Morphology,dynamic mechanical,and electrical properties of bio‐based poly(trimethylene terephthalate) blends,part 2: Poly(trimethylene terephthalate)/poly(ether esteramide)/polycarbonate blends

Bio‐based poly(trimethylene terephthalate) (PTT) and poly(ether esteramide) (PEEA) blends were prepared by melt processing with varying weight ratios (0–20 wt %) of polycarbonate (PC). The blends were characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), polarized light microscopy (PLM), and transmission electron microscopy (TEM). Electrostatic performance was also investigated for those PTT blends since PEEA is known as an ion conductive polymer. DMA suggests that PC is miscible with PEEA and selectively goes into PEEA phase in case of ternary blends of PTT/PEEA/PC. The glass transition temperature (T_g) for PC/PEEA is well predicted by Gordon Taylor equation. Addition of PC retards the electrostatic decay performance of PTT/PEEA blends by restricting the motion of ions in PEEA through increasing the T_g of PEEA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology,dynamic mechanical,and electrical properties of bio‐based poly(trimethylene terephthalate) blends,part 1: Poly(trimethylene terephthalate)/poly(ether esteramide)/polyethylene glycol 400 bis(2‐ethylhexanoate) blends

Bio‐based PTT and PTT blends with PEEA of two different ion contents (275 ppm Na and 3515 ppm Na) and PEG 400 bis (2‐ethylhexanoate) were prepared by melt processing. The blends were characterized by differential scanning calorimetry, dynamic mechanical analysis, transmission electron microscopy, and atomic force microscopy. Electro‐static performance was also investigated for those PTT blends since PEEA is known as an ion conductive polymer. Here we confirmed that PEG 400 bis (2‐ethylhexanoate) improves the static decay performance of PTT/PEEA blends. DMA strongly suggests that PEG 400 bis (2‐ethylhexanoate) and PEEA are miscible pairs, and PEG 400 bis (2‐ethylhexanoate) selectively goes into the PEEA phase rather than the PTT phase, which lowers the T_g of PEEA. Besides topographic analysis of morphology and phase separation, tunneling atomic force microscopy was also applied to see if we can observe the surface directly for the static dissipative material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The study of palm‐oil‐based bio‐polyol on the morphological,acoustic and mechanical properties of flexible polyurethane foams

The focus of this paper was to explore the acoustic properties of flexible polyurethane (FPU) foam modified by palm‐oil‐based polyol (POP). The presence of POP showed a marked influence on the microstructure and mechanical properties of FPU foam. A smaller mean pore diameter can be observed at lower POP content. Indeed, the introduction of POP caused a higher closed pore ratio and an increased air‐flow resistivity, which consequently improved the sound absorption coefficient and transmission loss. In particular, the acoustic performance of the all bio‐based FPU foam was enhanced at low frequency, and the density was lower than that of the reference foam. Additionally, the addition of POP also improved the compressive strength. Conversely, the tensile strength of FPU foam declined with increasing POP content. From this study, the outstanding acoustic ability of bio‐based FPU foam has been proved, with additional advantages of lower density and higher compressive strength. © 2019 Society of Chemical Industry     

Structure and properties of bio‐based polyamide 109 treated with superheated water

The structure and properties of bio‐based polyamide 109 (PA109) after treatment with superheated water (140 °C ≤ T ≤ 280 °C) were investigated and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, wide‐angle X‐ray diffraction, scanning electron microscopy and small‐angle X‐ray scattering. Below 170 °C, the hydrothermal treatment was considered to be a physical process, which exerted an annealing effect on PA109. It led to an increase in melting temperature, lamellar thickness and crystallinity, while the macromolecular structure, crystal structure and the order of crystalline regions were not affected. Above 170 °C, complete melting/dissolution of PA109 occurred with partial hydrolysis. Due to the high temperature and long reaction time, the hydrolysis reaction became more and more prominent, and the resin was completely hydrolyzed into oligomers at 280 °C. Also, above 170 °C, the hydrothermal treatment was accompanied by a chemical process and the melting temperature and molecular weight decreased progressively. Notably, the crystal structure was not altered, but the degree of perfection of crystals and the order of crystalline regions were broken, especially above 200 °C. The hydrolytic degradation reaction was significantly affected by temperature, while both time and the water to polyamide ratio were secondary factors which influenced it to a minor extent. The process could be considered as a typical nucleophilic substitution reaction which takes place step by step inducing the molecular weight to decrease gradually. Overall, this study provides a ‘green’ route for the processing, recycling and treatment of environmentally friendly polyamides based on hydrothermal treatment technology. © 2019 Society of Chemical Industry     

