Rosin-based self-healing functionalized composites with two-dimensional polyamide for antimicrobial and anticorrosion coatings.

The design of polymer-based composites possessing good mechanical and self-healing properties remains a challenge in the development of high-performance self-healing materials. In this study, we used two-dimensional polyamide (2DPA), biomass rosin ester, and a dynamic crosslinking agent poly (urethane-urea) as raw materials, and prepared biomass rosin-based composites via in situ polymerization. The composites with 1 wt% 2DPA exhibited excellent self-healing properties (self-healing efficiency of 94 % after 24 h at 80 °C) and mechanical properties (tensile strength = 7.8 MPa). Moreover, the composites were applied to anticorrosion and antimicrobial coatings, which possessed excellent anticorrosion and antimicrobial properties. This study provides a new strategy for developing high-performance bio-based self-healing composites.

Preparation and pH Detection Performance of Rosin-Based Fluorescent Polyurethane Microspheres.

Rosin-based fluorescent polyurethane emulsion (FPU) was prepared using isophorone diisocyanate, ester of acrylic rosin and glycidyl methacrylate, 1,5-dihydroxy naphthalene (1,5-DN), and 1,4-butanediol as the raw materials. Then, rosin-based fluorescent polyurethane microspheres (FPUMs) were successfully prepared by suspension polymerization method using FPU as the main material, azodiisobutyronitrile as the initiator, and gelatin as the dispersant. FPUMs were characterized by Fourier transform infrared spectra, thermogravimetric analysis, optical microscopy, scanning electron microscopy and fluorescence spectra, and the response performance of FPUMs to pH was studied. The results showed that FPUMs were successfully prepared. With the increase of the level of 1,5-DN, the particle size of FPUMs increased gradually, and the fluorescence intensity increased first and then decreased. When the level of 1,5-DN was 3 wt.%, the average particle size was 49.3 µm, the particle distribution index (PDI) was 1.05, and the fluorescence intensity was the largest (3662 a.u.). The fluorescence intensity of FPUMs increased linearly with the decrease of pH, which can be used for pH detection in solution. Furthermore, the FPUMs exhibited good thermal stability, anti-interference and recoverability.

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

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.

Preparation and Properties of Hydrophilic Rosin-Based Aromatic Polyurethane Microspheres.

Hydrophilic aromatic polyurethane (HAPU) microspheres were prepared through dispersion polymerization of a rosin-based polyurethane dispersion with C=C and styrene (St). The effects of the monomer ratio (i.e., waterborne rosin-based aromatic polyurethane (WRPU) to St), dispersant level, and reaction temperature on the properties of the microspheres were investigated; the effects of pH and adsorption temperature on the adsorption capacity of Orange II were also studied. The microspheres were characterized using Fourier transform infrared spectroscopy, energy-dispersive spectrometry, thermogravimetric analysis, laser particle size analysis, and scanning electron microscopy. The results showed that HAPU microspheres have been successfully synthesized and the produced microspheres exhibited good thermal stability and monodispersion. The optimum reaction conditions for the preparation of the microspheres were determined as a monomer ratio (m WRPU/m St) of 6:4 with 8 wt % poly(vinyl pyrrolidine) (on the basis of the mixed monomer) at 80 °C for 8 h. Under these conditions, the average particle size of the synthetic microspheres was 120 nm and the particle size distribution index was 0.442. The microspheres' adsorption capacity for Orange II reached 17.53 mg·g-1 when the solid-liquid ratio was 1 g·L-1, with an initial concentration of 100 mg·L-1 at pH 5, and the adsorption was conducted at 313 K for 3 h.

Enhancing the colloidal stability and surface functionality of molybdenum disulfide (MoS2) nanosheets with hyperbranched polyglycerol for photothermal therapy.

