Effect of Modified Natural Rubber on the Mechanical and Thermal Properties of Poly(Lactic Acid) and Its Composites with Nanoparticles from Biowaste.

The brittle behavior of poly(lactic acid) (PLA) and PLA composites with inorganic filler limits their applications; the addition of a toughening agent, such as a rubbery phase, was selected to transform the brittle to ductile behavior for versatility in various applications. This work aims to study the properties of PLA and PLA composite with filled nanosized hydroxyapatite (nHA) after adding modified natural rubber (MoNR), which acts as a toughening agent. MoNR refers to poly(acrylic acid-co-acrylamide)-grafted deproteinized natural rubber. nHA was prepared from fish scales. Its characteristics were investigated and was confirmed to be comparable to those of commercial grade. PLA-MoNR at various MoNR contents and PLA/nHA composites with/without MoNR were prepared by melt mixing. Their morphology, mechanical, and thermal properties were observed and investigated. Samples with MoNR added showed the dispersion of spherical particles, indicating incompatibility. However, the mechanical properties of PLA-MoNR, which had MoNR added at 10 phr, showed toughening behavior (increased impact strength by more than two times compared to that of neat PLA). The PLA/nHA composite with MoNR showed the same result. The addition of MoNR in the composite increased its impact strength by 1.27 times compared to the composite without MoNR. MoNR can be a stress concentrator, resulting in toughened PLA and PLA/nHA composite.

Preparation of Crosslinked Poly(acrylic acid-co-acrylamide)-Grafted Deproteinized Natural Rubber/Silica Composites as Coating Materials for Controlled Release of Fertilizer.

The crosslinked poly(acrylic acid-co-acrylamide)-grafted deproteinized natural rubber/silica ((PAA-co-PAM)-DPNR/silica) composites were prepared and applied as coating materials for fertilizer in this work. The crosslinked (PAA-co-PAM)-DPNR was prepared via emulsion graft copolymerization in the presence of MBA as a crosslinking agent. The modified DPNR was mixed with various contents of silica (10 to 30 phr) to form the composites. The existence of crosslinked (PAA-co-PAM) after modification provided a water adsorption ability to DPNR. The swelling degree values of composites were found in the range of 2217.3 ± 182.0 to 8132.3 ± 483.8%. The addition of silica in the composites resulted in an improvement in mechanical properties. The crosslinked (PAA-co-PAM)-DPNR with 20 phr of silica increased its compressive strength and compressive modulus by 1.61 and 1.55 times compared to the unloaded silica sample, respectively. There was no breakage of samples after 80% compression strain. Potassium nitrate, a model fertilizer, was loaded into chitosan beads with a loading percentage of 40.55 ± 1.03% and then coated with the modified natural rubber/silica composites. The crosslinked (PAA-co-PAM)-DPNR/silica composites as the outer layers had the ability of holding water in their structure and retarded the release of fertilizer. These composites could be promising materials for controlled release and water retention that would have potential for agricultural application.

The Effect of Silver Nanoparticles/Titanium Dioxide in Poly(acrylic acid-co-acrylamide)-Modified, Deproteinized, Natural Rubber Composites on Dye Removal.

This work aims to enhance the dye-removal performance of prepared poly(acrylic acid-co-acrylamide)-modified, deproteinized, natural rubber ((PAA-co-PAM)-DPNR) through incorporation with silver nanoparticles/titanium dioxide. The (PAA-co-PAM)-DPNR was prepared by emulsion-graft copolymerization with a grafting efficiency of 10.20 ± 2.33 to 54.26 ± 1.55%. The composites based on (PAA-co-PAM)-DPNR comprising silver nanoparticles and titanium dioxide ((PAA-co-PAM)-DPNR/Ag-TiO2) were then prepared by latex compounding using the fixed concentration of AgNO3 (0.5 phr) and varying concentrations of TiO2 at 1.0, 2.5, and 5.0 phr. The formation of silver nanoparticles was obtained by heat and applied pressure. The composites had a porous morphology as they allowed water to diffuse in their structure, allowing the high specific area to interact with dye molecules. The incorporation of silver nanoparticles/titanium dioxide improved the compressive modulus from 1.015 ± 0.062 to 2.283 ± 0.043 KPa. The (PAA-co-PAM)-DPNR/Ag-TiO2 composite with 5.0 phr of TiO2 had a maximum adsorption capacity of 206.42 mg/g, which increased by 2.02-fold compared to (PAA-co-PAM)-DPNR. The behavior of dye removal was assessed with the pseudo-second-order kinetic model and Langmuir isotherm adsorption model. These composites can maintain their removal efficiency above 90% for up to five cycles. Thus, these composites could have the potential for dye-removal applications.

Preparation of Poly(acrylic acid-co-acrylamide)-Grafted Deproteinized Natural Rubber and Its Effect on the Properties of Natural Rubber/Silica Composites.