Recent trends in (ligno)cellulose dissolution using neoteric solvents: switchable,distillable and bio‐based ionic liquids

Recent years have witnessed the use of different ionic liquids for biomass processing, either at the level of lignocellulose pre‐treatment, to fractionate biomass in its main components, separating hemicellulose and lignin from cellulose, or directly in cellulose decrystallization by dissolving it in the ionic liquid and subsequent precipitation by adding anti‐solvents. Yet, most of the ILs employed in these strategies (e.g. imidazolium‐based solvents) are (still) expensive for such applications, and provide discussable ecological footprints. In an attempt to combine the highly useful generated knowledge with novel neoteric solvents with improved properties, economics, availability and ecology, several new trends have appeared in these areas during recent years. They comprise the use of switchable ILs, based on strong organic bases and CO₂, the application of distillable ILs, as well as the use of bio‐based and low‐cost ILs and deep‐eutectic‐solvents (DES), e.g. choline chloride‐based derivatives. Apart from other emerging uses, for all these solvents some preliminary applications in biomass processing involving pretreatments, cellulose dissolution and other applications have been successfully reported. This Minireview contextualizes these recent trends and discusses them with emphasis on future use of them in biorefineries and biomass valorization. © 2013 Society of Chemical Industry     

Physicochemical and adsorptive properties of fast‐pyrolysis bio‐chars and their steam activated counterparts

BACKGROUND: This study investigated steam‐activation as a technology for adding value to fast‐pyrolysis bio‐chars. Due to short residence times in the fluidized‐bed pyrolyzer, required to maximize bio‐oil production, the bio‐char structure tends to be underdeveloped thereby impacting its full potential application as a value‐added co‐product. RESULTS: The bio‐chars of several substrates from a fluidized‐bed fast pyrolyzer and their respective corresponding steam‐activated counterparts were characterized for their surface areas and metal ion adsorption (copper, cadmium, nickel and zinc). Surface areas increased with activation from negligible to 136–793 m² g^?1 of material, with concomitant pore development evidenced by scanning electron microscopy and mathematical modeling. Affinity to Cu²⁺ was highest with adsorption efficiencies for 1 mmol L^?1 solutions ranging from 60–85%. Metal ion adsorption performance was feedstock dependent and increased with activation, possibly due to improved access to highly reactive adsorption sites associated with the inorganic material in the feedstock. CONCLUSION: Because of their higher yields and metal ion uptake, broiler litter and alfalfa stems could be the feedstock of choice when considering upgrading fast pyrolysis bio‐char for metal ion uptake. However, if the development of large surface areas is required, guayule bagasse and soybean straw could be the preferred feedstock. Published 2010 by John Wiley and Sons, Ltd.     

Synthesis and photo‐polymerization of bio‐based furanic compounds functionalized by 2‐hydroxypropyl methacrylate group(s)

Bio‐based compounds (FmHPM and FdHPM) with a furan backbone and photo‐polymerizable 2‐hydroxypropyl methacrylate (HPM) group(s) were synthesized from carbohydrate‐derived furanyl alcohols (furan‐2‐methanol and furan‐2,5‐dimethanol) and their photo‐polymerizing behaviors and mechanical properties after photo‐polymerization were investigated. Half time values (t_1/2) of bio‐based FmHPM and FdHPM were 10.4 s and 3.0 s and their shrinkage ratios were 3.0 and 6.1% during photo‐polymerization, respectively. Tensile‐shear strength of glass and polycarbonate joints bonded by bio‐based furanic compounds appeared in range of 0.2–0.6 MPa and pencil hardness of film coated by bio‐based furanic compounds after photo‐polymerization showed 2H–3H. Newly synthesized bio‐based furanic compounds allowed the feasibility to alternate petroleum‐based Bis‐GMA/TEGDMA, photo‐polymerizable composition widely utilized in a variety of applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of a novel bio‐based benzoxazine resin with excellent low‐temperature curing ability

