Biodegradable biocomposites from poly(butylene adipate‐co‐terephthalate) and miscanthus: Preparation,compatibilization, and performance evaluation

Miscanthus fibers reinforced biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) matrix‐based biocomposites were produced by melt processing. The performances of the produced PBAT/miscanthus composites were evaluated by means of mechanical, thermal, and morphological analysis. Compared to neat PBAT, the flexural strength, flexural modulus, storage modulus, and tensile modulus were increased after the addition of miscanthus fibers into the PBAT matrix. These improvements were attributed to the strong reinforcing effect of miscanthus fibers. The polarity difference between the PBAT matrix and the miscanthus fibers leads to weak interaction between the phases in the resulting composites. This weak interaction was evidenced in the impact strength and tensile strength of the uncompatibilized PBAT composites. Therefore, maleic anhydride (MAH)‐grafted PBAT was prepared as compatibilizer by melt free radical grafting reaction. The MAH grafting on the PBAT was confirmed by Fourier transform infrared spectroscopy. The interfacial bonding between the miscanthus fibers and PBAT was improved with the addition of 5 wt % of MAH‐grafted PBAT (MAH‐g‐PBAT) compatibilizer. The improved interaction between the PBAT and the miscanthus fiber was corroborated with mechanical and morphological properties. The compatibilized PBAT composite with 40 wt % miscanthus fibers exhibited an average heat deflection temperature of 81 °C, notched Izod impact strength of 184 J/m, tensile strength of 19.4 MPa, and flexural strength of 22 MPa. From the scanning electron microscopy analysis, better interaction between the components can be observed in the compatibilized composites, which contribute to enhanced mechanical properties. Overall, the addition of miscanthus fibers into a PBAT matrix showed a significant benefit in terms of economic competitiveness and functional performances. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45448.     

Formulation and characterization of compatibilized poly(lactic acid)‐based blends and their nanocomposites with silver‐loaded kaolinite

Biodegradable polymer nanocomposites have been developed in this study as materials for use in the packaging of moisture‐sensitive products. Poly(lactic acid) (PLA) was the main component of the nanocomposites with poly(butylene adipate‐co‐terephthalate) (PBAT) as flexibility enhancer. Tetrabutyl titanate was also added as a compatibilizer to enhance the interfacial affinity between PLA and PBAT by inducing the formation of some PLA/PBAT via transesterification during the melt blending process, thereby improving the mechanical properties of the blends. Silver‐loaded kaolinite synthesized via chemical reduction was also incorporated into the compatibilized blends for further property improvement. Herein, we report a novel biodegradable quaternary nanocomposite system with intercalated‐exfoliated clay dispersion that was uniquely achieved by increasing the interlamellar space between kaolinite layers through silver nanoparticle insertion. The resultant nanocomposites containing as little as 4 phr modified clay reduced the elongation at break from 213.0 ± 5.85% to 53.8 ± 1.81%, enhanced thermal stability (initial decomposition temperature increased from 378 °C to 399 °C) and exhibited a water vapor permeability reduction of 41.85%. On the basis of these properties, the developed nanocomposites are considered to be promising candidates for use in bio‐packaging applications to replace non‐biodegradable and petro‐based plastics. © 2014 Society of Chemical Industry     

Nanocomposites of PBAT and cellulose nanocrystals modified by in situ polymerization and melt extrusion

Cellulose nanocrystals (CNC) were successfully grafted with a low molecular weight poly(butylene glutarate) through an in situ polymerization procedure. The grafting treatment decreased the CNC hydrophilic character and increased the onset of their thermal degradation by approximately 20°C, thus increasing the possibilities of CNC application. Composites of grafted and nongrafted CNC with a poly(butylene‐adipate‐co‐terephthalate) (PBAT) matrix were prepared by melt extrusion. The CNC addition led to an increase of 50% of the tensile elastic modulus of the PBAT. In addition, dynamic mechanical thermal analysis showed that the composite with CNC retained its high modulus even at temperatures far above the glass transition temperature of PBAT. At 60°C the storage modulus of the composite with CNC was approximately 200% higher than that of the pure PBAT. Thus, in this work, nanocomposites of improved properties were obtained through a combination of in situ polymerization and melt extrusion. POLYM. ENG. SCI., 56:1339–1348, 2016. © 2016 Society of Plastics Engineers     

