Biodegradable Natural Rubber Based on Novel Double Dynamic Covalent Cross-Linking

In this paper, biodegradable epoxidized natural rubber containing cyclic carbonate groups (CNR) was prepared by the reaction between epoxidized natural rubber (ENR) and carbon dioxide. Dynamic disulfide bonds and a boronic ester structure were successfully constructed and then the cross-linking network was formed by the thermally initiated “click” reaction between thiol groups of the cross-linker and the residual epoxy groups of ENR. As a result of the exquisite double dynamic covalent structure, the material exhibits high self-healing efficiency. Moreover, by virtue of the cyclic carbonate structure of the CNR, the natural rubber was confirmed to be biodegradable according to the biodegradable measurement. To the best of our knowledge, natural rubber with biodegradable and self-healing characteristics was obtained for the first time

Cloning, expression and characterization of COI1 gene (AsCOI1) from Aquilaria sinensis (Lour.) Gilg

Aquilaria sinensis, a kind of typically wounding-induced medicinal plant with a great economical value, is widely used in the production of traditional Chinese medicine, perfume and incense. Coronatine-insensitive protein 1 (COI1) acts as a receptor in jasmonate (JA) signaling pathway, and regulates the expression of JA-responsive genes in plant defense. However, little is known about the COI1 gene in A. sinensis. Here, based on the transcriptome data, a full-length cDNA sequence of COI1 (termed as AsCOI1) was firstly cloned by RT–PCR and rapid-amplification of cDNA ends (RACE) strategies. AsCOI1 is 2330 bp in length (GenBank accession No. KM189194), and contains a complete open frame (ORF) of 1839 bp. The deduced protein was composed of 612 amino acids, with a predicted molecular weight of 68.93 kDa and an isoelectric point of 6.56, and was predicted to possess F-box and LRRs domains. Combining bioinformatics prediction with subcellular localization experiment analysis, AsCOI1 was appeared to locate in nucleus. AsCOI1 gene was highly expressed in roots and stems, the major organs of agarwood formation. Methyl jasmonate (MeJA), mechanical wounding and heat stress could significantly induce the expression level of AsCOI1 gene. AsCOI1 is an early wound-responsive gene, and it likely plays some role in agarwood formation

Molecular Dynamic and Dissipative Particle Dynamic Simulation on the Miscibility of NR/CR Blends

Natural rubber (NR) exhibits good elasticity, flexural resistance, wear resistance, and excellent mechanical properties, and it has been widely used in aerospace, transportation, medical, and health fields. For NR, however, the resistance to thermal-oxidation and ozone aging is fairly poor. Although aging properties of NR can be significantly improved with the incorporation of chloroprene rubber (CR) according to some references, the miscibility between NR and CR, the morphologies of the binary blends, and so on are revealed ambiguously. In this work, molecular dynamics simulation (MD) and dissipative particle dynamics (DPD) simulation were carried out to predict the compatibility between natural rubber and chloroprene rubber in view of Flory–Huggins parameters. The morphologies of the blends were obtained with the use of the DPD method. The simulation results were furtherly examined by means of Fourier transform infrared spectroscopy (FT-IR) and dynamic mechanical analysis (DMA). It was found that the miscibility between NR and CR is poor. Nevertheless, the miscibility could be improved when the content of CR is 50% or 90%. In addition, spinodal decomposition with a critical temperature of 390 K would take place according to the phase diagram. Microphase structure such as spherical, lamellar, and bicontinuous phases can be found with different contents of CR in the blends with the results of morphologies analysis

Molecular Dynamic and Dissipative Particle Dynamic Simulation on the Miscibility of NR/CR Blends

Natural rubber (NR) exhibits good elasticity, flexural resistance, wear resistance, and excellent mechanical properties, and it has been widely used in aerospace, transportation, medical, and health fields. For NR, however, the resistance to thermal-oxidation and ozone aging is fairly poor. Although aging properties of NR can be significantly improved with the incorporation of chloroprene rubber (CR) according to some references, the miscibility between NR and CR, the morphologies of the binary blends, and so on are revealed ambiguously. In this work, molecular dynamics simulation (MD) and dissipative particle dynamics (DPD) simulation were carried out to predict the compatibility between natural rubber and chloroprene rubber in view of Flory–Huggins parameters. The morphologies of the blends were obtained with the use of the DPD method. The simulation results were furtherly examined by means of Fourier transform infrared spectroscopy (FT-IR) and dynamic mechanical analysis (DMA). It was found that the miscibility between NR and CR is poor. Nevertheless, the miscibility could be improved when the content of CR is 50% or 90%. In addition, spinodal decomposition with a critical temperature of 390 K would take place according to the phase diagram. Microphase structure such as spherical, lamellar, and bicontinuous phases can be found with different contents of CR in the blends with the results of morphologies analysis

