Self-Healing Polymers and Vitrimers

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Processing and Engineering".

Deadline for manuscript submissions: closed (30 April 2022) | Viewed by 20043

Special Issue Editors

Department of Polymer Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
Interests: microphase separation and self-assembly in multicomponent polymer systems; synthesis and characterization of polyhedral oligomeric silsesquioxane (POSS) monomers and POSS-containing polymers; shape memory, self-healing, and reprocessing properties of polymers; dynamics of polymers in bulk by solid NMR spectroscopy (1H, 13C, 29Si, 15N and 2H NMR)
Special Issues, Collections and Topics in MDPI journals
Department of Polymer Materials and Engineering, Hainan University, Haikou 570228, China
Interests: microphase separation and self-assembly in multicomponent polymer systems; biodegradable crosslinked polymers; intermolecular interaction; molecular dynamics (MD) simulation

Special Issue Information

Dear Colleagues,

Recently, self-healing polymers and vitrimers have attracted considerable interest from investigators. Inspired by the fact that biological tissues can heal injury, preparing these synthetic materials with self-healing properties in order to maintain the mechanical strength and structural integrity of materials against injury and damage is of interest. Vitrimers are a class of crosslinked polymer networks that contain dynamic chemical bonds. Their reprocessing can be achieved via the exchange of dynamic bonds. At service temperature, vitrimers behave as conventional thermosets. Nonetheless, the exchanges of dynamic bonds can be triggered at elevated temperatures. As a consequence, the thermosets display weldability, thermoplasticity or malleability. According to the exchange mechanism of dynamic bonds, covalent adaptable networks (CANs) of vitrimers can be divided into: i) dissociative and ii) associative types. Intrinsic self-healing of polymers and reprocessing of vitrimers can be achieved via the introduction of reversible and dynamic covalent or non-covalent bonds. Dynamic covalent bonds include transesterification, disulfide metathesis, trithiocarbonate exchange, transcarbamoylation, transamination of vinylogous amides or urethanes, imine exchange, hindered urea bonds, etc. Dynamic non-covalent bonds, such as hydrogen bonds, metal–ligand coordination and π–π stacking, are also employed to achieve self-healing of polymers or reprocessing of vitrimers.

This Special Issue is concerned with synthesis, characterization, structure and properties of self-healing polymers and vitrimers. Topics of interest include, but are not limited to, the following:

  1. Synthesis of new self-healing polymers;
  2. Design of new vitrimers;
  3. New dynamic chemistries for self-healing of polymers and reprocessing of vitrimers;
  4. Characterization of self-healing behavior;
  5. Multiphase design of self-healing polymers;
  6. Property improvent of vitrimers;
  7. Applications of self-healing polymers and vitrimers.

Hopefully, contributions focus on synthesis, mechanisms, physical and functional properties, and/or applications of the materials. These research articles can help to compile this Special Issue to reflect the current state-of-the-art advances in this area. Both original contributions and reviews are welcome.

Dr. Sixun Zheng
Dr. Rentong Yu
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Self-healing
  • Vitrimer
  • Reprocessing
  • Dynamic covalent bonds
  • Dynamic non-covalent bonds
  • Associative dynamic chemistry
  • Dissociative dynamic chemistry.

Published Papers (6 papers)

