Analysis and evaluation of biobased polyester of PTT/PBAT blend: thermal,dynamic mechanical,interfacial bonding,and morphological properties

Novel blends were prepared from biobased poly(trimethylene terephthalate) (PTT) and poly(butylene adipate‐co‐terephthalate) (PBAT) using a twin screw extrusion process as a function of different weight ratios. Thermal stability, mechanical, and interfacial properties of PTT/PBAT blends were investigated using a thermogravimetric analyzer and mechanical analyzer. Phase behavior and surface morphology of the blends were characterized using scanning electron microscopy. Interfacial bonding value of the PTT/PBAT blend was evaluated from the Pukanszky empirical relationship. Viscoelastic properties of PTT/PBAT blends were investigated using the dynamic mechanical analyzer. PTT/PBAT blend exhibited higher thermal stability than the neat PTT matrix. The entire blend showed better interfacial adhesion between the matrixes. Storage and loss modulus of the PTT/PBAT blend reduces with increasing PBAT content. PTT/PBAT blend exhibited higher impact energy than the neat PTT matrix, because of its flexible and amorphous nature of PBAT polymer and increasing toughness. Copyright © 2016 John Wiley & Sons, Ltd.     

Synergistic effect of compatibilizer and sepiolite on the morphology of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(butylene succinate) blends

Blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(butylene succinate) (PBS) with different PHBV/PBS weight ratios (100/0, 75/25, 50/50 and 0/100) were elaborated by melt mixing. The morphological investigation of the different samples, in comparison with that of neat PHBV and neat PBS, pointed out that PHBV/PBS blends form a biphasic system over the whole composition range. Low amount of compatibilizing agent (5 wt%), obtained by grafting maleic anhydride (MA) onto PHBV, i.e. PHBV-g-MA, was used for improving the miscibility between the two components of the blend. The incorporation of a fibrous filler as the sepiolite, easily dispersible in a polymer matrix, was also investigated. The morphology of the different blends as well as the evolution of their material properties were discussed in terms of the sepiolite and compatibilizing agent contents. The dispersion of PBS in the PHBV matrix markedly became finer with incorporation of sepiolite and PHBV-g-MA, due to enhanced interactions between the components. This paper highlighted a synergistic effect induced by the presence of both compatibilizer and sepiolite leading to an improved miscibility of the two blend components. The resulting properties were correlated with the morphology observed for the different blends.     

Cellulose acetate butyrate as multifunctional additive for poly(butylene succinate) by melt blending: Mechanical properties, biomass carbon ratio, and control of biodegradability

We have evaluated the plasticizing effect of poly(butylene succinate) (PBS) and cellulose acetate butyrate (CAB). PBS and CAB were mixed with a melt-kneading machine. The tensile strength and strain at break in the case of the blend with 10% CAB in the PBS matrix were 547% and 35 MPa. It showed that CAB acted as a plasticizer for PBS. The biomass carbon ratio of the blends measured by accelerator mass spectrometry based on ASTM D6866 showed that the biomass carbon derived from a part of the CAB corresponded to the theoretical value of the polymer blend. The biodegradation of PBS with the CAB melt blend powders was evaluated by a microbial oxidative degradation analyzer under controlled compost conditions based on ISO 14855-2. PBS with 10% CAB was not degraded within 60 days due to the addition of CAB that could control the biodegradability of the PBS.     

Formation and morphology of cellulose acetate butyrate (CAB)/polyolefin and CAB/polyester in situ microfibrillar and lamellar hybrid blends

Cellulose acetate butyrate (CAB)/iPP (isotactic polypropylene), CAB/HDPE (high density polyethylene), CAB/PET (poly ethylene terephthalate), CAB/PTT (poly trimethylene terephthalate), CAB/PBT (poly butylenes terephthalate) and CAB/IPET-PEG (poly(ethylene terephthalate-co-isophthalate)-poly(ethylene glycol)) in situ microfibrillar and lamellar hybrid blends at a weight ratio of 80/20 were prepared by melt extrusion. Microfibrillar and lamellar hybrid morphologies of CAB/polyolefin and CAB/polyester blends under different force fields were investigated. The formation process of in situ microfibrillar and lamellar hybrid blends were analyzed and proposed.     

Physico-Mechanical Properties of Biodegradable Rubber Toughened Polymers

Summary: In this study, blends of poly(lactic acid) (PLA) with poly(butylene adipate-co-terephthalate) (PBAT) were studied for their mechanical and thermal properties as a function of the PBAT content. Tensile testing, impact testing, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMTA) and scanning electron microscopy (SEM) were used to characterize the blends. It was observed that PLA/PBAT blends maintained quite high modulus and tensile strength compared to pure PLA. Small amounts of PBAT improved the elongation at break and the impact resistance showing a debonding effect typical of rubber toughened systems.     