Laboratory antimicrobial activity of cinnamaldehyde and pomegranate‐based polycaprolactone films

Polycaprolactone (PCL) was incorporated separately with cinnamaldehyde (CNMA), pomegranate methanolic extract (PME), freeze dried arils of pomegranate (FDAP), and seed flour of pomegranate (SF) to form antimicrobial films to be used for active food packaging. PCL–CNMA films completely inactivated growth of the artificially inoculated Escherichia coli and Staphylococcus aureus, whether at 5% or 10% concentrations (wt/wt of polymer), at all studied temperatures (4, 20, and 37 °C). PCL–PME films (10% wt/wt of polymer) delayed the growth of E. coli and S. aureus for up to 7 and 6 days, respectively, at 37 °C. Two‐day delays in the growth of both bacteria were achieved with FDAP and SF films (10% wt/wt of polymer) at 20 °C. The release of CNMA was slower than the release of PME during film processing, as measured by Fourier transform infrared spectroscopy. Thus, CNMA and pomegranate‐based films perhaps should be planned further for use in controlled release food packaging. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45347.     

Effect of different biopolymers and polymers on the mechanical and permeation properties of extruded PHBV cast films

The biopolymer poly‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate (PHBV) is a promising material for packaging applications but its high brittleness is challenging. To address this issue, PHBV was blended with nine different biopolymers and polymers in order to improve the processing and mechanical properties of the films. Those biopolymers were TPS, PBAT, a blend of PBAT + PLA, a blend of PBAT + PLA + filler, PCL and PBS, and the polymers TPU, PVAc, and EVA. The extruded cast films were analyzed in detail (melting temperature, crystallinity, mechanical properties, permeation properties, and surface topography). A decrease in crystallinity and Young's modulus and an increase in elongation at break and permeability were observed with increasing biopolymer/polymer concentration. In PHBV‐rich blends (≥70 wt % PHBV), the biopolymers/polymers PCL, PBAT, and TPU increased the elongation at break while only slightly increasing the permeability. Larger increases in the permeability were found for the films with PBS, PVAc, and EVA. The films of biopolymer/polymer‐rich blends (with PBAT, TPU, and EVA) had significantly different properties than pure PHBV. A strong effect on the properties was measured assuming that at certain biopolymer/polymer concentrations the coherent PHBV network is disrupted. The interpretation of the permeation values by the Maxwell–Garnett theory confirms the assumption of a phase separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46153.     

Influence of processing conditions on mechanical properties of blends of styrenic block copolymer and poly(phenylene oxide): Miscibility and microdomain size

The effect of processing conditions on mechanical properties of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) and poly(2,6‐dimethy‐1,4‐phenylene oxide) (PPO) blends were investigated. Differential scanning calorimetry and small angle X‐ray scattering were used to study the miscibility and d‐spacing of the blends. The processing temperature plays an important role in mechanical properties. PPO works as filler and weakens mechanical properties when the processing temperature is below 230 °C. As the processing temperature exceeds 230 °C, PPO incorporates into the PS blocks of SEBS and the performance enhances with increasing temperature due to a better miscibility. The strong shear stress is beneficial to the dispersion of PPO into SEBS matrix and more PPO incorporates into PS blocks during melt processing, resulting in the better mechanical properties and a larger d‐spacing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46123.     

The influence of cross‐linking reaction on the mechanical and thermal properties of polyarylene ether nitrile

The processing of cross‐linked polyarylene ether nitrile (PEN), which has a triazine rings structure, has been investigated under different reaction times and temperatures. In this study, the PEN films prepared by the tape‐casting formed the thermally stable triazine rings by catalytic cross‐linking reaction gradually, which was characterized by Fourier transform infrared spectroscopy. The chemical cross‐linking reaction occurred as the CN group absorption of PEN at 2221 cm⁻¹ decreased and a new absorption peak, at 1682 cm⁻¹, was observed, and the absorption peak intensity would be progressively larger, with the extension of the processing time. After the formation of cross‐linking networks, the cross‐linking degree and thermal and mechanical properties of the processed films were improved substantially, compared with the untreated films. The film with added ZnCl₂ as the catalyst was more rapidly cross‐linked, and its properties were better than that without catalyst at the same treatment conditions. The glass‐transition temperature (T_g) of PEN films processed at 350°C for 4 h (213.65°C) was higher than that of PEN films before the treatment (161°C), and the tensile strength was also improved significantly. The PEN was processed at 350°C for 2 h, whose initial decomposition temperature increases by about 10°C, compared with that of untreated film, at one time. The rheology behavior of the cross‐linked films was processed on dynamic rheometer to monitor and track the process of polymer cross‐linking reaction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Melt extruded nanocomposites of polybutylene adipate‐co‐terephthalate (PBAT) with phenylbutyl isocyanate modified cellulose nanocrystals

