interesting double melting peak that has been observed previously in other cyclic acetal–cyclic ester copolymers. , A potential explanation for this double melting phenomenon is the presence of lamellae with two different thicknesses. − The glass transition temperature ( T g ) of poly( 1 - co - 3 ) copolymers is between those of poly 1 and poly 3 homopolymers (Figure A,E), with the T g ranging from −44.3 to 21.5 °C when the copolymer composition changes from 16% to 64% incorporation of 1 . Similarly, the DSC thermograms for poly( 1 - co - 2 ) are shown in Figure B and the data are summarized in Figure E.…”

supporting

confidence: 61%

“…ε-Caprolactone (Scheme A, 3 ) is a promising cyclic ester monomer for cROCOP with levoglucosan that can be synthesized from 5-hydroxymethyl furfural, a lignocellulosic biomass-based platform chemical . The homopolymer of 3 , polycaprolactone, is a commercially produced polyester with widespread applications in the fields of drug delivery, tissue engineering, medical devices, sutures, etc. , The cROCOP of levoglucosan with ε-caprolactone will enable facile access to acetal-ester polysaccharides with potential as biomaterials for applications such as drug delivery, tissue engineering, gene therapy, etc. , Additionally, the incorporation of levoglucosan and ε-caprolactone in a gradient or blocky fashion will enable access to fully biobased copolymers with hard and soft segments that can be utilized as thermoplastic elastomers (TPEs). , Notably, the cROCOP of cyclic acetals with cyclic esters has been the subject of a handful of studies, where 1,3-dioxolane is commonly copolymerized with either ε-caprolactone or l -lactide. − Although these studies demonstrate the successful formation of an acetal-ester copolymer, monomer reactivity ratios are not determined for the assessment of the copolymer microstructure. Taken together, these factors have led us to explore the cROCOP of levoglucosan and ε-caprolactone with low toxicity polymerization catalysts to obtain novel sugar-based copolymers.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Biobased Copolymers via Cationic Ring-Opening Copolymerization of Levoglucosan Derivatives and ε-Caprolactone

2023

View full text Add to dashboard Cite

Simultaneous ring-opening copolymerization is a powerful strategy for the synthesis of highly functional copolymers from different types of cyclic monomers. Although copolymers are essential to the plastics industry, environmental concerns associated with current fossil-fuel-based synthetic polymers have led to an increasing interest in the use of renewable feedstock for polymer synthesis. Herein, we report a scalable synthetic platform to afford unique polysaccharides with different pendant functional groups from biomass-derived levoglucosan and ε-caprolactone via cationic ring-opening copolymerization (cROCOP). Biocompatible and recyclable bismuth triflate was identified as the optimal catalyst for cROCOP of levoglucosan. Copolymers from tribenzyl levoglucosan and ε-caprolactone, as well as from tribenzyl and triallyl levoglucosan, were successfully synthesized. The tribenzyl levoglucosan monomer composition ranged from 16% to 64% in the copolymers with ε-caprolactone and 22% to 79% in the copolymers with triallyl levoglucosan. The allylic levoglucosan copolymer can be utilized as a renewably derived scaffold to modify copolymer properties and create other polymer architectures via postpolymerization modification. Monomer reactivity ratios were determined to investigate the copolymer microstructure, indicating that levoglucosan-based copolymers have a gradient architecture. Additionally, we demonstrated that the copolymer glass transition temperature (T g, ranging from −44.3 to 33.8 °C), thermal stability, and crystallization behavior could be tuned based on the copolymer composition. Overall, this work underscores the utility of levoglucosan as a bioderived feedstock for the development of functional sugar-based copolymers with applications ranging from sustainable materials to biomaterials.

show abstract

supporting

confidence: 61%

mentioning

confidence: 99%

Biobased Copolymers via Cationic Ring-Opening Copolymerization of Levoglucosan Derivatives and ε-Caprolactone

2023

View full text Add to dashboard Cite

show abstract

“…A variety of poly(acetal ‐co‐ ester)s with different monomers, compositions, and sequences was then synthesized to demonstrate the generality of the above mechanism (entries 10–20 in Table 3). [ 79 ] The screened cyclic acetals and lactones are listed in Scheme . It is noteworthy that the co‐polymerizability of these cyclic acetals with CL contradicted their homo‐polymerizability which was revealed in the earlier reports.…”

Section: Synthesis Of Polyacetal‐based Copolymers and Their Potential...mentioning

confidence: 99%

“…Interestingly, the sequences were demonstrated to be reversibly transformable between alternating and random upon heating and cooling. [ 79 ]…”

Section: Synthesis Of Polyacetal‐based Copolymers and Their Potential...mentioning

confidence: 99%

Ring‐Opening Polymerization of Cyclic Acetals: Strategy for both Recyclable and Degradable Materials

Shen

Chen

et al. 2023

Macromol. Rapid Commun.