A novel bio‐based benzoxazine resin (diphenolic acid/furfurylamine benzoxazine resin, PDPA‐F‐Boz) was prepared by using bio‐based diphenolic acid, furfurylamine and paraformaldehyde as raw materials. The structure of DPA‐F‐Boz monomer was characterized by Fourier transform infrared spectroscopy, ¹H NMR and ¹³C NMR, and then its curing reaction and the thermal stability of the cured PDPA‐F‐Boz were analyzed. Compared with the traditional fossil‐based benzoxazine (bisphenol A/aniline benzoxazine, BPA‐A‐Boz) and the bio‐based benzoxazine (diphenolic acid/aniline benzoxazine, DPA‐A‐Boz), DPA‐F‐Boz monomer showed the lowest curing temperature, and PDPA‐F‐Boz had the highest residual char ratio at 800 °C and the lowest degradation rate at the peak temperature. Meanwhile, the total heat release, peak heat release rate and heat release capacity of PDPA‐F‐Boz were much lower than those of PBPA‐A‐Boz and PDPA‐A‐Boz. Thus, PDPA‐F‐Boz showed excellent low‐temperature curing ability and thermal stability. © 2019 Society of Chemical Industry     

Using fish scales (Sardina pilchardus) within ethylene‐propylene‐diene ter monomer rubber as bio‐based filler

Proper management of waste bio‐based materials is an important subject to protect the environment in a sustainable manner. In this study, ethylene‐propylene‐diene monomer (EPDM) composites with different fish scale content were prepared and properties of these composites were investigated. Mechanical tests, gel content, curing, and thermal properties were analyzed. In addition, rheological and morphological analyses were also carried out. It was seen that EPDM rubber and fish scale composite have a good compatibility. The addition of fish scale improved the mechanical properties of the final material. Moreover, an increase in gel content and in swelling ratio was obtained for the composite samples containing fish scale. Moving die rheometer tests are concluded that fish scale has acted like an agent that improves the vulcanization process. Thermal gravimetric analysis result pointed out that the thermal stability of the composite developed is higher than neat EPDM. It was concluded that 40 phr fish scale content gives best results. The kinetic study demonstrated that fish scale is compatible with the matrix and improves the vulcanization process. The results have shown that using the fish scale as a bio‐based filler is a facile and green way to accommodate the bio‐based wastes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46698.     

A novel bio‐based phthalonitrile resin derived from catechin: synthesis and comparison of curing behavior with petroleum‐based counterpart

The development of bio‐based thermosetting resins with good thermal stability can potentially afford sustainable polymers as replacements for petroleum‐based polymers. We report a practical route to a novel catechin‐based phthalonitrile resin precursor (CA‐Ph), which contains free phenolic hydroxyl groups that result in ‘self‐curing’ at elevated temperatures to afford a thermostable polymer. Comparison of the performance of this CA‐Ph resin with that of a conventional petroleum‐based bisphenol A phthalonitrile resin (BPA‐Ph; containing 5 wt% of the curing agent 4,4′‐diaminodiphenylsulfone) revealed that CA‐Ph exhibits a lower melting point and curing temperature. Cured CA‐Ph resin retains 95% of its weight at 520 °C under a nitrogen atmosphere, which compares favorably with results obtained for BPA‐Ph resin that retains 95% of its weight at a lower temperature of 484 °C. Kinetic results indicated that the curing reactions of both CA‐Ph and BPA‐Ph systems follow an autocatalytic mechanism. These results suggest that catechin is a useful bio‐based feedstock for the preparation of self‐curing and thermally stable phthalonitrile resins for advanced technological applications. © 2017 Society of Chemical Industry     

Characterisation of the mixture product of ether‐soluble fraction of bio‐oil (ES) and bio‐diesel

A method of upgrading the properties of bio‐oil with bio‐diesel has been taken in this article. Firstly, the unpopular pyrolytic lignin fraction is extracted from bio‐oil using ether, the rest ether‐soluble fraction of bio‐oil, named ES is mixed with bio‐diesel according to emulsification. The optimal conditions for obtaining a stable ES/bio‐diesel mixture are with octanol surfactant dosage of 3% by volume; initial ES to bio‐diesel ratio of 4:6 by volume; stirring intensity of 1200 rpm; mixing time of 15 min and mixing temperature at 30°C. Additionally, selected fuel properties such as viscosity, water content and acid number are measured for characterising the ES/bio‐diesel mixture. Thermogravimetric analysis (TGA) has been used to further evaluate the thermal properties. Data from the TGA and Fourier transform infrared spectroscopy (FTIR) analyses confirm the presence or absence of certain group of chemical compounds in the mixture. Proton and carbon atoms assignments are further confirmed by ¹H NMR (nuclear magnetic resonance) and ¹³C NMR analysis, respectively. © 2011 Canadian Society for Chemical Engineering     

