Synthesis of novel L-lactic acid-based plasticizers and their effects on the flexibility, crystallinity, and optical transparency of poly(lactic acid).

Using bio-based plasticizers derived from biomass resources to replace traditional phthalates can avoid the biotoxicity and non-biodegradability caused by the migration of plasticizers during the application of plastics. In this study, L-lactic acid and levulinic acid were employed as the major biomass monomer to successfully fabricate L-lactic acid-based plasticizers (LBL-n, n = 1.0, 1.5, 2.0, 2.5) containing a diverse number of lactate groups. The plasticizing mechanism was explained, manifesting that L-lactic acid-based plasticizers containing a substantial number of lactate groups could effectively improve the flexibility of poly (lactic acid) (PLA), and the elongation at break was 590 %-750 %. Compared to LBL-1.5 plasticized-PLA films, the tensile strength and modulus of ketonized-LBL-1.5 (KLBL-1.5) plasticized-PLA films increased to 59 % and 163 %, indicating the ketal functionality of plasticizers enhanced the strength of PLA. Meanwhile, the increment of lactate groups and the introduction of the ketal group in the plasticizer increased the crystallization, migration, and volatilization stability of plasticized-PLA films and also kept their outstanding optical transparency. Besides, the biodegradability of KLBL-1.5 was investigated by active soil and Tenebrio molitor experiments, and its degradation products were characterized. The findings indicated that KLBL-1.5 was fully decomposed. Taken together, this paper offers new promise for developing high-efficiency and biodegradable plasticizers.

Study on Properties and Degradation Behavior of Poly (Adipic Acid/Butylene Terephthalate-Co-Glycolic Acid) Copolyester Synthesized by Quaternary Copolymerization.

At present, the development and usage of degradable plastics instead of traditional plastics is an effective way to solve the pollution of marine microplastics. Poly (butylene adipate-co-terephthalate) (PBAT) is known as one of the most promising biodegradable materials. Nevertheless, the degradation rate of PBAT in water environment is slow. In this work, we successfully prepared four kinds of high molecular weight polyester copolyesters (PBATGA) via quaternary copolymerization. The results showed that the intrinsic viscosity of PBATGA copolymers ranged from 0.74 to 1.01 dL/g with a glycolic acid content of 0-40%. PBATGA copolymers had excellent flexibility and thermal stability. The tensile strength was 5~40 MPa, the elongation at break was greater than 460%, especially the elongation at break of PBATGA10 at 1235%, and the thermal decomposition temperature of PBATGA copolyesters was higher than 375 °C. It was found that PBATGA copolyester had a faster hydrolysis rate than PBAT, and the weight loss of PBATGA copolymers showed a tendency of pH = 12 > Lipase ≈ pH = 7 > pH = 2. The quaternary polymerization of PBAT will have the advantage of achieving industrialization, unlike the previous polymerization process. In addition, the polymerization of PBATGA copolyesters not only utilizes the by-products of the coal chemical industry, but also it can be promising in the production of biodegradable packaging to reduce marine plastic pollution.

Fabrication of Coral-like Polyaniline/Continuously Reinforced Carbon Nanotube Woven Composite Films for Flexible High-Stability Supercapacitor Electrodes.

