scholarly journals Dynamic Semi IPNs with Duple Dynamic Linkers: Self-Healing, Reprocessing, Welding, and Shape Memory Behaviors

Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1679
Author(s):  
Yanning Zeng ◽  
Weiming Yang ◽  
Shuxin Liu ◽  
Xiahui Shi ◽  
Aoqian Xi ◽  
...  

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.

2021 ◽  
Author(s):  
Boyeong Kang ◽  
Julia Kalow

In dynamic materials, the reversible condensation between boronic acids and diols provides adaptability, self-healing ability, and responsiveness to small molecules and pH. Recent work has shown that the thermodynamics and kinetics of bond exchange determine the mechanical properties of dynamic polymer networks. However, prior studies have focused on how structural and environmental factors influence boronic acid–diol binding affinity, and design rules for tuning the kinetics of this dynamic bond are lacking. In this work, we investigate the effects of diol (or polyol) structure and salt additives on the rate of bond exchange, binding affinity, and the mechanical properties of the corresponding polymer networks. To better mimic the environment of polymer networks in our small-molecule model systems, we incorporated proximal amide groups, which are used to conjugate diols to polymers, and included salts commonly found in buffers. Using one-dimensional selective exchange spectroscopy (1D EXSY), we find that both proximal amides and buffering anions induce significant rate acceleration consistent with internal and external catalysis, respectively. This rate acceleration is reflected in the stress relaxation of gels formed using PEG modified with different alcohols, and in the presence of salts containing acetate or phosphate. These findings contribute to the fundamental understanding of the boronic ester dynamic bond and offer new molecular strategies to tune the macromolecular properties of dynamic materials.


2016 ◽  
Vol 4 (32) ◽  
pp. 5394-5404 ◽  
Author(s):  
I. Dueramae ◽  
M. Nishida ◽  
T. Nakaji-Hirabayashi ◽  
K. Matsumura ◽  
H. Kitano

A novel type of shape memory polyurethane (SMPU) with high mechanical properties and biodegradability was constructed using a lactone copolymer (poly(ε-caprolactone-co-γ-butyrolactone), PCLBL), a diol- or triol-based chain extender (1,5-pentanediol, glycerol and 2-amino-2-hydroxymethyl-1,3-propanediol) and a diisocyanate cross-linker (1,6-hexamethylene diisocyanate).


2020 ◽  
Vol 90 (21-22) ◽  
pp. 2399-2410 ◽  
Author(s):  
Shahbaj Kabir ◽  
Hyelim Kim ◽  
Sunhee Lee

This study has investigated the physical properties of 3D-printable shape memory thermoplastic polyurethane (SMTPU) filament and its 3D-printed sinusoidal pattern obtained by fused deposition modeling (FDM) technology. To investigate 3D filaments, thermoplastic polyurethane (TPU) and SMTPU filament were examined by conducting infrared spectroscopy, x-ray diffraction (XRD), dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC) and a tensile test. Then, to examine the 3D-printed sinusoidal samples, a sinusoidal pattern was developed and 3D-printed. Those samples went through a three-step heating process: (a) untreated state; (b) 5 min heating at 70°C, cooling for 30 min at room temperature; and (c) a repeat of step 2. The results obtained by the three different heating processes of the 3D-printed sinusoidal samples were examined by XRD, DMTA, DSC and the tensile test to obtain the effect of heating or annealing on the structural and mechanical properties. The results show significant changes in structure, crystallinity and thermal and mechanical properties of SMTPU 3D-printed samples due to the heating steps. XRD showed the increase in crystallinity with heating. In DMTA, storage modulus, loss modulus and the tan σ peak position also changed for various heating steps. The DSC result showed that the Tg for different steps of the SMTPU 3D-printed sample remained almost the same at around 51°C. The tensile property of the TPU 3D-printed sinusoidal sample decreased in terms of both load and elongation with increased heating processes, while for the SMTPU 3D-printed sinusoidal sample, the load decreased but elongation increased about 2.5 times.


2016 ◽  
Vol 7 (47) ◽  
pp. 7278-7286 ◽  
Author(s):  
Jian Zhao ◽  
Rui Xu ◽  
Gaoxing Luo ◽  
Jun Wu ◽  
Hesheng Xia

The poly(siloxane-urethane) elastomers with microphase separation structure and Diels–Alder bonds show high healing efficiency, good mechanical property and good biocompatibility.


2021 ◽  
Vol 171 ◽  
pp. 113978
Author(s):  
Ya-zhou Xu ◽  
Pan Fu ◽  
Song-lin Dai ◽  
Hai-bo Zhang ◽  
Liang-wu Bi ◽  
...  

2004 ◽  
Vol 370 (1-2) ◽  
pp. 288-292 ◽  
Author(s):  
A Bartolotta ◽  
G Di Marco ◽  
M Lanza ◽  
G Carini ◽  
G D’Angelo ◽  
...  

2005 ◽  
Vol 475-479 ◽  
pp. 1001-1004
Author(s):  
Ninglin Zhou ◽  
Xiao Xian Xia ◽  
Li Li ◽  
Shao Hua Wei ◽  
Jian Shen

A novel exfoliated polyurethane (PU)/clay Interpenetrating Polymer Networks (IPNs) nanocomposite has been synthesized with polyurethane and organoclay. MTPAC is used as swelling agent to treat Na-montmorillonite for forming organoclay. The results indicate that there is very good compatibility between organoclay and PU. Nanoscale silicate dispersion was analyzed by XRD. The mechanical properties of the nanocomposites have been measured by tensile testing machine. The nanocomposites show obviously improved physical and mechanical properties when compared with the pure polymer. Additionally, PU /MTPAC- clay shows lower water absorption properties than pure PU do. In addition, the reinforcing and intercalating mechanism of silicate layers in polyurethane matrix are discussed.


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