Stereocomplex formation between enantiomeric PLA–PEG–PLA triblock copolymers: Characterization and use as protein‐delivery microparticulate carriers

Two enantiomeric triblock ABA copolymers composed of poly(L ‐lactide)–poly(ethylene glycol)–poly(L ‐lactide) (PLLA–PEG–PLLA) and poly(D ‐lactide)–poly(ethylene glycol)–poly(D ‐lactide) (PDLA–PEG–PDLA) were synthesized with two different middle‐block PEG chain lengths by ring‐opening polymerization of L ‐lactide and D ‐lactide in the presence of PEG, respectively. A pair of enantiomeric triblock copolymers were combined to form a stereocomplex by a solvent‐casting method. The triblock copolymers and their stereocomplexes were characterized by ¹H‐ and ¹³C‐NMR spectroscopy and gel permeation chromatography. Their crystalline structures and crystalline melting behaviors were analyzed by the wide‐angle X‐ray diffraction method and differential scanning calorimetry. The stereocomplex formed between a pair of enantiomeric triblock copolymers exhibited a higher crystalline melting temperature with a distinctive 3/1 helical crystalline structure. PLLA–PEG–PLLA and its stereocomplex with PDLA–PEG–PDLA were used to fabricate a series of microspheres encapsulating a model protein drug, bovine serum albumin (BSA). They were prepared by a double‐emulsion solvent‐evaporation method. The morphological aspects of the microspheres were characterized and BSA release profiles from them were investigated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1615–1623, 2000     

Thermo‐oxidative stabilization of poly(lactic acid)‐based nanocomposites through the incorporation of clay with in‐built antioxidant activity

In this work, an innovative approach to overcome the issue of the poor thermo‐oxidative stability of polymer/clay nanocomposites is proposed. Specifically, biodegradable poly(lactic acid) (PLA)‐based nanocomposites, containing organo‐modified clay with in‐built antioxidant activity, were prepared. Through a two‐step chemical protocol, a hindered phenol antioxidant was chemically linked to the ammonium quaternary salt which was then intercalated between the clay platelets [(AO)OM‐Mt]. The nanocomposites were characterized and their thermo‐oxidative stability during melt processing and under long‐term thermal test conditions was investigated. PLA nanocomposites containing the (AO)OM‐Mt showed higher oxidative stability, along with better clay dispersion, compared to PLA‐nanocomposites containing commercial clay and a free hindered phenol antioxidant. Obtained results can be explained considering that (AO)OM‐Mt may act locally, at the interface, between the silicate layers and the polymer macromolecules, thus contributing to the observed improved stability of the polymer both during processing and under long‐term thermal‐oxidative conditions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44974.     

Synthesis and characterization of azo‐based acrylate polymers for use as nonlinear optical materials

In this work, high molecular weight azo polymers were synthesized by incorporating the azo monomer into a base polymer through their reactive functional groups. Copolymers of methyl methacrylate and methacrylic acid (with varying concentrations of carboxylic acid group) were synthesized. These were then reacted with epoxy‐terminated azo molecule by carboxylic acid–epoxy reaction. The functionalized systems show excellent film homogeneity and optical clarity. The series of copolymers were characterized using FTIR, NMR, UV–vis spectrometry, gel permeation chromatography, elemental analysis, thermogravimetric analysis, and differential scanning calorimetry. The polymer films coated on ITO glass slides were poled and their order parameters were calculated to check the stability of oriented dipoles. Temporal stability, checked up to 120 h under ambient conditions, was found to be excellent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 425–431, 2007     

Thermosetting foam with a high bio‐based content from acrylated epoxidized soybean oil and carbon dioxide

