Thionolactone as a Resin Additive to Prepare (Bio)degradable 3D Objects via VAT Photopolymerization**

Gil, Noémie; Thomas, Constance; Mhanna, Rana; Mauriello, Jessica; Maury, Romain; Leuschel, Benjamin; Malval, Jean‐Pierre; Clément, Jean‐Louis; Gigmès, Didier; Lefay, Catherine; Soppera, Olivier; Guillaneuf, Yohann

doi:10.1002/anie.202117700

Cited by 29 publications

(38 citation statements)

References 42 publications

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“…Recently, Thoniyot et al reported that the insertion of an ester unit in poly(acrylic acid) via the use of MDO led to an interesting degree of biodegradability (27.50% in 28 days) in standard conditions (OECD 301F) compared to no biodegradation for the reference poly(acrylic acid). Our group also reported preliminary results of biodegradation for degradable 3D objects obtained using DOT as an additive using homemade compost . In this study, PS3 and Copo3 were finally tested for bacterial degradation.…”

Section: Resultsmentioning

confidence: 85%

“…Our group also reported preliminary results of biodegradation for degradable 3D objects obtained using DOT as an additive using homemade compost. 43 In this study, PS3 and Copo3 were finally tested for bacterial degradation. As said previously, the biodegradation of polystyrene has been investigated using a wide range of fungi, microbes, and invertebrates.…”

Section: Thermal and Mechanical Properties Of P(s-co-dot)mentioning

confidence: 99%

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Degradable Polystyrene via the Cleavable Comonomer Approach

et al. 2022

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Polystyrene (PS) is a major commodity polymer widely used in various applications ranging from packaging to insulation thanks to its low cost, high stiffness, and transparency as well as its relatively high softening temperature. Similarly to all polymers prepared by radical polymerization, PS is constituted of a C–C backbone and thus is not degradable. To confer degradability to such materials, the copolymerization of vinyl monomers with a cyclic monomer that could undergo radical ring-opening is an efficient method to introduce purposely cleavable bonds into the polymer backbone. Dibenzo[c,e]-oxepane-5-thione (DOT) is a cyclic thionolactone monomer known for its efficient copolymerization with acrylate derivatives but so far could not be incorporated into PS backbones. From a theoretical study combining density functional theory (DFT) and kinetic models using the PREDICI software, we showed that the modification of experimental conditions could overcome these limitations and that high molar mass degradable polystyrene (M w close to 150 000 g·mol–1) could be prepared via statistical insertion of thioester groups into the polymer backbone. This copolymerization process is compatible with conventional free radical polymerization and reversible deactivation radical polymerization (RDRP) techniques such as nitroxide mediated polymerization (NMP). Thanks to favorable reactivity ratios allowing only a few mol % of thioester units to be randomly incorporated, there was no major modification of the thermal and mechanical properties of the PS. The degradation of such PS could be performed in tetrahydrofuran (THF) at room temperature (RT) in 1 h using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a base, leading to oligomers with M n close to 2000 g·mol–1. We successfully demonstrate further applicability of these copolymerization systems for the phototriggered decomposition of PS in solution as well as the synthesis of cross-linked PS networks degradable into soluble side products.

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Section: Resultsmentioning

confidence: 85%

Section: Thermal and Mechanical Properties Of P(s-co-dot)mentioning

confidence: 99%

Degradable Polystyrene via the Cleavable Comonomer Approach

et al. 2022

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“…41 DOT is compatible with both FRP and RDRP and affords degradation via cleavage of the backbone thioester by, for example, primary amines, strong bases, or thiols. Very recently, Guillaneuf et al used DOT in crosslinked systems and reported that a 3D-printed poly(pentaerythritol triacrylate) 42 and a poly(styrene-co-divinylbenzene) 41 both underwent degradation with 2 wt % and 5 mol % of DOT, respectively. However, there has been neither a systematic study to optimize the ratio of DOT to crosslinker to achieve degradability nor a confirmation of the reverse gel-point model for radically made networks.…”

Section: ■ Introductionmentioning

confidence: 99%

Fully Degradable Polyacrylate Networks from Conventional Radical Polymerization Enabled by Thionolactone Addition

et al. 2022

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We report the preparation of degradable polymer networks by conventional free radical copolymerization of n-butyl acrylate with a crosslinker (1 mol %) and dibenzo[c,e]oxepane-5thione (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 (2−3 mol %) cannot be degraded. This data confirms the recently proposed reverse gel-point model for networks prepared by free radical polymerization and demonstrates the importance of considering copolymerization kinetics when designing fully degradable gels. Notably, 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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“…67 TARO monomers have also found a use in producing degradable cross-linked materials through uncontrolled radical polymerization. 68,71 Incorporation of only 4 mol% of DOT into acrylate-based networks led to the ability to completely degrade the insoluble materials. The low incorporation allowed for the retention of the physical properties of the network, compared to non-degradable controls, and 3D-print some of the structures.…”

Section: Reviewmentioning

confidence: 99%

“…-2-Methoxyethoxyacrylamide 67 N,N-Dimethylacrylamide 63,66,70 N,N-Diethylacrylamide 66 N-3-(N-4-Sulfobutyl-N,N-dimethylammonium) propylacrylamide 66 Acrylonitrile 63,66Pentaerythritol triacrylate71 Styrene 69,72 N-Methylmaleimide65 Alternating copolymerization between the thiocarbonyl species and the vinyl comomomer N-Phenylmaleimide 65 N-Pentafluorophenylmaleimide65 …”

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confidence: 99%