View full text Add to dashboard Cite

To cope with the severe plastic waste crisis, massive efforts are made to develop sustainable polymer materials whose degradation involves a disposing and decomposing to small molecule (DDM) and/or a chemical recycling to monomer (CRM) process. Polyacetals, a type of pH-responsive polymers, are degradable under acidic conditions, while highly stable under neutral and basic circumstances. As for their synthesis, the cationic ring-opening polymerization (CROP) of cyclic acetals is an elegant and promising approach, though suffering from fatal side reactions and polymerization-depolymerization equilibrium. Recent development in CRM restimulates the interest in the long-forgotten CROP method due to its inherent depolymerization characteristics. In terms of the end-of-life options, polyacetals are recyclable materials with both DDM and CRM potentials. They not only expand the scope of materials for closed-loop recycling but also help to tune the degradation properties of traditional polyesters and polyolefins. This review aims to discuss the synthesis of various polyacetals by CROP and their degradation properties from the perspectives of 1) polymerization of cyclic acetals, dioxepins, and hemiacetal esters, 2) copolymerization of cyclic acetals with heterocyclic or vinyl monomers, and 3) degradation and recycling properties of the related polymers.

show abstract

“…Our group recently examined the cationic copolymerization of cyclic acetals (such as 2-methyl-1,3-dioxepane) and cyclic esters (such as ε-caprolactone and δ-valerolactone) using EtSO 3 H as a protonic acid catalyst, and we determined that the reaction proceeds via mechanisms involving the AM mechanism and transacetalization (Scheme A). , In addition, monomer sequences of copolymers from multiblock sequences containing isolated cyclic ester units can be transformed into alternating sequences through controlling the transacetalization reactions and polymerization–depolymerization equilibrium, which is achieved by vacuuming or a temperature change. Basko and co-workers reported the cationic copolymerization of 1,3-dioxolane and lactide using CF 3 SO 3 H as a catalyst .…”

Section: Introductionmentioning

confidence: 99%

Cationic Ring-Opening Copolymerization of Cyclic Acetals and 1,3-Dioxolan-4-ones via the Activated Monomer Mechanism and Transacetalization Reaction

2023

Self Cite

View full text Add to dashboard Cite

Cationic ring-opening copolymerization of cyclic acetals and 1,3-dioxolan-4-ones (DOLOs) was examined with a particular focus on elucidating the polymerization mechanisms. Cationic copolymerization of 1,3-dioxepane and 5-methyl-1,3-dioxolan-4-one successfully proceeded with CF3SO3H as a protonic acid catalyst, yielding copolymers. The main portion of these copolymers exhibited number-average molecular weight values greater than 104 (except for oligomer peaks). Detailed structural analyses of the copolymers were performed by NMR spectrometry and electrospray ionization mass spectrometry. The result suggested that copolymerization occurs via an activated monomer mechanism involving the reaction of a hydroxy group and a proton-attached DOLO. In addition, acid-catalyzed transacetalization reactions with hemiformal chain ends and formal moieties most likely occurred during copolymerization, resulting in consecutive formal structures in the main chain.

show abstract

Unzipping and scrambling reaction‐induced sequence control of copolymer chains via temperature changes during cationic ring‐opening copolymerization of cyclic acetals and cyclic esters

Cited by 7 publications

References 35 publications

Biobased Copolymers via Cationic Ring-Opening Copolymerization of Levoglucosan Derivatives and ε-Caprolactone

Biobased Copolymers via Cationic Ring-Opening Copolymerization of Levoglucosan Derivatives and ε-Caprolactone

Ring‐Opening Polymerization of Cyclic Acetals: Strategy for both Recyclable and Degradable Materials

Cationic Ring-Opening Copolymerization of Cyclic Acetals and 1,3-Dioxolan-4-ones via the Activated Monomer Mechanism and Transacetalization Reaction

Contact Info

Product

Resources

About