A resilient, thermosetting foam system with a bio‐based content of 96 wt % (resulting in 81% of C₁₄) was successfully developed. We implemented a pressurized carbon dioxide foaming process that produces polymeric foams from acrylated epoxidized soybean oil (AESO). A study of the cell dynamics of uncured CO₂/ AESO foams proved useful to optimize cure conditions. During collapse, the foam's bulk density increased linearly with time, and the cell size and cell density exhibited power‐law degradation rates. Also, low temperature foaming and cure (i.e. high viscosity) are desirable to minimize foam cell degradation. The AESO was cured with a free‐radical initiator (tert‐butyl peroxy‐2‐ethyl hexanoate, T_i ～ 60°C). Cobalt naphtenate was used as an accelerator to promote quick foam cure at lower temperature (40–50°C). The foam's density was controlled by the carbon dioxide pressure inside the reactor and by the vacuum applied during cure. The viscosity increased linearly during polymerization. The viscosity was proportional to the extent of reaction before gelation, and the cured foam's structure showed a dependence on the time of vacuum application. The average cell size increased and the cell density decreased with foam expansion at a low extent of cure; however, the foam expansion became limited and unhomogeneous with advanced reaction. When vacuum was applied at an intermediate viscosity, samples with densities ～ 0.25 g/cm³ were obtained with small (<1 mm) homogeneous cells. The mechanical properties were promising, with a compressive strength of ～ 1 MPa and a compressive modulus of ～ 20 MPa. The new foams are biocompatible. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Development of a bio‐based composite material from soybean oil and keratin fibers

A novel bio‐based composite material, suitable for electronic as well as automotive and aeronautical applications, was developed from soybean oils and keratin feather fibers (KF). This environmentally friendly, low‐cost composite can be a substitute for petroleum‐based composite materials. Keratin fibers are a hollow, light, and tough material and are compatible with several soybean (S) resins, such as acrylated epoxidized soybean oil (AESO). The new KFS lightweight composites have a density ρ ≈ 1 g/cm³, when the KF volume fraction is 30%. The hollow keratin fibers were not filled by resin infusion and the composite retained a significant volume of air in the hollow structure of the fibers. Due to the retained air, the dielectric constant, k, of the composite material was in the range of 1.7–2.7, depending on the fiber volume fraction, and these values are significantly lower than the conventional silicon dioxide or epoxy, or polymer dielectric insulators. The coefficient of thermal expansion (CTE) of the 30 wt % composite was 67.4 ppm/°C; this value is low enough for electronic application and similar to the value of silicon materials or polyimides used in printed circuit boards. The water absorption of the AESO polymer was 0.5 wt % at equilibrium and the diffusion coefficient in the KFS composites was dependent on the keratin fiber content. The incorporation of keratin fibers in the soy oil polymer enhanced the mechanical properties such as storage modulus, fracture toughness, and flexural properties, ca. 100% increase at 30 vol %. The fracture energy of a single keratin fiber in the composite was determined to be about 3 kJ/m² with a fracture stress of about 100–200 MPa. Considerable improvements in the KFS composite properties should be possible by optimization of the resin structure and fiber selection. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1524–1538, 2005     

Poly(ethylene glycol) methyl ether methacrylate‐graft‐chitosan nanoparticles as a biobased nanofiller for a poly(lactic acid) blend: Radiation‐induced grafting and performance studies

In this study, we aimed to modify chitosan (CS) as a novel compatible bio‐based nanofiller for improving the compatibility including the thermal and mechanical properties of poly(lactic acid) (PLA). The modification of CS with poly(ethylene glycol) methyl ether methacrylate (PEGMA) was done by radiation‐induced graft copolymerization. The effects of the dose rate, irradiation dose, and PEGMA concentration on the degree of grating (DG) were investigated. The chemical structure, packing structure, thermal stability, particle morphology, and size of the PEGMA‐graft‐chitosan nanoparticles (PEGMA‐graft‐CSNPs) were characterized by fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, and transmission electron microscopy. The compatibility of the PEGMA‐graft‐CSNP/PLA blends was also assessed by field emission scanning electron microscopy. The PEGMA‐graft‐CSNPs exhibited a spherical shape with the DG and particle sizes in the ranges of 3–145% and 35–104 nm, respectively. The PEGMA‐graft‐CSNPs showed compatible with PLA because of the grafted PEGMA segment. A model case study of the PEGMA‐graft‐CSNP/PLA blend demonstrated the improvement not only the compatibility but also thermal stability flexibility, and ductility of PLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42522.