Biodegradable Foaming Material of Poly(butylene adipate-co-terephthalate) (PBAT)/Poly(propylene carbonate) (PPC)

A biodegradable blend foaming material of poly(butylene adipate-co-terephthalate)(PBAT)/poly(propylene carbonate)(PPC)was successfully prepared by chemical foaming agent and screw extrusion method.First,PBAT was modified by bis(tert-butyl dioxy isopropyl)benzene(BIBP)for chain extension,and then the extended PBAT(E-PBAT)was foamed with PPC using a twin(single)screw extruder.By analyzing the properties of the blends,we found that Young’s modulus increased from 58.8 MPa of E-PBAT to 244.7 MPa of E-PBAT/PPC 50/50.The viscosity of the polymer has a critical influence on the formation of cells.Compared with neat PBAT(N-PBAT),the viscosity of E-PBAT increased by 3396 Pa·s and E-PBAT/PPC 50/50 increased by 8836 Pa·s.Meanwhile,the dynamic mechanical analysis(DMA)results showed that the storage modulus(E’)at room temperature increased from 538 MPa to 1650 MPa.The various phase morphologies(“sea-island”,“quasi-co-continuous”and“cocontinuous”)and crystallinity of the blends affected the spread velocity of gas and further affected the foaming morphology in E-PBAT/PPC foam.Therefore,through the analysis of phase morphology and foaming mechanism,we concluded that the E-PBAT/PPC 70/30 component has both excellent strength and the best foaming performance.     

Elevated ductility,optical, and air barrier properties of poly (butyleneadipate‐co‐terephthalate) bio‐based films via novel thermoplastic starch feature

It is important to develop high performances biodegradable polymers to eliminate the “white pollution” evoked by petroleum‐based polymer. Thermoplastic starch (TPS) with nano‐ellipse configuration was fabricated to reinforce the performances of poly (butylene adipate co‐terephthalate) (PBAT) biocomposites. Effects of tartaric acid (TA) (0.5% wt) on the structure of TPS and compatibility for PBAT were evaluated by Fourier‐transform infrared spectroscopy (FTIR), viscosity and rheological measurement, dynamic mechanical analysis (DMA) and scanning electron microscope (SEM), respectively. They revealed that TA reduced the molecular weight of starch and shear viscosity of TPS were beneficial for TPS dispersing in PBAT matrix with 184‐nm averaged diameter. PBAT/TPS‐TA (70:30 wt%) biocomposite films were blew with different blow‐up ratio. The morphology of films presented that nano‐TPS‐TA wrapped in the PBAT matrix and deformed from ball to capsule feature without agglomeration. Compared with those of PBAT film, the increment in elongation at break of PBAT/TPS‐TA film was 100%. The air permeability and UV‐VIS transmittance of PBAT/TPS‐TA films decreased from 6.92 × 10^?9 to 3.72 × 10^?9 cm³·cm·cm^?2 s^?1 Pa^?1 and 47.6% to 23.5%, respectively. This study proposed a facile approach to fabricate low‐cost PBAT films with significant improved mechanical, optical, and air barrier properties for commercial application. Mechanism for nanoparticles of TPS‐TA motivated the elevated performances was proposed, synchronously.     

Thermal degradation of poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) and their blends upon melt processing

Poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are biodegradable aliphatic polyesters, which being semicrystalline and thermoplastic can be processed by conventional methods. Their blends give interesting materials for industrial packaging applications, due to their increased ductility as PBAT content increases. However, like many aliphatic polyesters, the PLA matrix degrades upon melt processing thus affecting the thermo-mechanical features of the blended material. In this work, we studied the effect of processing at high temperature on the molecular weight distribution, morphology, and thermo-mechanical properties of both homopolymers, as well as the PLA/PBAT 75/25 blend. Notably, different processing conditions were adopted in terms of temperature (range 150-200 °C) and other relevant processing parameters (moisture removal and nitrogen atmosphere). Analysis of PLA/PBAT blends indicated that intermolecular chain reactions took place under strong degradative conditions of PLA, yielding PLA/PBAT mixed chains (copolymers). Increasing amounts of copolymers resulted in improved phase dispersion and increased ductility, as SEM and mechanical tests indicated. Conversely, reduced PLA degradation with less copolymer formation, afforded higher modulus materials, owing to poorer dispersion of the soft phase (PBAT) into the PLA matrix.     

Technology Trends in Biodegradable Polymers: Evidence from Patent Analysis

The public and governmental awareness regarding more sustainable products have gained significant momentum in the last decade and are directing the future research of the next generation of materials and processes. In such a setting, biodegradable polymers are regarded as one of the technologies driving the innovation and current market growth because they provide an additional end of life option. Tracing the evolving trends of these emerging technologies will help researchers, investors, and policy makers to better evaluate the opportunities of the technology as well as to understand the technology's changing characteristics. Therefore, within this study, we perform bibliographic analyses based on patent information to delineate the current research landscape and to anticipate the future development trends by focusing on the cases of poly(lactic acid) (PLA), poly(hydroxyalkanoates) (PHAs), polycaprolactone (PCL), poly(butylene succinate) (PBS), and poly(butylene adipate-co-terephthalate) (PBAT). The following findings were made: First, PLA gets the highest attention from both academia and industry. Second, the overall international presence of biodegradable polymer patents is high, especially in the field of PHAs. Third, technology maturity and technology strength show that PLA is the most promising technology at present in technological terms, whereas PHAs, PCL, and PBS are uncertain technologies and PBAT has a rather low development potential.     

