Room Temperature Self‐Healing Methyl Phenyl Silicone Rubbers Based on the Metal–Ligand Cross‐Link: Synthesis and Characterization

Yu, Dajiang; Zhao, Xinxin; Zhou, Chuanjian; Zhang, Chen; Zhao, Shigui

doi:10.1002/macp.201600519

Cited by 26 publications

(17 citation statements)

References 28 publications

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“…Polymer–metal complexes (PMCs; in other words, metal centers bound by polymers exhibiting ligation properties) have gained considerable attention in view of the expressed kinetic lability of metal–ligand bonds, particularly when this bonding includes the labile metal centers in Taube’s definition (for instance, aluminum(III), , iron(II,III), − cobalt(II), , nickel(II), zinc(II), ,− and copper(II)) . In such systems, the consequence of coordination bond breaking–coordination bond making plays the role of a zipper, which unzips during the damage of SHMs and zips up upon SH (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Structural Features of Polymer Ligand Environments Dramatically Affect the Mechanical and Room-Temperature Self-Healing Properties of Cobalt(II)-Incorporating Polysiloxanes

et al. 2021

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Cobalt(II)-pyridinedicarboxamide-co-polydimethylsiloxane (Co-Py-PDMSs) and cobalt(II)-bipyridinedicarboxamide-co-polydimethylsiloxane (Co-Bipy-PDMSs) polymer−metal complexes were prepared by complexation between Py-PDMSs or Bipy-PDMSs ligands and cobalt(II); the metal content in these complexes varied from 0.09 to 2.41 wt %. The Co II binding patterns (the Co−N Py and Co−O coordination in Co-Py-PDMSs and Co−N Bipy in Co-Bipy-PDMSs) were established by UV−vis and IR methods and by comparison with model Co II complexes exhibiting relevant O,N,O-and N,N-coordination environments, respectively. The mechanical properties of the polymer−metal complexes were controlled by the coordination of Py-PDMSs or Bipy-PDMSs to Co II at various metal-toligand molar ratios (1:(1−6)) and by the variation of the polydimethylsiloxane unit length (M n : 850−900, 5000, or 25 000 g•mol −1 ). Utilization of the chelated Py-PDMSs and Bipy-PDMSs polymer ligands, which are capable of tri-or bidentate binding of Co II , led to (2−4)-fold increases in tensile strength (up to 1.75 MPa) and much higher elongation at break ((2−3)-fold increase up to 2100%) compared with the previously reported Co II -based polymer− ligand systems featuring monodentate ligation entities. Changing the main-chain ligand from Py-PDMSs to Bipy-PDMSs led to an increase in tensile strength of (2−4)-fold in comparison with Py-PDMS and a lower hysteresis (4%). The room temperature selfhealing efficiency was up to 96% for Co-Py-PDMSs and 40% for Co-Bipy-PDMSs, as measured for a polydimethylsiloxane unit with M n = 25 000 g•mol −1 .

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Section: Introductionmentioning

confidence: 99%

Structural Features of Polymer Ligand Environments Dramatically Affect the Mechanical and Room-Temperature Self-Healing Properties of Cobalt(II)-Incorporating Polysiloxanes

et al. 2021

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“…Taking the synthesis of silicone oil with 40% phenyl content as an example, the phenyl content = 3 × I 5 /(1.5 × I 5 + (I 1 + I 2 )), I 5 , I 1 and I 2 is the integrated intensity of peak 5 and peak 2 in the 1 H NMR spectrum of Figure 1 c. The phenyl content of the obtained silicone oil is in accordance with the phenyl content of the feed ( Figure 1 c,d). The synthesis process of silicone oil in our research group is relatively mature and we can achieve the synthesis of silicone oil with different phenyl content [ 34 , 35 ].…”

Section: Resultsmentioning

confidence: 99%

The Effect of Phenyl Content on the Liquid Crystal-Based Organosilicone Elastomers with Mechanical Adaptability

