Polymers2016, 8(6), 207; doi:10.3390/polym8060207 (registering DOI) - published 27 May 2016 Show/Hide Abstract
Abstract: This paper describes a very simple strategy towards self-stabilized poly(acrylic acid)-block-poly(hexafluorobutyl acrylate) (PAA-b-PHFBA) block copolymer particles via reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization-induced self-assembly. Hexafluorobutyl acrylate (HFBA) monomer conversion and number-average molar mass of PAA-b-PHFBA increased gradually with the increase in the pH value of the aqueous phase. When pH < 10, the molecular weight distributions of PAA-b-PHFBA were narrow, however, when the pH was raised to 11.55, PAA-b-PHFBA block copolymers had a broader distribution (ĐM = 1.82) with a serious trailing toward the low molecular weight. Furthermore, the morphology and size of PAA-b-PHFBA latex particles were measured by transmission electron microscopy and dynamic light scattering. The results indicated that the PAA-b-PHFBA latex particles had a clear spherical core-shell structure and the latex particles’ size increased with the increase of pH value.
Polymers2016, 8(6), 206; doi:10.3390/polym8060206 (registering DOI) - published 27 May 2016 Show/Hide Abstract
Abstract: Tris(4-(thiophen-2-yl)phenyl)amine- and dithienylpyrrole-based copolymers (P(TTPA-co-DIT) and P(TTPA-co-BDTA)) were electropolymerized on ITO electrode by applying constant potentials of 1.0, 1.1, and 1.2 V. Spectroelectrochemical investigations revealed that P(TTPA-co-DIT) film displayed more color changes than P(TTPA-co-BDTA) film. The P(TTPA-co-DIT) film is yellow in the neutral state, yellowish-green and green in the intermediate state, and blue (1.2 V) in highly oxidized state. The ∆Tmax of the P(TTPA-co-DIT) and P(TTPA-co-BDTA) films were measured as 60.3% at 1042 nm and 47.1% at 1096 nm, respectively, and the maximum coloration efficiency (η) of P(TTPA-co-DIT) and P(TTPA-co-BDTA) films were calculated to be 181.9 cm2·C−1 at 1042 nm and 217.8 cm2·C−1 at 1096 nm, respectively, in an ionic liquid solution. Dual type electrochromic devices (ECDs) consisting of P(TTPA-co-DIT) (or P(TTPA-co-BDTA)) anodic copolymer, ionic liquid-based electrolyte, and poly(3,4-(2,2-diethylpropylenedioxy)thiophene) (PProDOT-Et2) cathodic polymer were constructed. P(TTPA-co-BDTA)/PProDOT-Et2 ECD showed high ΔTmax (48.1%) and high coloration efficiency (649.4 cm2·C−1) at 588 nm. Moreover, P(TTPA-co-DIT)/PProDOT-Et2 and P(TTPA-co-BDTA)/PProDOT-Et2 ECDs displayed satisfactory optical memory and long term switching stability.
Abstract: Carbon microparticles were produced from organosolv lignin at 2000 °C under argon atmosphere following oxidative thermostabilisation at 250 °C. Scanning electron microscopy, X-ray diffraction, small-angle X-ray scattering, and electro-conductivity measurements revealed that the obtained particles were electrically conductive and were composed of large graphitic domains. Poly(lactic acid) filled with various amounts of lignin-derived microparticles showed higher tensile stiffness increasing with particle load, whereas strength and extensibility decreased. Electric conductivity was measured at filler loads equal to and greater than 25% w/w.
Abstract: The photostability of poly(vinyl chloride), PVC, containing various Schiff base metal complexes (0.5% by weight) was investigated. Various indices corresponding to a number of functional groups were monitored with irradiation of polymeric films to determine their photostabilization activities. The quantum yield of the chain scission (Φcs) of modified polymeric films was found to be (1.15–4.65) × 106. The surface morphology of a PVC sample was investigated by the use of atomic force microscope (AFM). The photostability of PVC films in the presence of Schiff base additives was found to follow the following order: PVC < PVC + CuL2 < PVC + CdL2 < PVC + ZnL2 < PVC + SnL2 < PVC + NiL2. Various mechanisms for PVC films photostability containing the Schiff base additives have been suggested.
Abstract: Biomacromolecule activity is usually related to its ability to keep a specific structure. However, in solution, many parameters (pH, ionic strength) and external compounds (polyelectrolytes, nanoparticles) can modify biomacromolecule structure as well as acid/base properties, thus resulting in a loss of activity and denaturation. In this paper, the impact of neutral and charged nanoparticles (NPs) is investigated by Monte Carlo simulations on polypeptide (PP) chains with primary structure based on bovine serum albumin. The influence of pH, salt valency, and NP surface charge density is systematically studied. It is found that the PP is extended at extreme pH, when no complex formation is observed, and folded at physiological pH. PP adsorption around oppositely-charged NPs strongly limits chain structural changes and modifies its acid/base properties. At physiological pH, the complex formation occurs only with positively-charged NPs. The presence of salts, in particular those with trivalent cations, introduces additional electrostatic interactions, resulting in a mitigation of the impact of negative NPs. Thus, the corona structure is less dense with locally-desorbed segments. On the contrary, very limited impact of salt cation valency is observed when NPs are positive, due to the absence of competitive effects between multivalent cations and NP.
Abstract: The microstructure of compression molded Estane 5703 films exposed to 11%, 45%, and 80% relative humidity and 70 °C for 1 and 2 months has been studied by small-angle neutron scattering (SANS), Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Scattering data indicated increase of the interdomain distance and domain size with a higher humidity and longer aging time. GPC data showed a progressive shortening of polyurethane chains with increasing humidity and aging time. The shortening of the polyurethane chains caused a drop of the glass transition temperature of soft segments, and promoted crystallization of the soft segments during long-time storage of the aged samples at room temperature. FTIR showed a substantial increase in the number of inter-urethane H-bonds in the aged samples. This correlates with the increase of the hard domain size and the degree of phase separation as measured by SANS. The data collected reveals that the reduced steric hindrance caused by hydrolysis of ester links in polybutylene adipate residues promotes the organization of hard segments into domains, leading to the increase of domain size and distance, as well as phase segregation in aged Estane. These findings provide insight into the effects of humidity and thermal aging on the microstructure of aged polyester urethane from molecular to nanoscale level.