Thermal-healable and shape memory metallosupramolecular poly(n-butyl acrylate-co-methyl methacrylate) materials

Wang, Zhenhua; Fan, Wenru; Tong, Rui; Lu, Xili; Xia, Hesheng

doi:10.1039/c4ra02843k

Cited by 68 publications

(61 citation statements)

References 37 publications

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“…These reversible behaviors endow supramolecular polymers with versatile functions, such as facile processing/recycling, 6,7 self-healing, [8][9][10][11][12] shape memory [13][14][15][16][17][18][19] and high responsivity to stimuli. Based on the smart "switchable" shape behavior of shape memory polymers when exposed to external stimuli, multifunctional polymers showing electroactive [25][26][27] or magnetoactive 28,29 shape memory effect, or combining shape memory behavior with other different functionalities, such as degradability, 30,31 controlled drug release, 32 thermochromism 33,34 and self-healing, [35][36][37][38][39][40] have been developed in recent years. Based on the smart "switchable" shape behavior of shape memory polymers when exposed to external stimuli, multifunctional polymers showing electroactive [25][26][27] or magnetoactive 28,29 shape memory effect, or combining shape memory behavior with other different functionalities, such as degradability, 30,31 controlled drug release, 32 thermochromism 33,34 and self-healing, [35][36][37][38][39][40] have been developed in recent years.…”

Section: Introductionmentioning

confidence: 99%

Intelligent rubber with tailored properties for self-healing and shape memory

et al. 2015

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A strategy of combining covalent and non-covalent cross-links to construct multifunctional rubber materials with intelligent self-healing and shape memory ability is demonstrated. The rubbers were prepared by self-assembly of complementary polybutadiene oligomers bearing carboxylic acid and amine groups through reversible ionic hydrogen bonds via acid-base reaction, and then further covalently cross-linking by tri-functional thiol via thiol-ene reaction. The resulting polymers exhibit self-healing and shape memory functions owing to the reversible ionic hydrogen bonds. The covalent cross-linking density can be tuned to achieve tailorable mechanical and stimuli-responsive properties: a low covalent cross-linking density remains the rubber remarkable self-healing capability at ambient temperature without any external stimulus, while a high covalent cross-linking density improves the mechanical strength and induces shape memory behavior, but effective self-healing needs to be triggered at high temperature. This strategy might open a promising pathway to fabricate intelligent multifunctional polymers with versatile functions. 9 and 9.2 mol%, respectively. Fig. 2b shows the typical FTIR spectra of pristine PB, PB-NH 2 , PB-COOH, and PB-COOH/NH 2 . For PB-NH 2 and PB-COOH, the presence of absorbance at 3382 cm -1 corresponding to -NH 2 stretching vibration and 1714cm -1 corresponding to C=O stretching vibration indicates the incorporation of amine and carboxylic acid groups into the PB backbone, respectively. For the prepared supramolecular polymer PB-COOH/NH 2 , the peak at 1714 cm -1 for neutral COOH almost completely disappears, and a new peak at 1570 cm -1 emerges, which can be attributed to carboxylate anions arising from proton transfer reaction (acid-base reaction) between carboxylic acid groups on PB-COOH and amine groups on PB-NH 2 , thus confirming the formation of ionic hydrogen bonds in the supramolecular polymers. Fig. 2 (a) 1 H NMR spectra of PB, PB-NH 2 and PB-COOH in CDCl 3 , (b) FTIR spectra of PB, PB-NH 2 , PB-COOH and supramolecular polymer PB-COOH/NH 2 .11 observed with the increase of the frequency. At low frequencies, the supramolecular interactions are able to break and re-form at the time scale probed, which is longer than the lifetime of the dynamic bonds, thus leading to a viscoelastic liquid behavior. At higher frequencies, however, the experimental time is not long enough for the supramolecular interactions to dissociate, thus the polymers exhibit elastic-like behavior. Furthermore, the crossover frequency (ω cross ) between G′ and G″ (tan δ=1) shifts to lower frequencies with the increase in covalent cross-linking density for all three samples. The lifetime of the reversible supramolecular networks can be measured as the inverse of the crossover frequency (ω cross ) of G′ and G″ (τ=1/ω). 64 Thus, the supramolecular networks with higher covalent cross-linking density possess longer life time arising from the decrease of the polymer chain mobility, which is consistent with the DSC results. Fi...

