Lignin valorization by forming toughened thermally stimulated shape memory copolymeric elastomers: Evaluation of different fractionated industrial lignins

Lignin‐based thermal responsive dual shape memory copolymeric elastomers were prepared with a highly branched prepolymer (HBP, A₂B₃ type) via a simple one‐pot bulk polycondensation reaction. The effect of fractionated lignin type (with good miscibility in the HBP) on copolymer properties was investigated. The thermal and mechanical properties of the copolymers were characterized by DMA, DSC, and TGA. Tensile properties were dominated by HBP <45% lignin content while lignin dominated >45% content. The copolymers glass transition temperature (T_g) increased with lignin content and lignin type did not play a significant role. Thermally stimulated dual shape memory effects (SME) of the copolymers were quantified by cyclic thermomechanical tests. All copolymers had shape fixity rate >95% and >90% shape recovery for all compositions. The copolymer shape memory transition temperature (T_trans) increased with lignin content and T_trans was 20°C higher than T_g. Lignin, a renewable resource, can be used as a netpoint segment in polymer systems with SME behavior. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41389.     

Curing copolymerization kinetics of styrene with maleated castor oil glycerides obtained from biodiesel‐derived crude glycerol

Kinetics of curing of maleated castor oil glycerides with styrene was studied by differential scanning calorimetry and rheology. The resin was synthesized from biodiesel‐derived crude glycerol. Curing rates were fitted to several empirical models (autocatalytic model, Kamal's model and a model with vitrification). The three models showed a good fitting with experimental data at conversions lower than 0.55 for temperatures ranging from 30 to 50°C. However, the model that includes vitrification showed a better fitting in the entire range of conversions and the same temperatures. At higher temperatures (50–60°C), some deviations were observed for the three models at low and high conversions. Gel times were obtained from rheological studies and the apparent activation energies were calculated thereof. Gel times were 300–2700 s. The values of apparent activation energy obtained for this castor oil‐based copolymer (47.2–52.3 kJ/mol) were within range of commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41344.     

Preparation and properties of functionalized graphene/waterborne polyurethane composites with highly hydrophobic

The long‐chain functionalized graphene nanoplatelets (FGN) were functionalized by isophorone diisocyanate and then octadecylamine, the graphene functionalized/waterborne polyurethane (WPU) composites were prepared by solution mixture. The results showed that the FGN achieved good dispersion with exfoliated and intercalated nanostructure and strong interfacial adhesion with WPU, which made the nano–composites have a significant enhancement of thermal stability and mechanical properties at low FGN loadings. With 1.5% of FGN added, the tensile strength of the composites reached the maximum of 17 MPa, which improved by 41.6%, the water absorption of the composites is only 6.7%. With the incorporation of 2 wt % FGN, and the static contact angle of the composites reached to about 120°, showing the high hydrophobicity. At the same time, the volume resistivity of the composites was changed from 2.34 × 10¹² Ω·cm to 3.77 × 10⁹ Ω·cm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42005.     

Enhanced thermoelectric performance by alcoholic solvents effects in highly conductive benzenesulfonate‐doped poly(3,4‐ethylenedioxythiophene)/graphene composites

Benzenesulfonate‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT‐Bzs)/graphene thermoelectric (TE) composites with various graphene filler contents were synthesized in five different kinds of solvents. Dodecylbenzenesulfonic acid (DBSA) was used to achieve good dispersion of graphene into the PEDOT matrix. Among the synthesized PEDOT materials, the one synthesized in methanol (PEDOT‐MeOH) had the highest electrical conductivity. X‐ray photoelectron spectroscopy (XPS) analysis showed almost the same charge carrier concentration for all PEDOT materials. However, the X‐ray diffraction (XRD) analysis highlighted the enhancement of PEDOT chain stacking by shorter‐chain alcoholic solvents, as a result of which the carrier mobility and electrical conductivity were increased. The electrical conductivity and the Seebeck coefficient of the PEDOT/graphene composites were significantly improved with increasing the graphene content, which strongly depended on increased carrier mobility. The thermal conductivity of the composites exhibited relatively small changes, attributed to phonon scattering effects. The maximum TE efficiency of the PEDOT‐MeOH/graphene composite with 75 wt % graphene showed a substantially improved value of 1.9 × 10^?2, higher than that of the other PEDOT/graphene composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42107.     

Photodynamic antifungal activities of nanostructured fabrics grafted with rose bengal and phloxine B against Aspergillus fumigatus

This study demonstrates that nanostructured fabrics grafted with rose bengal (RB) and phloxine B (PB) have photodynamic antifungal effects on Aspergillus fumigatus. RB and PB were attached to vinyl benzyl chloride, and, subsequently, this was polymerized with acrylic acid and styrene sulfonic acid to produce long, water‐soluble polymers to attach to the fabric surface. This gave high grafting yield and photodynamic antifungal activity against A. fumigatus. In RB and PB microdilution tests, there was no visible turbidity at 63 µmol/L. When polymerized RB and PB were incorporated into fabrics, the actions of polymerized RB and PB resulted in less hyphal growth and germination of conidia on A. fumigatus than the free RB and PB dyes. Nanostructured fabrics created by bonding RB‐ or PB‐containing polymers to electrospun nylon mats exhibited higher concentrations of the dyes, equivalent to 86 µmol/L. The microstructured fabrics created by bonding RB‐ or PB‐containing polymers to spunbonded nylon nonwoven fabrics only exhibited the equivalent of 32 µmol/L of the dyes. The nanostructured fabrics had a specific surface area of 28.1 m²/g, whereas the microfabric had 1.5 m²/g. Thus, the nanostructured fabrics increased the surface area 18.7× and the reflectance percent 16.2× when compared with the microstructured fabrics. This resulted in much higher photodynamic antifungal activity against A. fumigatus. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42114.     