This work aims to enhance the polarity of natural rubber by grafting copolymers onto deproteinized natural rubber (DPNR) to improve its compatibility with silica. Poly(acrylic acid-co-acrylamide)-grafted DPNR ((PAA-co-PAM)-DPNR) was successfully prepared by graft copolymerization with acrylic acid and acrylamide in the latex stage, as confirmed by FTIR. The optimum conditions to obtain the highest conversion, grafting efficiency, and grafting percentage were a reaction time of 360 min, a reaction temperature of 50 °C, and an initiator concentration of 1.0 phr. The monomer conversion, grafting efficiency, and grafting percentage were 91.9-94.1, 20.8-38.9, and 2.1-9.9%, respectively, depending on the monomer content. It was shown that the polarity of the natural rubber increased after grafting. The (PAA-co-PAM)-DPNR was then mixed with silica to prepare DPNR/silica composites. The presence of the (PAA-co-PAM)-DPNR and silica in the composites was found to improve the mechanical properties of the DPNR. The incorporation of 10 phr of silica into the (PAA-co-PAM)-DPNR with 10 phr monomer increased its tensile strength by 1.55 times when compared to 10 phr of silica loaded into the DPNR. The silica-filled (PAA-co-PAM)-DPNR provided s higher storage modulus, higher Tg, and a lower tan δ peak, indicating stronger modified DPNR/silica interactions and greater thermal stability when compared to silica-filled DPNR.

Chitosan/carboxymethylcellulose-stabilized poly(lactide-co-glycolide) particles as bio-based drug delivery carriers.

Poly(lactide-co-glycolide) (PLGA) colloidal particles stabilized by complexes of two oppositely charged polysaccharides, chitosan (cationic, CS) and sodium carboxymethylcellulose (anionic, NaCMC), were fabricated. Dichloromethane containing dissolved PLGA was first emulsified in an aqueous phase containing mixtures of CS and NaCMC. Evaporation of dichloromethane from the resulting emulsion led to CS/NaCMC-covered-PLGA particles. CS and NaCMC contents affected the short-term stability of PLGA particles and also their intrinsic characteristics. The particles displayed pH-dependent characteristic. Zeta potential varied from +54 to -50 mV when pH was varied from 3 to 10. CS/NaCMC-covered-PLGA particles showed colloidal stability, over a wider pH range as compared to CS-covered-PLGA particles. Curcumin, a model hydrophobic drug, was encapsulated into the particles up to 10 wt% of PLGA. The CS/NaCMC-covered-PLGA particles loaded with curcumin showed delayed release in mildly acidic conditions and faster release in neutral and basic conditions. Cytotoxicity experiments were carried out with human colorectal carcinoma cells.

Synthesis of poly(methyl methacrylate) core/chitosan-mixed-polyethyleneimine shell nanoparticles and their antibacterial property.

The core-shell nanoparticles possessing poly(methyl methacrylate) (PMMA) core coated with chitosan (CS), polyethyleneimine (PEI), and chitosan-mixed-polyethyleneimine (CS/PEI) shells were synthesized in this work. The emulsifier-free emulsion polymerization triggered by a redox initiating system from t-butylhydroperoxide (TBHP) and amine groups on CS and/or PEI was used as a synthetic method. In the CS/PEI systems, the amount of CS was kept constant (0.5g), while the amount of PEI was varied from 0.1 to 0.5g. The surface and physico-chemical properties of prepared nanoparticles were then examined. FTIR spectra indicated the presence of grafted PMMA on CS and/or PEI, and the weight fraction of incorporated PEI in the CS/PEI nanoparticles. All nanoparticles were spherical in shape with uniform size distribution illustrated by scanning electron microscopy (SEM). The introduction of PEI to CS nanoparticles yielded the higher monomer conversion, grafting efficiency, and grafting percentage compared with the CS nanoparticles. The size of CS/PEI nanoparticles was smaller than the original CS and PEI nanoparticles, and tended to decrease with increasing amount of PEI introduced. The introduction of PEI also brought the higher colloidal stability to the nanoparticles as indicated by zeta-potential measurement and isoelectric point analysis. The nanoparticles exhibited a promising antibacterial activity against Staphylococcus aureus and Escherichia coli. The nanoparticle-bacteria interaction was studied via SEM. The results suggested that they would be useful as effective antibacterial agents.

Gene delivery efficacy of polyethyleneimine-introduced chitosan shell/poly(methyl methacrylate) core nanoparticles for rat mesenchymal stem cells.

This work investigated polyethyleneimine (PEI)-introduced chitosan (CS) (CS/PEI) nanoparticles as non-viral carrier of plasmid DNA for rat mesenchymal stem cells (MSCs). The CS/PEI nanoparticles were prepared by the emulsifier-free emulsion polymerization of methyl methacrylate monomer induced by a small amount of t-butyl hydroperxide in the presence of different concentrations of PEI mixed with CS. The resulting nanoparticles were characterized by their surface properties and buffering capacity. In vitro gene transfection was also evaluated. The introduction of PEI affected the surface charge, dispersing stability and buffering capacity of the nanoparticles. The CS/PEI nanoparticles formed a complex upon mixing with a plasmid DNA of luciferase. The complex enhanced the level of gene transfection and prolonged the time period of expression for MSCs, compared with those of plasmid DNA-original CS and PEI nanoparticles. Cytotoxicity of CS/PEI complexes with plasmid DNA was significantly low, depending on the amount of PEI introduced. It is concluded that the CS/PEI nanoparticle was a promising carrier for gene delivery of MSCs.