Traditional commodity polymers are widely used in several disposable or short‐life items and take hundreds of years to decompose in nature. These polymers could be replaced in several uses by biodegradable polymers, like polybutylene adipate‐co‐terephthalate (PBAT) studied in this work. For this, nonetheless, it is necessary to improve some of the PBAT properties, like mechanical resistance and barrier properties. In this work, cellulose nanocrystals (CNC) were incorporated in PBAT with this intention, through melt extrusion. Aiming to avoid CNC aggregation during the drying and extrusion process, a CNC chemical modification with phenylbutyl isocyanate was done. It was possible to obtain PBAT‐CNC melt extruded composites with an elastic modulus 55% higher and water vapor permeability 63% lower than the values of the pure polymer, without compromising PBAT biodegradation. Therefore, the composites prepared with these enhanced properties have great potential as substitutes for traditional commodity polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43678.     

Strengthening of poly(butylene adipate-co-terephthalate) by melt blending with a liquid crystalline polymer

Poly(butylene adipate-co-terephthalate) (PBAT) is a soft biodegradable polymer with a low melting temperature. PBAT has been melt-blended with a liquid crystalline polymer (LCP) aiming at preparing a new biodegradable polymer blend with improved mechanical properties. The phase structure and crystalline morphologies of the PBAT/LCP blends were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). It was found that the LCP domains are precisely dispersed in the PBAT matrix and that these domains act as the nuclei for PBAT crystallization. The nonisothermal crystallization temperature from the melt was dramatically shifted from 50°C to about 95°C by the addition of 20% LCP. In addition, the tensile modulus of the prepared blends increases gradually with increasing LCP content, indicating the excellent strengthening effects of LCP on the PBAT matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

LDPE composite films incorporating ceramic powder emitting far‐infrared radiation for advanced food‐packaging applications

A ceramic powder that emits far‐infrared radiation (FIR) was incorporated into low‐density polyethylene (LDPE) via melt‐compounding and subsequent melt‐extrusion processes. To investigate the feasibility of as‐prepared LDPE/FIR composite films for use in packaging applications, the composite films were characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, FIR emissivity and emissive power, antimicrobial activity assays, and storage tests. The physical properties and antimicrobial activities of the composite films were found to strongly correlate with the changes in the chemical and morphological structures that originate from different contents of FIR ceramic powder. A higher content of FIR ceramic powder in the LDPE/FIR composite film provided increased FIR emissivity and emission power of the composite and resulted in good antimicrobial activity. Storage tests also showed that incorporation of FIR ceramic powder into LDPE film was an effective method for maintaining the freshness of lettuce. Furthermore, the incorporation of FIR ceramic powder into LDPE films induced higher thermal stability and crystallinity and enhanced their barrier properties, which suggest these LDPE/FIR composite films are potential candidates for advanced packaging materials for the food and medical industries. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43102.     

Experimental investigation of the rheological behaviors of polypropylene in a capillary flow

