Mechanistic investigation of cyclic ketene acetal radical ring-opening homo- and co-polymerization and preparation of PEO graft copolymers with tunable composition

Du, Yifeng; Du, Yuhui; Lazzari, Stefano; Reimers, Tom; Konradi, Rupert; Holcombe, Thomas W.; Coughlin, E. Bryan

doi:10.1039/d2py00986b

Cited by 10 publications

(6 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Also, semi-batch copolymerization of MTC and NVP was reported to achieve linear copolymers with uniform insertion of ester groups along the chain. 41 Herein, to tackle the very slow hydrolytic degradations of MDO-, BMDO-, and MPDL-containing copolymers, we sought to substitute these CKAs by MTC to take advantage of its hydrophilic properties due to its oligo(ethylene glycol)like structure once opened. We applied this methodology to P(CKA-co-MI) and P(CKA-co-VE) copolymers, which represent two of the most promising rROP copolymerization systems ever developed in terms of CKA content and functionalization possibilities.…”

Section: Introductionmentioning

confidence: 99%

“…More recently, P(MTC- co -MDO) copolymers were prepared while MTC was successfully copolymerized with gaseous ethylene by cobalt-mediated radical copolymerization and reversible addition-fragmentation chain transfer (RAFT) to yield degradable copolymers. Also, semi-batch copolymerization of MTC and NVP was reported to achieve linear copolymers with uniform insertion of ester groups along the chain …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Increasing the Hydrophilicity of Cyclic Ketene Acetals Improves the Hydrolytic Degradation of Vinyl Copolymers and the Interaction of Glycopolymer Nanoparticles with Lectins

et al. 2023

View full text Add to dashboard Cite

Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) with traditional vinyl monomers allows the synthesis of degradable vinyl copolymers. However, since the most commonly used CKAs are hydrophobic, most degradable vinyl copolymers reported so far degrade very slowly by hydrolysis under physiological conditions (phosphate-buffered saline, pH 7.4, 37 °C), which can be detrimental for biomedical applications. Herein, to design advanced vinyl copolymers by rROP with high CKA content and enhanced degradation profiles, we reported the copolymerization of 2-methylene-1,3,6-trioxocane (MTC) as a CKA with vinyl ether (VE) or maleimide (MI) derivatives. By performing a point-by-point comparison between the MTC/VE and MTC/MI copolymerization systems, and their counterparts based on 2-methylene-1,3-dioxepane (MDO) and 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), we showed negligible impact on the macromolecular characteristics and similar reactivity ratios, suggesting successful substitution of MDO and BMDO by MTC. Interestingly, owing to the hydrophilicity of MTC, the obtained copolymers exhibited a faster hydrolytic degradation under both accelerated and physiological conditions. We then prepared MTC-based glycopolymers, which were formulated into surfactant-free nanoparticles, exhibiting excellent colloidal stability up to 4 months and complete degradation under enzymatic conditions. Importantly, MTC-based glyconanoparticles also showed a similar cytocompatibility toward two healthy cell lines and a much stronger lectin affinity than MDO-based glyconanoparticles.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Increasing the Hydrophilicity of Cyclic Ketene Acetals Improves the Hydrolytic Degradation of Vinyl Copolymers and the Interaction of Glycopolymer Nanoparticles with Lectins

et al. 2023

View full text Add to dashboard Cite

show abstract

“…Since the 1980s, this concept has gained significant attention as a method to incorporate degradable building blocks into the backbone of otherwise intractable vinyl-based polymers. , A variety of cyclic compounds such as macrocyclic allyl sulfides (MAS) − have emerged as candidates to impart degradability into various polymers. Another classic example is the copolymerization of acrylates with cyclic ketene acetals (CKA) as a method of introducing cleavable ester bonds. − Despite their utility, CKAs have modest copolymerization reactivity leading to low yields and nonrandom incorporation. Recently, Gutekunst and Roth , pioneered a thionolactone monomer, dibenzo[ c , e ]-oxepane-5-thione (DOT), that efficiently copolymerizes with acrylate derivatives and inserts degradable thioesters into the polymer backbone.…”