Graphene networks and their influence on free-volume properties of graphene-epoxidized natural rubber composites with a segregated structure: rheological and positron annihilation studies

Epoxidized natural rubber-graphene (ENR-GE) composites with segregated GE networks were successfully fabricated using the latex mixing combined in situ reduced technology. The rheological behavior and electrical conductivity of ENR-GE composites were investigated. At low frequencies, the storage modulus (G′) became frequency-independent suggesting a solid-like rheological behavior and the formation of GE networks. According to the percolation theory, the rheological threshold of ENR-GE composites was calculated to be 0.17 vol%, which was lower than the electrical threshold of 0.23 vol%. Both percolation thresholds depended on the evolution of the GE networks in the composites. At low GE concentrations (<0.17 vol%), GE existed as individual units, while a "polymer-bridged GE network" was constructed in the composites when GE concentrations exceeded 0.17 vol%. Finally, a "three-dimensional GE network" with percolation conductive paths was formed with a GE concentration of 0.23 vol%, where a remarkable increase in the conductivity of ENR-GE composites was observed. The effect of GE on the atom scale free-volume properties of composites was further studied by positron annihilation lifetime spectroscopy and positron age momentum correlation measurements. The motion of ENR chains was retarded by the geometric confinement of "GE networks", producing a high-density interfacial region in the vicinity of GE nanoplatelets, which led to a lower ortho-positronium lifetime intensity and smaller free-volume hole size

Polydopamine-Coated Natural Rubber Sponge for Highly Efficient Vapor Generation

The global water crisis is becoming more and more serious, and solar steam generation has recently been investigated for clean water production and wastewater treatment. However, the efficiency of solar vapor transfer is still low. It is a great challenge to find photothermal materials which simultaneously have high energy transfer efficiency, facile production, and are low cost. To address this, we propose a method which is simple, low cost and suitable for large-scale preparation to fabricate the photothermal materials based on using recycled natural rubber sponge (NRS) coated with polydopamine (PDA). X-ray photoelectron spectroscopy analysis confirmed that when the PDA coated the surface of the NRS, the hydrophilicity of the sponge was significantly improved. Scanning electron microscopy characterization showed that the PDA-coated natural rubber sponge (PNRS) maintained the porous 3D skeleton of the pristine sponge. As a result, PNRS exhibits excellent photothermal properties, a very high evaporation rate of 1.35 kg m−2 h−1, and an energy transfer efficiency of 84.6% can be achieved under a light intensity of 1 sun (1 kW m−2). It is worth noting that the vapor generation of PNRS is still at a high level with 1.06 and 1.09 kg m−2 h−1 in the corrosive liquids of 1 M H2SO4 and 0.5 M NaOH, respectively. The photothermal materials based on using recycled NRS have good application prospects in seawater desalination and the purification of wastewater, which also provides a new method for the recycling of waste NRS

Synthesis of PNIPAAm-g-P4VP Microgel as Draw Agent in Forward Osmosis by RAFT Polymerization and Reverse Suspension Polymerization to Improve Water Flux

Microgels have unique and versatile properties allowing their use in forward osmosis areas as a draw agent. In this contribution, poly(4-vinylpyridine) (P4VP) was synthesized via RAFT polymerization and then grafted to a poly(N-Isopropylacrylamide) (PNIPAAm) crosslinking network by reverse suspension polymerization. P4VP was successfully obtained by the quasiliving polymerization with the result of nuclear magnetic resonance and gel permeation chromatography characterization. The particle size and particle size distribution of the PNIPAAm-g-P4VP microgels containing 0, 5, 10, 15 and 20 wt% P4VP were measured by means of a laser particle size analyzer. It was found that all the microgels were of micrometer scale and the particle size was increased with the P4VP load. Inter/intra-molecular-specific interactions, i.e., hydrogen bond interactions were then investigated by Fourier infrared spectroscopy. In addition, the water flux measurements showed that all the PNIPAAm-g-P4VP microgels can draw water more effectively than a blank PNIPAAm microgel. For the copolymer microgel incorporating 20 wt% P4VP, the water flux was measured to be 7.48 L∙m−2∙h−1

