Water activated healing of thiolene boronic ester coatings

Souza, Mandy de; Dubois, Charlotte; Zhang, Jingyan; Varley, Russell J.

doi:10.1016/j.porgcoat.2019.105424

Cited by 3 publications

(3 citation statements)

References 21 publications

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“…[ 3,5,17–20 ] Later, catalyst‐free dynamic exchange chemistries, such as disulfide linkages, imine bonds, dynamic Meldrum's acid‐derived linkages, boronic esters and enamine linkages, emerged as great alternatives as they circumvent catalyst leaching and miscibility concerns. [ 21–44 ] Expanding upon work by Du Prez and co‐workers on vinylogous urethane, Christensen et al. pioneered the use of diketoenamine to create vitrimeric materials.…”

Section: Introductionmentioning

confidence: 99%

Diketoenamine‐Based Vitrimers via Thiol‐ene Photopolymerization

Dugas

Walker

Shankar

et al. 2022

Macromol. Rapid Commun.

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Likened to both thermosets and thermoplastics, vitrimers are a unique class of materials that combine remarkable stability, healability, and reprocessability. Herein, this work describes a photopolymerized thiol‐ene‐based vitrimer that undergoes dynamic covalent exchanges through uncatalyzed transamination of enamines derived from cyclic β‐triketones, whereby the low energy barrier for exchange facilitates reprocessing and enables rapid depolymerization. Accordingly, an alkene‐functionalized β‐triketone, 5,5‐dimethyl‐2‐(pent‐4‐enoyl)cyclohexane‐1,3‐dione, is devised which is then reacted with 1,6‐diaminohexane in a stoichiometrically imbalanced fashion (≈1:0.85 primary amine:triketone). The resulting networks exhibit subambient glass transition temperature (Tg = 5.66 °C) by differential scanning calorimetry. Using a Maxwell stress‐relaxation fit, the topology‐freezing temperature (Tv) is calculated to be −32 °C. Small‐amplitude oscillatory shear rheological analysis enables to identify a practical critical temperature above which the vitrimer can be successfully reprocessed (Tv,eff). Via the introduction of excess primary amines, this work can readily degrade the networks into monomeric precursors, which are in turn reacted with diamines to regenerate reprocessable networks. Photopolymerization provides unique spatiotemporal control over the network topology, thereby opening the path for further investigation of vitrimer properties. As such, this work expands the toolbox of chemical upcycling of networks and enables their wider implementation.

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Section: Introductionmentioning

confidence: 99%

Diketoenamine‐Based Vitrimers via Thiol‐ene Photopolymerization

Dugas

Walker

Shankar

et al. 2022

Macromol. Rapid Commun.

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“…1−3 These materials have been widely used for the preparation of hydrogels and related polymer resins for applications such as tissue engineering and drug delivery, 3,4 optical devices, 5 solid polymer electrolytes, 6 and coatings. 7 Different methods were utilized to produce polymers with boronic ester cross-linking bonds. 2,8 One of the most common methods is the synthesis of diol-functionalized polymers and boronic acid-containing polymers separately and mixing them together.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Preparation of polymers containing boronic ester dynamic covalent bonds has been of interest because of their exceptional recyclability and self-healing properties. − These materials have been widely used for the preparation of hydrogels and related polymer resins for applications such as tissue engineering and drug delivery, , optical devices, solid polymer electrolytes, and coatings . Different methods were utilized to produce polymers with boronic ester cross-linking bonds. , One of the most common methods is the synthesis of diol-functionalized polymers and boronic acid-containing polymers separately and mixing them together. , The synthesis of each polymer resin or the mixing process generally involves using organic solvents, which intensifies the environmental and health concerns associated with the process. , Although using water as the dispersant phase in the system seems beneficial, the synthesis of materials containing boronic ester bonds in a water-based system has always been problematic because of the relatively high water solubility of monomers containing the boronic acid or diol functional groups. − Furthermore, the copolymerization of these monomers with water-insoluble monomers in water-based or emulsion systems usually results in the uncontrolled formation of hydrogels with a broad molecular weight distribution and low monomer conversion. , We prepared polymers containing boronic ester dynamic cross-linking bonds in an organic solvent (toluene) previously, where we attempted to use commercially available monomers with high biocontent .…”