Epoxide‐terminated hyperbranched polyether sulphone as triple enhancement modifier for DGEBA

Epoxide‐terminated hyperbranched polyether sulphones (EHBPESs) with different backbone structures were synthesized and used as tougheners for diglycidyl ether of bisphenol‐A (DGEBA) curing system, which result in nonphase‐separated cured networks. Effects of backbone structure (at comparable degree of polymerization) and loading contents on the mechanical and thermal properties of cured hybrids were investigated. The hybrid containing EHBPES3, which has the most flexible backbone, shows the best mechanical performance and highest glass transition temperature (T_g). Compared with unmodified system, the impact strength, tensile strength, elongation at break of the hybrid containing 5% EHBPES3 increased by 69.8%, 9.4%, and 60.2%, respectively. The balanced improvements were attributed to the increased crosslink density and fractional free volume as well as the unique inhomogeneous network structure because of incorporation of hyperbranched modifiers with proper structure and loading contents. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41910.     

Design and preparation of cross‐linked α‐methylstyrene acrylonitrile copolymer nanoparticles and their interfacial investigation with rubber

Cross‐linked α‐methylstyrene and acrylonitrile (MStAN) copolymer particles in a latex form were synthesized by free radical emulsion polymerization. The particles showed a narrow size distribution and an average diameter of 65 nm. The amount of the vinyl groups at the surface of the (MStAN) copolymer particles resulted from varied amount of the initiator (APS) and the cross‐linking agent (DVB) was detected by iodine titration method. When filled into ethylene propylene rubber (EPR), the MStAN nano‐particles exhibited excellent reinforcing capabilities, and with the increase of the vinyl groups at the surface of MStAN particles, the tensile stress of MStAN/EPR increased. Results demonstrated that the vinyl groups at the surface of the (MStAN) copolymer particles provided certain chemical interactions between the filler particles and the macromolecular chains of rubber matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41914.     

Conversion of polyhydroxybutyrate (PHB) to methyl crotonate for the production of biobased monomers

Within the concept of the replacement of fossil with biobased resources, bacterial polyhydroxybutyrate (PHB) can be obtained from volatile fatty acids (VFAs) from agro‐food waste streams and used as an intermediate toward attractive chemicals. Here we address a crucial step in this process, the conversion of PHB to methyl crotonate (MC), which can be converted via cross‐metathesis with ethylene to methyl acrylate and propylene, two important monomers for the plastics industry. The conversion of PHB to MC proceeds via a thermolysis of PHB to crotonic acid (CA), followed by an esterification to MC. At pressures below 18 bar, the thermolysis of PHB to CA is the rate‐determining step, where above 18 bar, the esterification of CA to MC becomes rate limiting. At 200°C and 18 bar, a full conversion and 60% selectivity to MC is obtained. This conversion circumvents processing and application issues of PHB as a polymer and allows PHB to be used as an intermediate to produce biobased chemicals. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42462.     

Crosslinkable micelles from diblock amphiphilic copolymers based on vinylbenzyl thymine and vinylbenzyl triethylammonium chloride

Polymeric micelles (PMs) composed of self‐assembled amphiphilic block copolymers were synthesized from vinylbenzyl thymine (VBT) and vinylbenzyl triethylammonium chloride (VBA) exhibiting improved physical stability. Three diblock copolymers of different chemical compositions and similar molecular weights (polydispersities below 1.5) were obtained via nitroxide mediated radical polymerization. Critical micelle concentration (CMC) was determined by dye micellization method, the shift of the absorption peak of the anionic (EY) due to the interactions with non‐assembled chains and auto‐assembled copolymers was followed. Polymeric systems exhibited good stability revealing that a higher proportion of cationic monomers in the diblock reduce the CMC. Furthermore, after the core of PMs was photocrosslinked by UV irradiation, the CMC decreases notably. Kinetic release studies using EY dye as probe demonstrated that both, higher VBA ratios in the polymer and higher UV‐irradiation, slow down the dye release. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41947.     

High‐mechanical‐strength ferrohydrogels with a magnetically dispersed phase as multifunctional crosslinkers

In this article, we report a facile strategy for preparing high‐mechanical‐strength ferrohydrogels containing magnetic nanoparticles homodispersed by a thermodynamically stable Pickering emulsion (PE). After the monomers were mixed with the PE, including methacryloxy propyl trimethoxyl silane emulsified by ferric oxide (Fe₂O₃) nanoparticles as the dispersed phase, hydrogels were synthesized by free‐radical polymerization. In contrast to conventional hydrogels crosslinked by a molecular crosslinker, in our new approach, the magnetic PE particles served as individual, multifunctional crosslinkers. Characterizations of the swelling behavior, the mechanical properties, and other properties indicated that our ferrohydrogels exhibited outstanding physical performances that were superior to those of traditional hydrogels and magnetic responsiveness. These ferrohydrogels may have applications in soft and controllable actuators. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41950.