The rheological characterization of polymer melts is strongly related to their material properties. In this study, we focused on the rheological behaviors of a polypropylene (PP) melt through a capillary die. With an advanced twin‐bore capillary rheometer with dies measuring 1.0, 0.5, and 0.25 mm in diameter, experiments were performed over a shear‐rate range of 3 × 10² to 5 × 10³ s^?1 at three temperatures, 210, 220, and 230 °C. The results demonstrate that the geometry dependence of the PP viscosity relied on the die diameter and the temperature of the PP melt. The viscosity values of the PP melt in the 0.25‐mm diameter die were higher than were those in the 0.5‐ and 1.0‐mm dies at 220 and 230 °C. However, the viscosity values in all of the tested dies were similar at 210 °C. The tendency for the viscosity to decrease as the temperature of the polymer melt increased weakened in the 0.25‐mm diameter die. As a result, the pressure applied to the PP melt in the 0.25‐mm diameter die increased; this caused a decrease in the free volume between molecules. On the basis of the Barus equation, the contribution of pressure to the changed viscosity in each die at each of the tested temperatures was calculated and was found to be as high as 32.86% in the 0.25‐mm die at 230 °C. Additionally, the effect of the wall slip on the geometry dependence of the PP viscosity in the tested dies was investigated with a modified Mooney method. The values of the slip velocity revealed that wall slip occurred only in the 0.25‐mm die at 210 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43459.     

Properties of poly(butylene adipate‐co‐terephthalate) and sunflower head residue biocomposites

Utilization of low‐value agricultural waste for polymer composite materials has great environmental and economical benefits. Sunflower head residue (SHR) as an agricultural waste may be used as a reinforcement in polymeric materials because of its fiber characteristics. In this work, composites of biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) and SHR were prepared via melt‐extrusion compounding. To improve interfacial compatibility, maleic anhydride (MA) grafted PBAT (PBAT‐g‐MA) was prepared and used as a compatibilizer for the PBAT/SHR composites. The effects of the concentrations of SHR and PBAT‐g‐MA on the morphology, mechanical properties, melt rheology, and water resistance of the composites were examined. Interfacial adhesion between phases in the PBAT/SHR composites was enhanced by the introduction PBAT‐g‐MA as interface‐strengthening agent, resulting in improved mechanical properties and moisture resistance of the composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44644.     

Structure and improved properties of PPC/PBAT blends via controlling phase morphology based on melt viscosity

Poly(propylene carbonate) (PPC)/poly(butylenes adipate-co-terephthalate) (PBAT) blends with various composition ratios were prepared via melt mixing using a twin-screw extruder. The effect of melt viscosities of polymers on mechanical behavior, interfacial interaction, thermal properties, rheological responses, and phase morphology was investigated. Results showed that the phase morphology and properties of PPC/PBAT blends were affected by the composition of the blends and the melt viscosities of the two polymers. Results of tensile tests, FTIR, and dynamic rheological measurement of PBAT-rich blends exhibited a better mechanical properties, intermolecular interactions, and compatibility when compared with PPC-rich blends due to the differences of their melt viscosities. Incorporating of PBAT effectively improved the T_g of PPC and the thermal stability of the blends. The T_c of PPC/PBAT blends markedly increased from 37.5 to 66.8 °C with addition of only 10 wt% PPC, indicating an enhanced crystallization ability of PBAT. The improvement of T_c was helpful for blown film extrusion. SEM microphotographs showed that the size of the dispersed phase particles is much smaller and the distribution is more uniform for PBAT-rich blends, compared with that in PPC-rich blends. The processing stability of blown film extrusion was improved by blending PPC with PBAT. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48924.     

Antimicrobial activity and biodegradation behavior of poly(butylene adipate‐co‐terephthalate)/clay nanocomposites

Poly(butylene adipate‐co‐terephthalate) (PBAT) nanocomposites films are prepared by a solution intercalation process using natural montmorillonite (MMT) and cetyltrimethylammonium bromide (CTAB)‐modified montmorillonite (CMMT). Cation exchange technique has been used for modification of MMT by CTAB and characterized by Fourier transform infrared analysis, thermo‐gravimetric analysis, and X‐ray diffraction (XRD) studies. CMMT gives better dispersion in the PBAT matrix than MMT and is confirmed by XRD and transmission electron microscopy. Because of better compatibility of CMMT, water vapor transmission rate of PBAT decreases more in the presence of CMMT than MMT. The biodegradability of PBAT and its nanocomposite films are studied in compost and from the morphological analysis it is apparent that the PBAT/CMMT shows a lower biodegradation rate in comparison to the PBAT/MMT. The antimicrobial activity of PBAT and its nanocomposite films is tested by an inhibition zone method. Because of the presence of the quaternary ammonium group of CTAB‐modified MMT, PBAT/CMMT nanocomposites show adequate antimicrobial activity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40079.     

