Development of novel soy-protein-based superabsorbent matrixes through the addition of salts

The addition of salts, like sodium bicarbonate (SB) or carbonate (SC), into the formulation of bioplastic materials may alter their hydrophilic character to a significant extent. Soy protein isolate (SPI) is a byproduct of the soybean oil industry, which, when properly blended with glycerol (GL), can be further processed through a lab-scale injection molding device. A maximum in the water uptake around 2250 or 2500% is obtained for bioplastics obtained when either SB or SC content is around 1 wt %, respectively. Thus, they exceed the limit to be considered superabsorbent materials (SAMs). Regarding their mechanical properties, a higher presence of SB within the SPI/GL matrix provides materials with a higher extensibility and lower Young's modulus. A higher water uptake is observed after replacing SB for SC in the formulation, probably related to a higher alkalinization of the material as well as to the high hydrophilicity of the carbonate. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47012.     

Thermal and mechanical behavior of unsaturated polyester [derived from poly(ethylene terephthalate) waste] and montmorillonite‐filled nanocomposites synthesized by in situ polymerization

Postconsumer poly(ethylene terephthalate) waste bottles were glycolyzed as precursors of unsaturated polyester resin (UPR) and their montmorillonite (MMT)‐filled nanocomposites. The glycolysis product (hydroxyl‐terminated oligomers) was converted into UPR with various acid contents. These resins were miscible with styrene and could be cured with peroxide initiators to produce thermosetting unsaturated polyester (UP). Nanocomposites composed of UP matrix and organically modified clay were prepared by in situ polymerization. These were characterized for thermal and dynamic mechanical properties. Transmission electron microscopy was also used to study the morphology at different length scales and showed the nanocomposites to be compromised of a random dispersion of intercalated/exfoliated aggregates throughout the matrix. With an increase in unsaturated acid content (for a fixed content of clay), the value of storage modulus varied from 2737 to 4423 MPa. The glass‐transition temperatures of these nanocomposites ranged from 54 to 78°C, and the crosslink density varied from 3.70 × 10⁵ to 5.72 × 10⁵ mol/m³. The X‐ray diffraction (XRD) of modified MMT exhibited a peak that vanished completely in the polymer nanocomposites. Thus, the XRD results apparently indicated a distortion of the platy layers of nanofiller in the UP nanocomposites. The nanocomposites showed higher modulus values (2737–4423 MPa) compared to the pristine polymer (2693 MPa). From thermogravimetric analysis, all of the nanocomposites were stable up to 200°C and showed a two‐stage degradation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigations of thermal degradation behavior and fire performance of halogen‐free flame retardant poly(1,4‐butylene terephthalate) composites

This work aims to develop halogen‐free poly(1,4‐butylene terephthalate) (PBT) composites with enhanced flame retardancy using ecofriendly flame retardants, aluminum hypophosphite (AHP) and melamine derivatives (melamine polyphosphate and melamine cyanurate). Microscale combustion calorimetry and thermal gravimetric analysis/infrared spectrometry (TG‐IR) technique were used to investigate the potential fire hazards of these PBT composites. For the PBT composites with the incorporation of AHP and melamine derivatives, the heat release capacity (HRC) which is an indicator of a material fire hazard was significantly reduced, and the intensities of a variety of combustible or toxic gases detected by TG‐IR technique were remarkably decreased. Moreover, a loading of 20 wt % flame retardant mixture fulfilled the PBT composites high limited oxygen index (LOI) and V‐0 classification in UL 94 testing. An intumescent flame retarded mechanism was speculated in this work, because numerous bubble‐like char residues were found on the surface of the samples containing flame retardant mixture after LOI testing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,characterization and use of polymer‐supported phase transfer catalyst in organic reactions

A polymer‐supported (PS) phase transfer catalyst, polyethylene‐g‐quaternary ammonium salt (PE‐g‐Q_N⁺), is prepared through a three‐step graft copolymerization of maleic anhydride (MAn) onto polyethylene (PE) by photochemical method using 1% benzophenone (Bz) as photosensitizer. Post grafted acid hydrolysis of polyethylene‐g‐maleic anhydride (PE‐g‐MAn) results in the preparation of PE‐g‐succinic acid which on further treatment with tetrabutylammonium bromide (TBAB) under basic conditions in tetrahydrofuran (THF) gives PE‐g‐Q_N⁺. Optimum conditions pertaining to maximum percentage of grafting have been evaluated as a function of concentration of maleic anhydride, amount of photosensitizer, and time of reaction. Maximum percentage of grafting (25%) was obtained using 3.57 mol of MAn and 0.5 mL of 1% Bz in 120 min. The PE and graft copolymers, PE‐g‐MAn, and PE‐g‐Q_N⁺ were characterized by FTIR Spectroscopy and thermogravimetric analysis (TGA). The ionic nature of quaternary ammonium salt, PE‐g‐Q_N⁺ has also been confirmed by conductance measurements. PE‐g‐Q_N⁺ reagent have been used successfully for polymerization, amidation, and esterification reactions. The products obtained were characterized by FTIR and H¹NMR spectral methods. The reagent was reused for the further reactions and it was observed that the polymeric reagent polymerize, amidate, and esterificate the compounds successfully but with little lower product yield. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Addition of 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl) imide to improve the thermal stability of regenerated cellulose