Molybdenum disulfide (MoS2) nanosheets are gaining increasing attention due to their attractive properties and myriads of potential applications. However, challenges in the enhancement of their colloidal stability and surface functionality still remain and significantly restrict their practical applications. Herein, we present a viable approach to functionalize MoS2 nanosheets with multihydroxy hyperbranched polyglycerol (HPG) shell by surface-initiated ring-opening polymerization technique. The grafting of HPG from the surface of MoS2 nanosheet yielded MoS2-g-HPG nanohybrid with excellent water dispersibility, good biocompatibility, and greatly enhanced colloidal stability against pH change, ionic strength variation and long-term storage. The MoS2-g-HPG also exhibited excellent light-to-heat conversion capability for in vitro photothermal therapy application. Meanwhile, the MoS2-g-HPG showed favorable surface functionality owing to its numerous surface hydroxyl groups, as demonstrated by the conjugation of functional molecules such as fluorescent dye rhodamine B. As such, this paper opens up new opportunities to empower MoS2 nanosheets and other two-dimensional inorganic nanosheets with desired properties for various applications.

Facile fabrication of magnetic carboxymethyl starch/poly(vinyl alcohol) composite gel for methylene blue removal.

This study presents a simple method to fabricate magnetic carboxymethyl starch/poly(vinyl alcohol) (mCMS/PVA) composite gel. The obtained mCMS/PVA was characterized by Fourier transform infrared (FTIR) spectra, vibrating-sample magnetometer (VSM) and scanning electron microscopy (SEM) measurements. The application of mCMS/PVA as an adsorbent for removal of cationic methylene blue (MB) dye from water was investigated. Benefiting from the combined merits of carboxymethyl starch and magnetic gel, the mCMS/PVA simultaneously exhibited excellent adsorption property toward MB and convenient magnetic separation capability. The effects of initial dye concentration, contact time, pH and ionic strength on the adsorption performance of mCMS/PVA adsorbent were investigated systematically. The adsorption process of mCMS/PVA for MB fitted pseudo-second-order model and Freundlich isotherm. Moreover, desorption experiments revealed that the mCMS/PVA adsorbent could be well regenerated in ethanol solution without obvious compromise of removal efficiency even after eight cycles of desorption/adsorption. Considering the facile fabrication process and robust adsorption performance, the mCMS/PVA composite gel has great potential as a low cost adsorbent for environmental decontamination.

Peach gum for efficient removal of methylene blue and methyl violet dyes from aqueous solution.

This study investigated the potential use of natural peach gum (PG) as alternative adsorbent for the removal of dyes from aqueous solutions. The PG showed high adsorption capacities and selectivity for cationic dyes (e.g., methylene blue (MB) and methyl violet (MV)) in the pH range 6-10. 98% of MB and MV could be adsorbed within 5 min, and both of the adsorptions reached equilibrium within 30 min. The dye uptake process followed the pseudo-second-order kinetic model. The intraparticle diffusion was not the sole rate controlling step. Equilibrium adsorption isotherm data indicated a good fit to the Langmuir isotherm model. Regeneration study revealed that PG could be well regenerated in acid solution. The recovered PG still exhibited high adsorption capacity even after five cycles of desorption-adsorption. On the basis of its excellent adsorption performance and facile availability, PG can be employed as an efficient low cost adsorbent for environmental cleanup.

Facile one-pot synthesis of iron oxide nanoparticles cross-linked magnetic poly(vinyl alcohol) gel beads for drug delivery.

In this paper, a facile one-pot strategy for scalable synthesis of robust magnetic poly(vinyl alcohol) (mPVA) gel beads is developed. Through dropwise addition of mixed aqueous solution of iron salts and PVA solution into alkaline (e.g., ammonia, NaOH, and KOH) solution, mPVA gel beads with uniform size and excellent superparamagnetic property can be fabricated based on the simultaneous formation of magnetic iron oxide nanoparticles (MIONs) and cross-link of PVA chains. Moreover, this approach can be extended to prepare dual- or multiresponsive gel beads through simply adding functional fillers into PVA solution (e.g., mPVA-PNIPAM gel beads that possess both magnetic and temperature responsibilities can be readily prepared by adding temperature responsive poly(N-isopropylacrylamide) (PNIPAM) into PVA solution). It is found that that the obtained mPVA gel beads exhibit high drug loading level (e.g., above 70%) after the treatment of freezing-thawing. Drug release experiments reveal that the drug release rate and amount of the mPVA gel beads can be tuned by operating the external magnetic field and adjusting the concentration of iron oxide nanoparticles and temperature (for mPVA-PNIPAM gel beads). The present work is of interest for opening up enormous opportunities to make full use of magnetic gel beads in drug delivery and other applications, because of their facile availability, cost-effective productivity, and tunable drug release performance.