ε-Thionocaprolactone: an accessible monomer for preparation of degradable poly(vinyl esters) by radical ring-opening polymerization

Ivanchenko, Oleksandr; Authesserre, Ugo; Coste, Guilhem; Mazières, Stéphane; Destarac, Mathias; Harrisson, Simon

doi:10.1039/d1py00080b

Cited by 36 publications

(77 citation statements)

References 41 publications

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“…[24][25][26] In the case of vinyl polymers, degradable bonds can be installed in the backbone by radical ring-opening polymerization (RROP) of cyclic monomers such as cyclic ketene acetals or allyl sulfide lactones. [27][28][29][30][31] Thionolactones, such as dibenzo[c,e]oxepane-5-thione (DOT) have been recently presented as a degradable comonomer which undergo RROP with acrylates, acrylamides, acrylonitrile, [32][33][34][35] as well as vinyl esters, 36 styrene and methacrylates. 37,38 DOT is compatible with both FRP and RDRP and affords degradation via cleavage of the backbone thioester.…”

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confidence: 99%

Fully degradable polymer networks from conventional radical polymerization of vinyl monomers enabled by thionolactone addition

Elliss

Dawson

Nisa

et al. 2022

Preprint

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We report the preparation of degradable polymer networks by conventional free radical copolymerization of n-butyl acrylate with a crosslinker and dibenzo[c,e]oxepane-5-thione (DOT) as a strand-cleaving comonomer. Addition of only 4 mol% of DOT imparts the synthesized networks with full degradability by aminolysis, whereas gels with less DOT (2 mol%) cannot be degraded, in excellent agreement with the recently proposed reverse gel-point model. Importantly, even though DOT significantly slows down the polymerization and delays gelation, it has a minimal effect on physical properties of the networks such as shear storage modulus, equilibrium swelling ratio, glass transition temperature or thermal stability.

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confidence: 99%

Fully degradable polymer networks from conventional radical polymerization of vinyl monomers enabled by thionolactone addition

Elliss

Dawson

Nisa

et al. 2022

Preprint

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“…Here, again, the weak unit formed is an ester. Thionolactones are cyclic monomers used in a specific polymerization process designed as TARO (Thiocarbonyl Addition Ring Opening) [ 201 , 202 , 203 ]. Thioester groups are formed in the main chain.…”

Section: Macromolecular Engineering To Favor Biodegradabilitymentioning

confidence: 99%

Spotlight on the Life Cycle of Acrylamide-Based Polymers Supporting Reductions in Environmental Footprint: Review and Recent Advances

Braun¹,

Coquery²,

Kieffer³

et al. 2021

Molecules

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Humankind is facing a climate and energy crisis which demands global and prompt actions to minimize the negative impacts on the environment and on the lives of millions of people. Among all the disciplines which have an important role to play, chemistry has a chance to rethink the way molecules are made and find innovations to decrease the overall anthropic footprint on the environment. In this paper, we will provide a review of the existing knowledge but also recent advances on the manufacturing and end uses of acrylamide-based polymers following the “green chemistry” concept and 100 years after the revolutionary publication of Staudinger on macromolecules. After a review of raw material sourcing options (fossil derivatives vs. biobased), we will discuss the improvements in monomer manufacturing followed by a second part dealing with polymer manufacturing processes and the paths followed to reduce energy consumption and CO2 emissions. In the following section, we will see how the polyacrylamides help reduce the environmental footprint of end users in various fields such as agriculture or wastewater treatment and discuss in more detail the fate of these molecules in the environment by looking at the existing literature, the regulations in place and the procedures used to assess the overall biodegradability. In the last section, we will review macromolecular engineering principles which could help enhance the degradability of said polymers when they reach the end of their life cycle.

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“…Other approaches have involved the use of a difunctional disulfide initiator (providing one cleavable unit in the centre of a (co)polymer) 29 and the step-growth polycondensations of α,ω-functional prepolymers through S-S coupling 8 or thiol oxidation. 30 Recently, thiocarbonyl addition-ring-opening (TARO) 31 radical polymerization of thionolactones was shown to introduce thioester backbone units into acrylate-, 31,32 acrylamide-, 31,33 maleimide-, 34 and vinyl ester- 35,36 based polymers. The method is compatible with reversible addition-fragmentation chain transfer (RAFT) radical polymerization (a major RDRP method) and thus enables the preparation of degradable copolymers with controlled architectures, including block copolymers.…”

Section: Introductionmentioning

confidence: 99%

Biocompatibility and Physiological Thiolytic Degradability of Radically-made Thioester-functional Copolymers

Bingham

Nisa

Gupta

et al. 2022

Preprint

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Being non-degradable, vinyl polymers have limited biomedical applicability. Unfortunately, backbone esters incorporated through conventional radical ring-opening methods do not undergo appreciable abiotic hydrolysis under physiologically relevant conditions. Here, PEG acrylate and di(ethylene glycol) acrylamide-based copolymers containing backbone thioesters were prepared through the radical ring-opening copolymerization of the thionolactone dibenzo[c,e]oxepin-5(7H)-thione. The thioesters degraded fully in the presence of 10 mM cysteine at pH 7.4, with the mechanism presumed to involve an irreversible S–N switch. Degradations with N-acetylcysteine and glutathione were reversible through the thiol–thioester exchange polycondensation of R–SC(=O)–polymer–SH fragments with full degradation relying on an increased thiolate:thioester ratio. Treatment with 10 mM glutathione at pH 7.2 (mimicking intracellular conditions) triggered an insoluble–soluble switch of a temperature-responsive copolymer at 37 °C and the release of encapsulated Nile Red (as a drug model) from core-degradable diblock copolymer micelles. Copolymers and their cysteinolytic degradation products were found to be non-cytotoxic, making thioester backbone-functional polymers promising for drug delivery applications.

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ε-Thionocaprolactone: an accessible monomer for preparation of degradable poly(vinyl esters) by radical ring-opening polymerization

Abstract: The 7-membered cyclic thionolactone, ε-thionocaprolactone (TCL), undergoes radical copolymerization with vinyl esters to form degradable copolymers. While most radical ring-opening monomers require laborious and low-yielding syntheses, TCL can be prepared...

Cited by 36 publications

References 41 publications

Fully degradable polymer networks from conventional radical polymerization of vinyl monomers enabled by thionolactone addition

Fully degradable polymer networks from conventional radical polymerization of vinyl monomers enabled by thionolactone addition

Spotlight on the Life Cycle of Acrylamide-Based Polymers Supporting Reductions in Environmental Footprint: Review and Recent Advances

Biocompatibility and Physiological Thiolytic Degradability of Radically-made Thioester-functional Copolymers

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