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Research

14 pages, 31118 KiB  
Article
Biodegradable Natural Rubber Based on Novel Double Dynamic Covalent Cross-Linking
by Qinggeng Jiang, Yi Gao, Lusheng Liao, Rentong Yu and Jianhe Liao
Polymers 2022, 14(7), 1380; https://doi.org/10.3390/polym14071380 - 29 Mar 2022
Cited by 8 | Viewed by 3973
Abstract
In this paper, biodegradable epoxidized natural rubber containing cyclic carbonate groups (CNR) was prepared by the reaction between epoxidized natural rubber (ENR) and carbon dioxide. Dynamic disulfide bonds and a boronic ester structure were successfully constructed and then the cross-linking network was formed [...] Read more.
In this paper, biodegradable epoxidized natural rubber containing cyclic carbonate groups (CNR) was prepared by the reaction between epoxidized natural rubber (ENR) and carbon dioxide. Dynamic disulfide bonds and a boronic ester structure were successfully constructed and then the cross-linking network was formed by the thermally initiated “click” reaction between thiol groups of the cross-linker and the residual epoxy groups of ENR. As a result of the exquisite double dynamic covalent structure, the material exhibits high self-healing efficiency. Moreover, by virtue of the cyclic carbonate structure of the CNR, the natural rubber was confirmed to be biodegradable according to the biodegradable measurement. To the best of our knowledge, natural rubber with biodegradable and self-healing characteristics was obtained for the first time. Full article
(This article belongs to the Special Issue Self-Healing Polymers and Vitrimers)
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18 pages, 2619 KiB  
Article
Nanocomposites of Polyhydroxyurethane with POSS Microdomains: Synthesis via Non-Isocyanate Approach, Morphologies and Reprocessing Properties
by Weiming Liu, Guohua Hang, Honggang Mei, Lei Li and Sixun Zheng
Polymers 2022, 14(7), 1331; https://doi.org/10.3390/polym14071331 - 25 Mar 2022
Cited by 16 | Viewed by 2210
Abstract
In this contribution, we reported the synthesis of a novel trifunctional POSS cyclic carbonate [POSS-3(5CC)]. With a difunctional five-member cyclic carbonate and a trifunctional polyetheramine as the precursor, the nanocomposites of polyhydroxyurethane (PHU) with POSS were synthesized. Transmission electron microscopy (TEM) showed that [...] Read more.
In this contribution, we reported the synthesis of a novel trifunctional POSS cyclic carbonate [POSS-3(5CC)]. With a difunctional five-member cyclic carbonate and a trifunctional polyetheramine as the precursor, the nanocomposites of polyhydroxyurethane (PHU) with POSS were synthesized. Transmission electron microscopy (TEM) showed that the nanocomposites of PHUs with POSS were microphase-separated; the spherical POSS microdomains via POSS-POSS interactions were generated with the size of 20~40 nm in diameter. After the introduction of POSS microdomains, the nanocomposites displayed improved thermal and mechanical properties. More importantly, the nanocomposites still displayed the reprocessing properties of vitrimers. Full article
(This article belongs to the Special Issue Self-Healing Polymers and Vitrimers)
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16 pages, 7059 KiB  
Article
Sustainable Polyurethane Networks Based on Rosin with Reprocessing Performance
by Jiawei Li, Weiming Yang, Zhao Ning, Bin Yang and Yanning Zeng
Polymers 2021, 13(20), 3538; https://doi.org/10.3390/polym13203538 - 14 Oct 2021
Cited by 20 | Viewed by 2348
Abstract
Rosin is an abundant natural product. In this paper, for the first time, a rosin derivative is employed as a monomer for the preparation of polyurethane vitrimers with improved properties. A novel rosin-based polyurethane vitrimers network was constructed by the reaction between isocyanates [...] Read more.
Rosin is an abundant natural product. In this paper, for the first time, a rosin derivative is employed as a monomer for the preparation of polyurethane vitrimers with improved properties. A novel rosin-based polyurethane vitrimers network was constructed by the reaction between isocyanates (HDI) as curing agent and monomers with alcohol groups modified from rosin. The dynamic rosin-based polyurethane vitrimers were characterized by FTIR and dynamic mechanical analysis. The obtained rosin-based polyurethane vitrimers possessed superior mechanical properties. Due to the dynamic urethane linkages, the network topologies of rosin-based polyurethane vitrimers could be altered, contributing self-healing and reprocessing abilities. Besides, we investigated the effects of healing time and temperature on the self-healing performance. Moreover, through a hot press, pulverized samples of 70%VPUOH could be reshaped several times, and the mechanical properties of the recycled samples were restored, with tensile strength being even higher than the of that of the original samples. Full article
(This article belongs to the Special Issue Self-Healing Polymers and Vitrimers)
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19 pages, 4587 KiB  
Article
Rosin-Based Epoxy Vitrimers with Dynamic Boronic Ester Bonds
by Yanning Zeng, Jiawei Li, Shuxin Liu and Bin Yang
Polymers 2021, 13(19), 3386; https://doi.org/10.3390/polym13193386 - 01 Oct 2021
Cited by 45 | Viewed by 3823
Abstract
Rosin is an abundantly available natural product. In this paper, for the first time, a rosin derivative is employed as the main monomer for preparation of epoxy vitrimers to improve the mechanical properties of vitrimers. Novel epoxy vitrimer networks with dynamic reversible covalent [...] Read more.