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Section: Introductionmentioning

confidence: 99%

Intelligent rubber with tailored properties for self-healing and shape memory

et al. 2015

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“…This polymer exhibited dual light-triggered functions of SM and damage healing through crystal melting and recrystallization. 27,28 Some research groups have investigated SM polymers containing Diels-Alder (DA) bonds. 25 The concept of using the SM function to aid crack closure has been applied to several intrinsic self-healing polymer systems based on reversible bonds.…”

Section: Introductionmentioning

confidence: 99%

Healable shape memory (thio)urethane thermosets

et al. 2015

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Urethane-thiourethane networks combining shape memory properties and the ability to self-heal under mild temperature conditions via Diels-Alder (DA) chemistry were developed. As a result of the shape recovery effect, no external force was needed to bring the fracture surfaces into intimate contact during the healing process. Four network architectures with DA net-points were evaluated. Two systems were composed of either bismaleimidic or bisfuranic semi-crystallized polycaprolactone chains acting as shape memory switching segments (T trans = T m ), whereas the other two networks consisted of bis-/trismaleimidic and trisfuranic monomers and displayed glass transitions for initiating shape recovery behaviour (T trans = T g ). The formation of the DA cross-links, the DA reversibility and shape memory assisted scratch healing of the materials were studied by FTIR and 1 H-NMR spectrometry, differential scanning calorimetry, optical microscopy and tensile measurements. The results indicated that the healing efficiency of scratches depends strongly on the shape recovery ability, without which crack closure and thus the healing reaction could not occur. Two materials were found to feature good shape memory properties as well as efficient scratch-healing capacities, showing mechanical recoveries of 70-80% and the almost complete disappearance of scratches after healing at a mild temperature of 60°C for 1-3 days. These materials could find applications in diverse fields such as self-healing coatings.Scheme 1 Chemical structures of the (thio)urethane multi-maleimide and multi-furan monomers and schematic depiction of the SM networks reversibly cross-linked by the DA reaction. Polymer Chemistry PaperThis journal is

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“…Wang et al copolymerized nBA and methyl methacrylate with a Mebip-containing acrylate via RAFT polymerization (approx. 3, 5, or 8% Mebip) [209]. Subsequent crosslinking with Zn(OTf) 2 led to a gel, whereas crosslinking with Eu(OTf) 3 resulted in a highly viscous material.…”

Section: Self-healing Metallopolymersmentioning

confidence: 92%

Intrinsic Self-Healing Polymers Based on Supramolecular Interactions: State of the Art and Future Directions

Enke

Döhler

Bode

et al. 2015

Self-Healing Materials

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Supramolecular polymers are an intriguing class of materials with dynamic behavior as a result of the presence of non-covalent bonds. These bonds include hydrogen bonds, metallopolymers, ionomers, host-guest as well as π-π interactions. The strength of these supramolecular bonds can be tuned by varying the binding motifs. Their reversible and dynamic character can be utilized to engineer self-healing polymers. This review briefly presents the preconditions for design of self-healing polymers and summarizes the development of supramolecular self-healing polymers based on various non-covalent interactions. Furthermore, challenges and perspectives for the understanding of self-healing mechanisms and the preparation of novel materials with enhanced properties are discussed.

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Thermal-healable and shape memory metallosupramolecular poly(n-butyl acrylate-co-methyl methacrylate) materials

Abstract: Thermal-induced shape memory and healing based on a metallosupramolecular polymer were realized.

Cited by 68 publications

References 37 publications

Intelligent rubber with tailored properties for self-healing and shape memory

Intelligent rubber with tailored properties for self-healing and shape memory

Healable shape memory (thio)urethane thermosets

Intrinsic Self-Healing Polymers Based on Supramolecular Interactions: State of the Art and Future Directions

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