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Design and Performance of 3D-Printed Hybrid Polymers Exhibiting Shape Memory and Self-Healing via Acrylate–Epoxy–Thiol–Ene Chemistry.

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Title: Design and Performance of 3D-Printed Hybrid Polymers Exhibiting Shape Memory and Self-Healing via Acrylate–Epoxy–Thiol–Ene Chemistry.
Authors: Acosta Ortiz, Ricardo1 (AUTHOR) ricardo.acosta@ciqa.edu.mx, Hernández Jiménez, Alan Isaac1 (AUTHOR), Ku Herrera, José de Jesús1 (AUTHOR), Yañez Macías, Roberto1 (AUTHOR), García Valdez, Aida Esmeralda1 (AUTHOR)
Source: Polymers (20734360). Oct2025, Vol. 17 Issue 19, p2594. 20p.
Subjects: Shape memory effect, Self-healing materials, Three-dimensional printing, Rapid prototyping, Photopolymers, Photopolymerization, Thermosetting composites, Polymeric composites
Abstract: This study presents a novel strategy for designing photocurable resins tailored for the additive manufacturing of smart thermoset materials. A quaternary formulation was developed by integrating bis(2-methacryloyl)oxyethyl disulfide (DADS) with an epoxy/thiol-ene system (ETES) composed of diglycidyl ether of bisphenol A (EP), pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), and 4,4′-methylenebis(N,N-diallylaniline) (ACA4). This unique combination enables the simultaneous activation of four polymerization mechanisms: radical photopolymerization, thiol-ene coupling, thiol-Michael addition, and anionic ring-opening, within a single resin matrix. A key innovation lies in the exothermic nature of DADS photopolymerization, which initiates and sustains ETES curing at room temperature, enabling 3D printing without thermal assistance. This represents a significant advancement over conventional systems that require elevated temperatures or post-curing steps. The resulting hybrid poly(acrylate–co-ether–co-thioether) network exhibits enhanced mechanical integrity, shape memory behavior, and intrinsic self-healing capabilities. Dynamic Mechanical Analysis revealed a shape fixity and recovery of 93%, while self-healing tests demonstrated a 94% recovery of viscoelastic properties, as evidenced by near-overlapping storage modulus curves compared to a reference sample. This integrated approach broadens the design space for multifunctional photopolymers and establishes a versatile platform for advanced applications in soft robotics, biomedical devices, and sustainable manufacturing. [ABSTRACT FROM AUTHOR]
Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Design and Performance of 3D-Printed Hybrid Polymers Exhibiting Shape Memory and Self-Healing via Acrylate–Epoxy–Thiol–Ene Chemistry.
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  Data: <searchLink fieldCode="AR" term="%22Acosta+Ortiz%2C+Ricardo%22">Acosta Ortiz, Ricardo</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> ricardo.acosta@ciqa.edu.mx</i><br /><searchLink fieldCode="AR" term="%22Hernández+Jiménez%2C+Alan+Isaac%22">Hernández Jiménez, Alan Isaac</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Ku+Herrera%2C+José+de+Jesús%22">Ku Herrera, José de Jesús</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Yañez+Macías%2C+Roberto%22">Yañez Macías, Roberto</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22García+Valdez%2C+Aida+Esmeralda%22">García Valdez, Aida Esmeralda</searchLink><relatesTo>1</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Polymers+%2820734360%29%22">Polymers (20734360)</searchLink>. Oct2025, Vol. 17 Issue 19, p2594. 20p.
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  Data: <searchLink fieldCode="DE" term="%22Shape+memory+effect%22">Shape memory effect</searchLink><br /><searchLink fieldCode="DE" term="%22Self-healing+materials%22">Self-healing materials</searchLink><br /><searchLink fieldCode="DE" term="%22Three-dimensional+printing%22">Three-dimensional printing</searchLink><br /><searchLink fieldCode="DE" term="%22Rapid+prototyping%22">Rapid prototyping</searchLink><br /><searchLink fieldCode="DE" term="%22Photopolymers%22">Photopolymers</searchLink><br /><searchLink fieldCode="DE" term="%22Photopolymerization%22">Photopolymerization</searchLink><br /><searchLink fieldCode="DE" term="%22Thermosetting+composites%22">Thermosetting composites</searchLink><br /><searchLink fieldCode="DE" term="%22Polymeric+composites%22">Polymeric composites</searchLink>
– Name: Abstract
  Label: Abstract
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  Data: This study presents a novel strategy for designing photocurable resins tailored for the additive manufacturing of smart thermoset materials. A quaternary formulation was developed by integrating bis(2-methacryloyl)oxyethyl disulfide (DADS) with an epoxy/thiol-ene system (ETES) composed of diglycidyl ether of bisphenol A (EP), pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), and 4,4′-methylenebis(N,N-diallylaniline) (ACA4). This unique combination enables the simultaneous activation of four polymerization mechanisms: radical photopolymerization, thiol-ene coupling, thiol-Michael addition, and anionic ring-opening, within a single resin matrix. A key innovation lies in the exothermic nature of DADS photopolymerization, which initiates and sustains ETES curing at room temperature, enabling 3D printing without thermal assistance. This represents a significant advancement over conventional systems that require elevated temperatures or post-curing steps. The resulting hybrid poly(acrylate–co-ether–co-thioether) network exhibits enhanced mechanical integrity, shape memory behavior, and intrinsic self-healing capabilities. Dynamic Mechanical Analysis revealed a shape fixity and recovery of 93%, while self-healing tests demonstrated a 94% recovery of viscoelastic properties, as evidenced by near-overlapping storage modulus curves compared to a reference sample. This integrated approach broadens the design space for multifunctional photopolymers and establishes a versatile platform for advanced applications in soft robotics, biomedical devices, and sustainable manufacturing. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.3390/polym17192594
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      – Code: eng
        Text: English
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        PageCount: 20
        StartPage: 2594
    Subjects:
      – SubjectFull: Shape memory effect
        Type: general
      – SubjectFull: Self-healing materials
        Type: general
      – SubjectFull: Three-dimensional printing
        Type: general
      – SubjectFull: Rapid prototyping
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      – SubjectFull: Photopolymers
        Type: general
      – SubjectFull: Photopolymerization
        Type: general
      – SubjectFull: Thermosetting composites
        Type: general
      – SubjectFull: Polymeric composites
        Type: general
    Titles:
      – TitleFull: Design and Performance of 3D-Printed Hybrid Polymers Exhibiting Shape Memory and Self-Healing via Acrylate–Epoxy–Thiol–Ene Chemistry.
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          Name:
            NameFull: Acosta Ortiz, Ricardo
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            NameFull: Hernández Jiménez, Alan Isaac
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            NameFull: Ku Herrera, José de Jesús
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            NameFull: Yañez Macías, Roberto
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            NameFull: García Valdez, Aida Esmeralda
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            – D: 01
              M: 10
              Text: Oct2025
              Type: published
              Y: 2025
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              Value: 17
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              Value: 19
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