Highly Stretchable Fully Biomass Autonomic Self-Healing Polyamide Elastomers and Their Foam for Selective Oil Absorption

Renewable polymers with self-healing ability, excellent elongation, hydrophobicity, and selective oil absorption attributes are of interest for an extensive range of applications, such as e-skin, soft robots, wearable devices, and cleaning up oil spills. Herein, two fully renewable eco-friendly polyamide (PA)-based self-healing elastomers (namely, PA36,IA, and PA36,36) were prepared by a facile and green one-pot melt polycondensation of itaconic acid (IA), PripolTM 1009, and PriamineTM 1075 monomers. The molecular structures of these PAs were analyzed by FITR, 1H NMR, and 13C NMR. The distinct structure of these PAs shows superior strain values (above 2300%) and high ambient temperature autonomous self-healing ability. Interestingly, the synthesized renewable PA36,36 showed zero water absorption values and hydrophobic properties with a contact angle of θ = 91° compared to the synthesized PA36,IA and other previously reported PAs. These excellent attributes are due to the low concentration of amide groups, the highly entangled main chains, the intermolecular diffusion, the manifold dangling chains, and the numerous reversible physical bonds within the renewable PAs. Furthermore, the hydrophobic properties may aid in the selective oil absorption of the PA36,36-based foam, for which PA36,36 foam is produced by the green supercritical carbon dioxide (scCO2) batch foaming process. The PA36,36 foam with a microporous cellular structure showed better absorption capacity and high stability in repeated use. Due to these advantages, these bio-based PAs have potential for the production of eco-friendly self-healing materials, superabsorbent foams, and other polymeric materials

Isothermal Crystallization Kinetics Study of Fully Aliphatic PA6 Copolyamides: Effect of Novel Long-Chain Polyamide Salt as a Comonomer

N1, N6-bis (4-aminobutyl) adipamide (BABA) diamine and sebacic acid (SA), also called BABA/SA polyamide salt, were used in a typical melt polymerization processes of polyamide 6 (PA6) to form a series of PA6-BABA/SA copolyamides. The effects of BABA/SA on the isothermal crystallization kinetics of PA6-BABA/SA were studied for the first time. An isothermal crystallization analysis demonstrates that the PA6-BABA/SA matrix provided a higher crystallization rate and shorter half-crystallization time than virgin PA6 did. The degree of crystallization of the PA6-BABA/SA30 matrix was also the lowest among all of the samples considered herein. This result is attributed to the high nucleation efficacy of a small amount of BABA/SA in the crystallization of PA6. Values of the Avrami exponent (n) from 1.84 to 3.91 were observed for all of the polyamide samples, suggesting that the crystallization was involved via a two- to three-dimensional growth mechanism. These findings deepen our understanding of the structure–property relationship of PA6-BABA/SA copolyamides, favoring their practical application

Synthesis of Low Melting Temperature Aliphatic-Aromatic Copolyamides Derived from Novel Bio-Based Semi Aromatic Monomer

This work investigated the synthesis of a novel low melting temperature polyamide 6 (PA6) copolyamide (PA6-BABT/SA) with different aliphatic/aromatic units weight content using a melt poly-condensation process. The bio-based aromatic N1,N4-bis(4-aminobutyl) terephthalamide diamine (BABT) and long-chain aromatic polyamide salt (BABT/SA, salt of BABT, and sebacic acid), components used for the synthesis of copolyamides, were obtained from bio-based monomers. For the first time, the pertinent BABT/SA aromatic polyamide salt was isolated as a white solid and completely characterized. By varying the weight ratio of BABT/SA salt, a series of copolyamides with different molecular weights and physical properties were prepared. The aromatic BABT/SA salt disrupted crystallization of the final copolyamides and lowered the onset of melting. The Fourier transform infrared spectroscopy and X-ray diffraction results indicated a steady decrease in the degrees of crystallinity with increasing BABT/SA salt segment ratio. Furthermore, compared to neat PA6, the obtained PA6-BABT/SA copolymers possessed a similar thermal stability and high transparency, but lower glass transition temperature around human body temperature. The PA6-BABT/SA copolymers with number-average molecular weight ≥30,000 Da presented good mechanical properties, specifically showing excellent tensile strength and elongation at break up to 105.2 MPa and 218.3%, respectively

Thermoreversible Switchlike Electrocatalytic Reduction of Tizanidine Based on a Graphene Oxide Tethered Stimuli-Responsive Smart Surface Supported Pd Catalyst

In this work, a graphene oxide (GRO)-based temperature-sensitive smart catalytic support material was developed by tethering biodegradable and hydrophilic poly(N-vinylcaprolactam) (PVCL) on a GRO (i.e., GRO-PVCL) surface. GRO-PVCL-supported palladium catalyst (i.e., Pd/GRO-PVCL) was then prepared for tizanidine (TZN) electroreduction. The impact of a temperature-sensitive smart surface on the electrochemical and electrocatalytic properties was examined. Moreover, when the large surface area, excellent electron transfer, and electrochemical catalysis abilities of GRO were combined with the responsive characteristics of PVCL, temperature-triggered reversible electrocatalysis of TZN with enhanced sensitivity has been proved. Results designated that GRO- PVCL exposed the hydrophilic surface at 20 degrees C, resulting in Pd NPs highly dispersed on the GRO-PVCL surface. Subsequently, the wettability of the Pd catalyst surface arbitrarily adapted to hydrophobicity at 40 degrees C, which highly enhanced the TZN reduction on the catalyst in electrochemical detection. The synergistic effect amid Pd and GRO-PVCL on Pd/GRO-PVCL improved the electrocatalytic activity of TZN. The detection of TZN with the Pd/GRO-PVCL modified electrode ranged from 0.02 to 276 mu M with a low detection limit of 0.0015 mu M at 40 degrees C. The Pd/GRO-PVCL modified electrode also possesses excellent stability, reproducibility, and anti-interference ability. Lastly, the modified electrode attained good recovery results in human urine and human plasma samples for the determination of TZN and also pharmacokinetics study in rat plasma.1

Effect of Bis (2-Aminoethyl) Adipamide/Adipic Acid Segment on Polyamide 6: Crystallization Kinetics Study

The crystallization behavior of novel polyamide 6 (PA6) copolyamides with different amounts of bis (2-aminoethyl) adipamide/adipic acid (BAEA/AA) segment was investigated. The wide-angle X-ray diffraction (WAXD) results showed that as the amount of BAEA/AA segment increased to 10 mole%, the crystalline forms of all PA6 copolyamide were transferred from the stable α-form to the unstable γ-form because of the complex polymer structure. According to studies of crystallization kinetics, the Avrami exponent (n) values for all copolyamide samples ranged from 1.43 to 3.67 under isothermal conditions, implying that the crystallization is involved in the two- to three-dimensional growth at a high temperature of isothermal condition. The copolyamides provided a slower crystallization rate and higher crystallization activation energy (ΔEa) than neat PA6. Polyamide containing 10 mole% of BEAE/AA content exhibited a unique crystallization behavior in the coexistence of the α and γ forms. These results deepen our understanding of the relationship between BAEA/AA content, crystal structure, and its crystallization behavior in low-melting PA6, and they make these types of copolyamides useful for their practical application