Rosin is an abundantly available natural product. In this paper, for the first time, a rosin derivative is employed as the main monomer for preparation of epoxy vitrimers to improve the mechanical properties of vitrimers. Novel epoxy vitrimer networks with dynamic reversible covalent boronic ester bonds are constructed by a reaction between thiols in 2,2′–(1,4–phenylene)–bis (4–mercaptan–1,3,2–dioxaborolane) (BDB) as a curing agent and epoxy groups in the rosin derivative. The rosin-based epoxy vitrimer networks are fully characterized by Fourier transform infrared spectroscopy (FTIR), an equilibrium swelling experiment, and dynamic mechanical analysis (DMA). The obtained rosin-based epoxy vitrimers possess superior thermostability and good mechanical properties. Due to transesterification of boronic ester bonds, rosin epoxy vitrimer network topologies can be altered, giving welding, recycle, self-healing, and shape memory abilities to the fabricated polymer. Besides, the effects of treating time and temperature on welding capability is investigated, and it is found that the welding efficiency of the 20% C-FPAE sample is >93% after treatment for 12 h at 160 °C. Moreover, through a hot press, the pulverized samples of 20% C-FPAE can be reshaped several times and most mechanical properties are restored after reprocessing at 200 °C for 60 min. Finally, chemical degradation is researched for the rosin-based epoxy vitrimers. Full article
(This article belongs to the Special Issue Self-Healing Polymers and Vitrimers)
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19 pages, 6573 KiB  
Article
Dynamic Semi IPNs with Duple Dynamic Linkers: Self-Healing, Reprocessing, Welding, and Shape Memory Behaviors
by Yanning Zeng, Weiming Yang, Shuxin Liu, Xiahui Shi, Aoqian Xi and Faai Zhang
Polymers 2021, 13(11), 1679; https://doi.org/10.3390/polym13111679 - 21 May 2021
Cited by 19 | Viewed by 2414
Abstract
Thermoset polymers show favorable material properties, while bringing about environmental pollution due to non-reprocessing and unrecyclable. Diels–Alder (DA) chemistry or reversible exchange boronic ester bonds have been employed to fabricate recycled polymers with covalent adaptable networks (CANs). Herein, a novel type of CANs [...] Read more.
Thermoset polymers show favorable material properties, while bringing about environmental pollution due to non-reprocessing and unrecyclable. Diels–Alder (DA) chemistry or reversible exchange boronic ester bonds have been employed to fabricate recycled polymers with covalent adaptable networks (CANs). Herein, a novel type of CANs with multiple dynamic linkers (DA chemistry and boronic ester bonds) was firstly constructed based on a linear copolymer of styrene and furfuryl methacrylate and boronic ester crosslinker. Thermoplastic polyurethane is introduced into the CANs to give a semi Interpenetrating Polymer Networks (semi IPNs) to enhance the properties of the CANs. We describe the synthesis and dynamic properties of semi IPNs. Because of the DA reaction and transesterification of boronic ester bonds, the topologies of semi IPNs can be altered, contributing to the reprocessing, self-healing, welding, and shape memory behaviors of the produced polymer. Through a microinjection technique, the cut samples of the semi IPNs can be reshaped and mechanical properties of the recycled samples can be well-restored after being remolded at 190 °C for 5 min. Full article
(This article belongs to the Special Issue Self-Healing Polymers and Vitrimers)
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21 pages, 5188 KiB  
Article
Influence of the Glass Transition Temperature and the Density of Crosslinking Groups on the Reversibility of Diels-Alder Polymer Networks
by Merlina Thiessen and Volker Abetz
Polymers 2021, 13(8), 1189; https://doi.org/10.3390/polym13081189 - 07 Apr 2021
Cited by 10 | Viewed by 3485
Abstract
The interest in self-healing, recyclable, and adaptable polymers is growing. This work addresses the reversibility of crosslink formation based on Diels-Alder reaction in copolymer networks containing furfuryl and maleimide groups, which represent the “diene” and the “dienophile,” respectively. The copolymers are synthesized by [...] Read more.
The interest in self-healing, recyclable, and adaptable polymers is growing. This work addresses the reversibility of crosslink formation based on Diels-Alder reaction in copolymer networks containing furfuryl and maleimide groups, which represent the “diene” and the “dienophile,” respectively. The copolymers are synthesized by atom transfer radical polymerization (ATRP) and free radical polymerization. The diene bearing copolymers are crosslinked either with a small molecule containing two dienophiles or with a dienophile bearing copolymer. The influence of the crosslinking temperature on the Diels-Alder reaction is analyzed. Furthermore, the influence of the glass transition temperature and the influence of the density of crosslinking groups on the thermo-reversibility of crosslinking are investigated by temperature dependent infrared spectroscopy and differential scanning calorimetry. It is shown that the reversibility of crosslinking is strongly influenced by the glass transition temperature of the system. Full article
(This article belongs to the Special Issue Self-Healing Polymers and Vitrimers)
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