Compatible and crystallization properties of poly(lactic acid)/poly(butylene adipate‐co‐terephthalate) blends

Differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and dynamic mechanical analysis (DMA) properties of poly(lactic acid)/ poly(butylene adipate‐co‐terephthalate) (PLA/PBAT) specimens suggest that only small amounts of poor PLA and/or PBAT crystals are present in their corresponding melt crystallized specimens. In fact, the percentage crystallinity, peak melting temperature and onset re‐crystallization temperature values of PLA/PBAT specimens reduce gradually as their PBAT contents increase. However, the glass transition temperatures of PLA molecules found by DSC and DMA analysis reduce to the minimum value as the PBAT contents of PLA_xPBAT_y specimens reach 2.5 wt %. Further morphological and DMA analysis of PLA/PBAT specimens reveal that PBAT molecules are miscible with PLA molecules at PBAT contents equal to or less than 2.5 wt %, since no distinguished phase‐separated PBAT droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLA/PBAT specimens, respectively. In contrast to PLA, the PBAT specimen exhibits highly deformable properties. After blending proper amounts of PBAT in PLA, the inherent brittle deformation behavior of PLA was successfully improved. Possible reasons accounting for these interesting crystallization, compatible and tensile properties of PLA/PBAT specimens are proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of biodegradable aliphatic–aromatic nanocomposites fabricated using maleic acid‐grafted poly[(butylene adipate)‐co‐terephthalate] and organically modified layered zinc phenylphosphonate

A new series of biodegradable aliphatic–aromatic nanocomposites containing maleic acid‐grafted poly[(butylene adipate)‐co‐terephthalate] (g‐PBAT) and organically modified layered zinc phenylphosphonate (m‐PPZn) were successfully synthesized through transesterification and polycondensation processes with covalent linkages between the polymeric and inorganic materials. Fourier transform infrared and ¹³C NMR spectra demonstrate the successful grafting of maleic acid to PBAT. The morphology of g‐PBAT/m‐PPZn nanocomposites was investigated using wide‐angle X‐ray diffraction and transmission electron microscopy. Results showed that the stacking layers of m‐PPZn were distributed and intercalated into the g‐PBAT polymer matrix. The incorporation of m‐PPZn into the g‐PBAT matrix significantly enhanced the storage modulus at ?70 °C as compared to that of neat g‐PBAT. A reduction in thermal stability was observed for all g‐PBAT/m‐PPZn systems, which is probably due to the lower thermal stability of m‐PPZn. The biodegradation of neat g‐PBAT copolymers and g‐PBAT/m‐PPZn nanocomposites was investigated using lipase from Pseudomonas sp. The degradation rates of neat g‐PBAT copolymers decrease in the order g‐PBAT‐80 > g‐PBAT‐50 > g‐PBAT‐20. The faster degradation rate of g‐PBAT‐80 is a result of the higher content of adipate acid units and the chain flexibility of the polymer backbone. Furthermore, the weight loss increases as the loading of m‐PPZn increases, indicating that the presence of m‐PPZn improves the degradation of the g‐PBAT copolymers. This result might be accounted for by the lower degree of crystallinity for g‐PBAT/m‐PPZn nanocomposites. © 2019 Society of Chemical Industry     

Synthesis,characterization, and properties of novel fluorine containing aromatic polyamides

A series of novel fluorine containing aromatic polyamides were synthesized by the direct polycondensation of various fluorine containing aromatic diamines and commercially available 5‐t‐butyl isophthalic acid. These polyamides have good solubility in several organic solvents such as dimethylformamide, N,N‐dimethylacetamide, 1‐Methyl‐2‐pyrrolidone, dimethyl sulfoxide, and tetrahydrofuran. The synthesized polymers exhibited inherent viscosities up to 0.93 dL/g and M_w up to 1,52,000 with PDI of 2.49. The polyamides exhibited good thermal stability up to 489°C for 10% weight loss in nitrogen and high glass transition temperature up to 273°C. Dynamic mechanical analysis showed a very good retention of storage modulus up to the glass transition temperature. The tan δ peak value at 1 Hz was used to calculate the T_g and these values are in good agreement with differential scanning calorimetry data. The polyamide films were flexible with tensile strength up to 72 MPa, elongations at break up to 14%, and modulus of elasticity up to 1.39 GPa depending on the exact repeating unit structure. X‐ray diffraction measurements indicate that these polyamides are semicrystalline. Rheology study showed same trend of melt viscosity behavior with different shear rate for all polymers. Water absorption study indicates the hydrophobic nature of the polymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hydrophobic nanocomposites of PBAT with Cl-fn-POSS nanofiller as compostable food packaging films