Section: Introductionmentioning

confidence: 99%

Controlled-Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers

Albanese,

Morris,

Read de Alaniz

et al. 2023

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Here, we present the synthesis and characterization of statistical and block copolymers containing α-lipoic acid (LA) using reversible addition–fragmentation chain-transfer (RAFT) polymerization. LA, a readily available nutritional supplement, undergoes efficient radical ring-opening copolymerization with vinyl monomers in a controlled manner with predictable molecular weights and low molar-mass dispersities. Because lipoic acid diads present in the resulting copolymers include disulfide bonds, these materials efficiently and rapidly degrade when exposed to mild reducing agents such as tris(2-carboxyethyl)phosphine (M n = 56 → 3.6 kg mol–1). This scalable and versatile polymerization method affords a facile way to synthesize degradable polymers with controlled architectures, molecular weights, and molar-mass dispersities from α-lipoic acid, a commercially available and renewable monomer.

show abstract

“…A viable alternative to conventional poly(acrylates) lies in the design of comonomers containing degradable functional groups . Several studies have demonstrated the copolymerization of cyclic ketene acetals (CKAs) with acrylates as a method of introducing cleavable ester bonds along each polymer chain. − Despite their utility, CKAs have a number of drawbacks, including (i) competing side reactions of the CKA that lead to noncleavable C–C bonds, (ii) poor reactivity with acrylates, and (iii) difficulty achieving high molecular weights (i.e., >100 kg mol –1 ) that are crucial for adhesive applications. ,, Other cyclic monomers that may overcome these challenges, such as thionolactones pioneered by Gutekunst and Roth or cyclic allyl sulfides, involve an expensive, multistep synthesis. An ideal degradable comonomer would be available at scale, readily copolymerize with acrylates, and contain a functional handle for optimizing adhesive performance.…”

mentioning

confidence: 99%

Building Tunable Degradation into High-Performance Poly(acrylate) Pressure-Sensitive Adhesives

et al. 2023

View full text Add to dashboard Cite

Pressure-sensitive adhesives (PSAs) based on poly-(acrylate) chemistry are common in a wide variety of applications, but the absence of backbone degradability causes issues with recycling and sustainability. Here, we report a strategy to create degradable poly(acrylate) PSAs using simple, scalable, and functional 1,2-dithiolanes as drop-in replacements for traditional acrylate comonomers. Our key building block is α-lipoic acid, a natural, biocompatible, and commercially available antioxidant found in various consumer supplements. α-Lipoic acid and its derivative ethyl lipoate efficiently copolymerize with n-butyl acrylate under conventional free-radical conditions leading to high-molecular-weight copolymers (M n > 100 kg mol −1 ) containing a tunable concentration of degradable disulfide bonds along the backbone. The thermal and viscoelastic properties of these materials are practically indistinguishable from nondegradable poly(acrylate) analogues, but a significant reduction in molecular weight is realized upon exposure to reducing agents such as tris (2-carboxyethyl) phosphine (e.g., M n = 198 kg mol −1 → 2.6 kg mol −1 ). By virtue of the thiol chain ends produced after disulfide cleavage, degraded oligomers can be further cycled between high and low molecular weights through oxidative repolymerization and reductive degradation. Transforming otherwise persistent poly(acrylates) into recyclable materials using simple and versatile chemistry could play a pivotal role in improving the sustainability of contemporary adhesives.

show abstract

Mechanistic investigation of cyclic ketene acetal radical ring-opening homo- and co-polymerization and preparation of PEO graft copolymers with tunable composition

Abstract: Radical ring-opening polymerization of cyclic ketene acetals (CKAs) led to homogeneous ester insertion during semi-batch reactions with N-vinyl pyrrolidone (NVP). Investigation of CKA radical transfer allowed for CKA–NVP graft copolymer preparation.

Cited by 10 publications

References 49 publications

Increasing the Hydrophilicity of Cyclic Ketene Acetals Improves the Hydrolytic Degradation of Vinyl Copolymers and the Interaction of Glycopolymer Nanoparticles with Lectins

Increasing the Hydrophilicity of Cyclic Ketene Acetals Improves the Hydrolytic Degradation of Vinyl Copolymers and the Interaction of Glycopolymer Nanoparticles with Lectins

Controlled-Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers

Building Tunable Degradation into High-Performance Poly(acrylate) Pressure-Sensitive Adhesives

Contact Info

Product

Resources

About