The electrochemical performance is significantly influenced by the structure and surface morphology of the electrode materials used in supercapacitors. Using the floating catalytic chemical vapor deposition (FCCVD) technique, a self-supporting, flexible layer of continuously reinforced carbon nanotube woven film (CNWF) was developed. Then, polyaniline (PANI) was formed in the conductive network of CNWF using cyclic voltammetry electrochemical polymerization (CVEP) in various aqueous electrolytes to produce a series of flexible CNWF/PANI composite films. The impacts of the CVEP period, electrolyte type, and electrolyte concentration on the surface morphology, doping degree, and hydrophilicity of CNWF/PANI composite films were thoroughly examined. The CNWF/PANI1-15C composite electrode, which was created using 15 cycles of CVEP in a solution of 1 M sodium bisulfate, displayed a distinctive coral-like PANI layer with a well-defined sharp nanoprotuberance structure, a 48% doping degree, and a quick reversible pseudocapacitive storage mechanism. At a current density of 1 A g-1, the energy density and specific capacitance reached 54.9 Wh kg-1 and 1098.0 F g-1, respectively, with a specific capacitance retention rate of 75.9% maintained at 10 A g-1. Both the specific capacitance and coulomb efficiency were maintained at 96.9% and more than 98.1% of their initial values after being subjected to 2000 cycles of galvanostatic charge and discharge, demonstrating excellent electrochemical cycling stability. The CNWF/PANI1-15C composite film, an ideal electrode material, offers a promising future in the field of flexible energy storage due to its exceptional mechanical properties (127.9 MPa tensile strength and 16.2% elongation at break).

Poly(Butylene Adipate/Terephthalate-Co-Glycolate) Copolyester Synthesis Based on Methyl Glycolate with Improved Barrier Properties: From Synthesis to Structure-Property.

The main problem of manufacturing with traditional biodegradable plastics is that it is more expensive than manufacturing with polymers derived from petroleum, and the application scope is currently limited due to poor comprehensive performance. In this study, a novel biodegradable poly(butylene adipic acid/terephthalate-co-glycolic acid) (PBATGA) copolyester with 25-60% glycolic acid units was successfully synthesized by esterification and polycondensation using cheap coal chemical byproduct methyl glycolate instead of expensive glycolic acid. The structure of the copolyester was characterized by ATR-FTIR, 1H NMR, DSC, and XRD; and its barrier property, water contact angle, heat resistance, and mechanical properties were tested. According to the experiment result, the PBATGA copolyesters showed improved oxygen (O2) and water vapor barrier character, and better hydrophilicity when compared with PBAT. The crystallization peaks of PBATGAs were elevated from 64 °C to 77 °C when the content of the GA unit was 25 mol %, meanwhile, the elongation at the break of PBATGA25 was more than 1300%. These results indicate that PBATGA copolyesters have good potentiality in high O2 and water vapor barrier and degradable packaging material.

Continuously Reinforced Carbon Nanotube Film Sea-Cucumber-like Polyaniline Nanocomposites for Flexible Self-Supporting Energy-Storage Electrode Materials.

The charge storage mechanism and capacity of supercapacitors completely depend on the electrochemical and mechanical properties of electrode materials. Herein, continuously reinforced carbon nanotube film (CNTF), as the flexible support layer and the conductive skeleton, was prepared via the floating catalytic chemical vapor deposition (FCCVD) method. Furthermore, a series of novel flexible self-supporting CNTF/polyaniline (PANI) nanocomposite electrode materials were prepared by cyclic voltammetry electrochemical polymerization (CVEP), with aniline and mixed-acid-treated CNTF film. By controlling the different polymerization cycles, it was found that the growth model, morphology, apparent color, and loading amount of the PANI on the CNTF surface were different. The CNTF/PANI-15C composite electrode, prepared by 15 cycles of electrochemical polymerization, has a unique surface, with a "sea-cucumber-like" 3D nanoprotrusion structure and microporous channels formed via the stacking of the PANI nanowires. A CNTF/PANI-15C flexible electrode exhibited the highest specific capacitance, 903.6 F/g, and the highest energy density, 45.2 Wh/kg, at the current density of 1 A/g and the voltage window of 0 to 0.6 V. It could maintain 73.9% of the initial value at a high current density of 10 A/g. The excellent electrochemical cycle and structural stabilities were confirmed on the condition of the higher capacitance retention of 95.1% after 2000 cycles of galvanostatic charge/discharge, and on the almost unchanged electrochemical performances after 500 cycles of bending. The tensile strength of the composite electrode was 124.5 MPa, and the elongation at break was 18.9%.