This article reports the influence of 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl) imide (BMITFSI) addition on the thermal and mechanical properties of regenerated cellulose. Scanning electron microscopy, Young's modulus values, thermogravimetric analysis, glass‐transition temperature values, and ultraviolet–visible spectroscopy were used to assess the effect of BMITFSI addition on the properties of regenerated cellulose. The addition of a room‐temperature ionic liquid, BMITFSI, during the dissolution of cellulose was found to enhance the thermal stability of regenerated cellulose. Compared to other reported plasticizers for regenerated cellulose, such as glycerol, glycols, water, mineral oil, and α‐monoglycerides, the low vapor pressure of BMITFSI led to a long performance with the least evaporation or leaching. In addition, the immiscible nature of BMITFSI in water and its stability against moisture made BMITFSI an effective plasticizer for regenerated cellulose over a broad range of surrounding humidities and temperature conditions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The phase behavior and thermal stability of blends of poly(styrene‐co‐methacrylic acid)/poly(styrene‐co‐ 4‐vinylpyridine)

The hydrogen bonding and miscibility behaviors of poly(styrene‐co‐methacrylic acid) (PSMA20) containing 20% of methacrylic acid with copolymers of poly(styrene‐co‐4‐vinylpyridine) (PS4VP) containing 5, 15, 30, 40, and 50%, respectively, of 4‐vinylpyridine were investigated by differential scanning calorimetry, thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). It was shown that all the blends have a single glass transition over the entire composition range. The obtained T_gs of PSMA20/PS4VP blends containing an excess amount of PS4VP, above 15% of 4VP in the copolymer, were found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are able to form interpolymer complexes. The FTIR study reveals presence of intermolecular hydrogen‐bonding interaction between vinylpyridine nitrogen atom and the hydroxyl of MMA group and intensifies when the amount of 4VP is increased in PS4VP copolymers. A new band characterizing these interactions at 1724 cm⁻¹ was observed. In addition, the quantitative FTIR study carried out for PSMA20/PS4VP blends was also performed for the methacrylic acid and 4‐vinylpyridine functional groups. The TGA study confirmed that the thermal stability of these blends was clearly improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal analysis of polymer ignition

Gas phase criteria for the onset of flaming combustion of solids in fires are used to locate a critical temperature T_cr in a nonisothermal analysis (TA) experiment that corresponds to the surface temperature of the solid at ignition in a fire test, T_ign. This critical TA temperature occurs at low conversion of solid to gaseous fuel so it is independent of the heating rate in the test or the thermal decomposition reaction model. However, T_cr depends on the thermal properties of the polymer and the conditions of the fire test in which the gas phase criteria were measured. Nonisothermal analysis data in nitrogen and air were obtained for 20 polymers by thermogravimetric analysis and microscale combustion calorimetry. The critical temperatures T_crs obtained from TA experiments compared favorably with analytic results for a simple polymer ignition model and finite element simulations and were in qualitative agreement with ignition temperatures measured in standardized fire tests.     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.     

Influence of alkali fiber treatment and fiber processing on the mechanical properties of hemp/epoxy composites

Industrial hemp fibers were treated with a 5 wt % NaOH, 2 wt % Na₂SO₃ solution at 120°C for 60 min to remove noncellulosic fiber components. Analysis of fibers by lignin analysis, scanning electron microscopy (SEM), zeta potential, Fourier transform infrared (FTIR) spectroscopy, wide angle X‐ray diffraction (WAXRD) and differential thermal/thermogravimetric analysis (DTA/TGA), supported that alkali treatment had (i) removed lignin, (ii) separated fibers from their fiber bundles, (iii) exposed cellulose hydroxyl groups, (iv) made the fiber surface cleaner, and (v) enhanced thermal stability of the fibers by increasing cellulose crystallinity through better packing of cellulose chains. Untreated and alkali treated short (random and aligned) and long (aligned) hemp fiber/epoxy composites were produced with fiber contents between 40 and 65 wt %. Although alkali treatment generally improved composite strength, better strength at high fiber contents for long fiber composites was achieved with untreated fiber, which appeared to be due to less fiber/fiber contact between alkali treated fibers. Composites with 65 wt % untreated, long aligned fiber were the strongest with a tensile strength (TS) of 165 MPa, Young's modulus (YM) of 17 GPa, flexural strength of 180 MPa, flexural modulus of 9 GPa, impact energy (IE) of 14.5 kJ/m², and fracture toughness (K_Ic) of 5 MPa m^1/2. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011