2022

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An elastomer with mechanical adaptability is a new kind of polymer material in which the increasing stress under continuous deformation is significantly inhibited in a large deformation area. Liquid crystal-based organosilicone elastomers, which can dissipate energy through reversible internal phase transition under external stimulation and have recoverable large deformation capacity, have drawn much interest as mechanical adaptability materials. However, there is no good way to control the mechanical adaptability at present. For this purpose, we prepared a new liquid crystal-based phenyl silicone rubber (LCMVPQ) using two-step click reactions and systematically explored the effect of phenyl content on its mechanical adaptability to achieve the regulation of mechanical adaptability. With an increase in phenyl content in the LCMVPQs, phenyl can hinder the rearrangement of the mesogenic units along the applied stress direction, which enables the adjustment of mechanical adaptability to meet the needs of different situations. In addition, the introduction of the liquid crystal phase impedes the internal friction of the molecular chain movement of the LCMVPQs and reduces the damping performance of silicone rubber. This research achieves the regulation of elastomers with mechanical adaptability and is expected to be applied in practical application fields.

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“…However, few reports are found about the functionalization of tetra‐PEG hydrogel, compared with other kinds of high‐strength hydrogels. Recently, we developed a method to functionalize the tetra‐PEG based hydrogel by taking advantage of polyurethane/polyurea (PU) chemistry and demonstrated the validity of this way . Because the formed tetra‐PEG based PU (TP) hydrogel can be considered as a platform to be introduced with various functional units, introduction of reversible sacrificial bonds into the TP hydrogel should be a valuable project to both improve the hydrogel's strength and endow the hydrogel with functions.…”

Section: Introductionmentioning

confidence: 99%

Bioinspired Tunable Sacrificial Bonds Endowing Tetra‐PEG Based PU Hydrogel with Tunable Mechanical Properties, Shape‐Memory, and Self‐Healing Functions

Lei

et al. 2018

Macro Materials & Eng

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Development of hydrogels with excellent and tunable mechanical properties combining with multifunctions is an intriguing issue in material science and engineering. Herein, bioinspired tunable sacrificial bonds are introduced into the tetra‐poly(ethylene glycol) (PEG) based polyurethane (PU) (TP) network to afford a hydrogel with tunable mechanical properties, shape‐memory, and self‐healing functions. The mussel‐inspired compound of Lysine‐dopamine (LDA) is introduced into the network of TP hydrogel through polyurethane/polyurea chemistry to form LDA‐tetra‐PEG‐PU (LTP) hydrogel. As catechol groups in LDAs can intermolecularly interact with each other and can also coordinate with ferric ions with different coordination ratios, these physical interactions with different strengths in the afforded LTP hydrogel construct kinds of sequentially tuned sacrificial bonds. As a result, these sacrificial bonds preferentially rupture prior to the covalent network upon external loading, which dissipate the energy and endow the hydrogel with advanced and postadjustable mechanical properties. This mechanism is investigated in detail. Furthermore, the LTP hydrogel shows multifunctions such as shape‐memory and self‐healing abilities. In addition, the tetra‐PEG based hydrogel shows remarkable thermoresponsiveness that the hydrogel distinctly contracts with the increase of the temperature. The improved mechanical strength and multifunctions should enlarge the application areas of the tetra‐PEG based hydrogel in various fields.

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Room Temperature Self‐Healing Methyl Phenyl Silicone Rubbers Based on the Metal–Ligand Cross‐Link: Synthesis and Characterization

Cited by 26 publications

References 28 publications

Structural Features of Polymer Ligand Environments Dramatically Affect the Mechanical and Room-Temperature Self-Healing Properties of Cobalt(II)-Incorporating Polysiloxanes

Structural Features of Polymer Ligand Environments Dramatically Affect the Mechanical and Room-Temperature Self-Healing Properties of Cobalt(II)-Incorporating Polysiloxanes

The Effect of Phenyl Content on the Liquid Crystal-Based Organosilicone Elastomers with Mechanical Adaptability

Bioinspired Tunable Sacrificial Bonds Endowing Tetra‐PEG Based PU Hydrogel with Tunable Mechanical Properties, Shape‐Memory, and Self‐Healing Functions

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