Section: Introductionmentioning

confidence: 99%

Recyclable Polymers with Boronic Ester Dynamic Bonds Prepared by Miniemulsion Polymerization

Tajbakhsh

Hajiali

Marić

2021

ACS Appl. Polym. Mater.

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Polymers with boronic ester dynamic covalent bonds were synthesized by nitroxide-mediated miniemulsion polymerization of isobornyl methacrylate (IBOMA), alkyl methacrylates (average aliphatic size of 13.0, C13MA), glycerol monomethacrylate (GMMA), and 4-vinylphenylboronic acid (VPBA). The miniemulsion polymerization of all monomers was enabled by the esterification reaction between GMMA and VPBA and the synthesis of (VPBA + GMMA) dimer prior to the polymerization. The formation of boronic ester dynamic covalent bonds was confirmed by rheological and mechanical measurements, indicating a higher stiffness by increasing the dimer content from 5% to 15% in the initial feed. Cross-linked polymers showed high reprocessing capability with a comparatively simple recycling process (at 80 °C for 45 min) and a high organic solvent absorbance of polymers (swelling ratio up to 153%). Furthermore, it was shown that the addition of VPBA and GMMA significantly improved the heat resistance of polymers up to 121 °C, compared to the IBOMA/C13MA copolymers (without GMMA and VPBA functional monomers).

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A healable polyethylene adhesive using poly(ethylene methacrylic acid) (EMAA) for three-layer pipe coatings

et al. 2021

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Poly(ethylene methacrylic acid) (EMAA) has been used here as a thermally activated healing agent (HA) in three layered polyolefinic (3LPO) pipe coatings for the first time. The EMAA (HA) is blended with a linear low density polyethylene (LLDPE) modified with maleic anhydride (MAH) to create a healable multi-functional adhesive (HAMA), which is used to bind the fusion bonded epoxy primer and high density polyethylene topcoat layers together. Different compositions of the HA and modified adhesive were trialled for their healing efficiency using three different healing conditions to explore the effect of increasing temperature and applied load or force. The standard healing protocol used a healing temperature of 110 °C and an applied load of 120 N for 60 min. A high temperature variant increased the temperature to 120 °C while a high load variant increased the applied force to 240 N. Using a 1:1 HAMA adhesive, healing efficiencies of about 70% were achieved for the standard healing condition. Increasing the applied load to 240 N decreased healing to between 64% and 68% depending on the healing measurement, but at 120 °C healing increased to between 82% and 84%. Regardless of the healing condition, overall healing efficiency increased with increasing EMAA (HA) concentration. This study also provided insight into the healing mechanism of the HAMA adhesives by highlighting some necessary features for healing. A bi-phasic microstructure consisting of large EMAA nodules with sufficient adhesion to the MAH-modified LLDPE was identified as being critical. Furthermore, increasing healing temperature increased healing efficiency due to the enhanced flow of EMAA and increased mobility of the polyethylene. Although these results are preliminary in nature, they do provide significant promise that multifunctional HAMA adhesives can be applied as simple, effective and repeatable 3LPO self-healing pipe coatings.

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Water activated healing of thiolene boronic ester coatings

Cited by 3 publications

References 21 publications

Diketoenamine‐Based Vitrimers via Thiol‐ene Photopolymerization

Diketoenamine‐Based Vitrimers via Thiol‐ene Photopolymerization

Recyclable Polymers with Boronic Ester Dynamic Bonds Prepared by Miniemulsion Polymerization

A healable polyethylene adhesive using poly(ethylene methacrylic acid) (EMAA) for three-layer pipe coatings

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