Antibacterial nanocomposite films of poly(butylene adipate-co-terephthalate) (PBAT) incorporated with different weight percentage of octakis(3-chloropropyl)octasilsesquioxane (chloropropyl functionalized POSS [Cl-fn-POSS]) nanofiller were prepared. The mechanical, thermal, morphological, barrier, and antimicrobial properties were examined. The mechanical properties of the nanocomposite films were enhanced by the addition of Cl-fn-POSS nanofiller. An optimum filler loading of 3 wt% is identified to be best suited for maximum enhancement in tensile strength (24 MPa for 3 wt% filled PBAT vs 11 MPa for neat PBAT) while a 1 wt% filler loading was adequate to double the tensile strength. The barrier properties (WVTR and oxygen transmission rate) of PBAT was improved by the presence of Cl-fn-POSS. A volume of 3 wt% filler loading results in 50% reduction of water permeation and 10% reduction in oxygen transmission. The thermogravimetric analyses of the nanocomposites indicated that the filler enabled the enhancement of thermal stability of PBAT. The nanocomposite films revealed antimicrobial activity with this activity increasing with increasing filler content. PBAT is compostable under suitable conditions and with a low weight percentage of filler that is largely made of silicon dioxide these nanocomposite films can find application as biodegradable food packaging material given their flexibility.     

Preparation and properties of melt‐processable polyimides based on fluorinated aromatic diamines and aromatic dianhydrides

Two series of melt‐processable polyimides were prepared from 4,4′‐bis(3‐amino‐5‐trifluoromethylphenoxy)biphenyl (m‐6FBAB) and 4,4′‐bis(4‐amino‐5‐trifluoromethylphenoxy) biphenyl (p‐6FBAB) with various aromatic dianhydrides. The effects of the chemical structures of the polyimides on their properties, especially the melt processability and organic solubility, were investigated. The experimental results demonstrate that some of the fluorinated aromatic polyimides showed good melt processability at elevated temperatures (250–360°C) with relatively low melt viscosities and could be melt‐molded to produce strong and tough polyimide sheets. Meanwhile, the polyimides showed excellent organic solubility in both polar aprotic solvents and common solvents to give stable polyimide solutions with high polymer concentrations and relatively low viscosities. Thus, we prepared high‐quality polyimide films by casting the polyimide solutions on glass plates followed by baking at relatively low temperatures. The polyimides derived from m‐6FBAB showed better melt processability and solubility than the p‐6FBAB based polymers. The melt‐processable polyimides showed a good combination of thermal stability and mechanical properties, with decomposition temperatures of 547–597°C, glass‐transition temperatures in the range 205–264°C, tensile strengths of 81.3–104.9 MPa, and elongations at break as high as 19.6%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal stability and degradation of biological terpolyesters over a broad temperature range

Because of high susceptibility to thermal degradation during conventional melt processing of poly(3‐hydroxybutyrate) (P3HB) homopolymer, incorporation of a second or third monomer unit in the polyester backbones is expected to reduce the melting temperature and crystallinity, resulting in a controlled thermal degradation with improved stability. In this work, random poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxyvalerate) (P3HB3HV4HV) terpolyesters biologically synthesized by Cupriavidus necator were investigated for the thermal stability and degradation over a broad temperature range (100–300°C) in comparison with P3HB homopolyester. The work revealed that below the complete melting point (around 150°C), the terpolyester exhibited a high thermal stability and became an amorphous semisolid suitable for conventional thermal processing. Size exclusion chromatography plus nuclear magnetic resonance analysis was used to examine the thermal degradation products and the vulnerability of different monomer units at high temperatures (240–290°C). We found that 3HV unit in P3HB3HV4HV copolymers was more vulnerable to thermal degradation than 3HB unit under air. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41715.