Enhanced Ozone Aging Resistance of Natural Rubber with 2-Mercaptobenzothiazole as the Constant-Viscosity Agent

For the actual storage and serving, a phenomenon of hardening and cracking always occurs in the natural rubber (NR), which sharply reduces the mechanical performance and hinders the further application of NR. Recently, some type of constant-viscosity agent has played a key role to be used for the treatment of NR, especially for the effect of ozone aging resistance. In this study, 2-mercaptobenzothiazole (MBT) was introduced into NR, and the constant viscosity and ozone aging resistance of NR with different contents of MBT were investigated using an accelerated storage experiment and an ozone aging experiment, respectively. The results indicated that the addition of MBT could improve the constant viscosity of NR in a certain degree. With the MBT content of 0.15%, NR/MBT-0.15 obtained a best ozone aging resistance and maintained the original high tensile strength. Therefore, it provided a promising route to design and prepare NR with high-quality ozone aging resistance

Natural Hollow Fiber-Derived Carbon Microtube with Broadband Microwave Attenuation Capacity

Constructing hierarchical structures is indispensable to tuning the electromagnetic properties of carbon-based materials. Here, carbon microtubes with nanometer wall thickness and micrometer diameter were fabricated by a feasible approach with economical and sustainable kapok fiber. The carbonized kapok fiber (CKF) exhibits microscale pores from the inherent porous templates as well as pyrolysis-induced nanopores inside the wall, affording the hierarchical carbon microtube with excellent microwave absorbing performance over broad frequency. Particularly, CKF-650 exhibits an optimized reflection loss (RL) of −62.46 dB (10.32 GHz, 2.2 mm), while CKF-600 demonstrates an effective absorption bandwidth (RL < −10 dB) of 6.80 GHz (11.20–18.00 GHz, 2.8 mm). Moreover, more than 90% of the incident electromagnetic wave ranging from 2.88 GHz to 18.00 GHz can be dissipated by simply controlling the carbonization temperature of KF and/or the thickness of the carbon-microtube-based absorber. These encouraging findings provide a facile alternative route to fabricate microwave absorbers with broadband attenuation capacity by utilizing sustainable biomass

Effect of Nonisoprene Degradation and Naturally Occurring Network during Maturation on the Properties of Natural Rubber

It well-known that the superior performance of natural rubber (NR) compared to its synthetic counterpart mainly derives from nonisoprene components and naturally occurring network, which varies during the progress of the maturation and thereby results in technically graded rubber with different properties. However, identifying the roles of these two factors in the forming of excellent performance of NR is still a challenge as they change simultaneously during the maturation process. Here, influences of naturally occurring networking and nonisoprene degradation on the components, structures and properties of NR were systematically investigated by tailored treatments of maturation. It was found that the maturation-induced formation of natural network structure contributes to the increase in initial plastic value, Mooney viscosity and gel content for un-crosslinked NR, while the decomposition of nonisoprene components plays a dominant role in improving the mechanical properties of vulcanized NR. Stress-strain curve and Mooney-Rivlin analysis demonstrate that the biodegradation of the nonisoprene components significantly boost the vulcanization process, which significantly increases the number of chemical cross-link networks and effective cross-link density of the material, greatly improving the mechanical properties of NR vulcanizates. This resulted in the tensile strength of TSR 10CV being able to reach 22.6 MPa, which is significantly improved compared to 15.8 MPa of TSR 3CV. Evidenced by tubular model fitting, the increase in chemical cross-linking points effectively reduces the movable radius of the molecular chain under dynamic loading, making the molecular chain more difficult to move, which suppresses the entropy change under dynamic loading and consequently endows NR excellent dynamic mechanical properties. This resulted in a significant decrease in the temperature rising of TSR 10CV to 3.3 °C, while the temperature rising of TSR 3CV was still as high as 14.5 °C. As a minor factor, the naturally occurring network improves the mechanical properties of vulcanizates in the form of sacrificial bonds