聚对苯二甲酸丙二醇酯的无卤阻燃化改性

聚对苯二甲酸丙二醇酯作为新型聚酯材料,具有非常优良的性能,但其易燃性很大的限制了它的应用范围。为了提高对苯二甲酸乙二醇酯的阻燃性能,本文以无卤膨胀型EPFR-300A为阻燃改性剂,马来酸酐接枝聚烯烃(POE-g-MAH)弹性体为增韧剂,对聚对苯二甲酸丙二醇酯树脂(PTT)进行阻燃改性。通过热重分析仪(TGA)、示差扫描量热仪(DSC)、扫描电子显微镜(SEM)、力学性能等技术手段研究了阻燃剂和增韧剂对PTT树脂力学、热学和阻燃性能的影响。结果表明,增韧剂POE和POE-g-MAH的添加提高了PTT树脂的综合力学性能。当质量分数相同时,POE-g-MAH对PTT树脂的增韧效果要优于POE,且当POE-g-MAH质量分数为7%时,综合力学性能最佳。当添加相同质量分数增韧剂,EPFR-300A质量分数达到20%时,阻燃PTT材料阻燃性能最佳,极限氧指数(LOI)达到28.0%,垂直燃烧阻燃等级达到UL94 V-0级。EPFR-300A阻燃剂与PTT树脂间相容性良好,可以有效地促进PTT树脂成炭并提高材料的阻燃性能。     

Porous structures of polymer films prepared by spin coating with mixed solvents under humid condition

We investigate the effects of interfacial energy between water and solvent as well as polymer concentration on the formation of porous structures of polymer films prepared by spin coating of cellulose acetate butyrate (CAB) in mixed solvent of tetrahydrofuran (THF) and chloroform under humid condition. The interfacial energy between water and the solvent was gradually changed by the addition of chloroform to the solvent. At a high polymer concentration (0.15 g/cm3 in THF), porous structures were limited only at the top surfaces of CAB films, regardless of interfacial energies, due to the high viscosity of the solution. At a medium concentration (approximately 0.08 g/cm3 in THF), CAB film had relatively uniform pores at the top surface and very small pores inside the film because of the mixing of the water droplets with THF solution. When chloroform was added to THF, pores at the inner CAB film had a comparable size with those at the top surface because of the reduced degree of the mixing between the water droplets and the mixed solvent. A further decrease in polymer concentration (0.05 g/cm3 in THF) caused the final films to have a two-layer porous structure, and the size of pores at each layer was almost the same.     

Morphology and properties of biodegradable poly (lactic acid)/poly (butylene adipate-co-terephthalate) blends with different viscosity ratio

Phase morphology exerts a tremendous influence on the properties of polymer blends. The development of the blend morphology depends not only on the intrinsic structure of the component polymers but also on extrinsic factors such as viscosity ratio, shearing force and temperature in the melt processing. In this study, various poly (butylene adipate-co-terephthalate) (PBAT) materials with different melt viscosity were prepared, and then poly (lactic acid) (PLA)/PBAT blends with different viscosity ratio were prepared in a counter-rotating twin-screw extruder under constant processing conditions. The influence of viscosity ratio on the morphology, mechanical, thermal and rheological properties of PLA/PBAT (70/30 w/w) blends was investigated. The experimental results showed that the morphology and properties of PLA/PBAT blends strongly depended on the viscosity ratio. Finer size PBAT phase were observed for viscosity ratio less than 1 (λ < 1) compared to samples with λ > 1. It was found that the interfacial tensions of PLA and PBAT were significantly different when the viscosity ratio was changed, the lowest interfacial tensions (0.12 mN/m) was obtained when the viscosity was 0.77. Additionally, the maximal tensile strength in PLA/PBAT blends were obtained when the viscosity ratio was 0.44, while the maximal impact properties were obtained when the viscosity ratio was 1.95.     

Preparation of PLA-based nanocomposites modified by nano-attapulgite with good toughness-strength balance

Polylactic acid (PLA) was modified by poly (butylene adipate-co-terephthalate) (PBAT) and nano-attapulgite (AT) using the melt blending technique. Ethylene-butyl acrylate-glycidyl methacrylate (E-BA-GMA) was used as a compatibilizer which can bond the AT nanoparticles with PLA/PBAT matrix by interaction between the epoxy and hydroxyl groups. The effects of the AT content on the mechanical properties, thermal properties, crystallinity and morphology of PLA/PBAT/ATT nanocomposites were investigated. The results showed that the tensile strength, elongation at break and impact strength of PLA/PBAT could be simultaneously increased by incorporating AT nanoparticles. PLA/PBAT/AT nanocomposites possessed higher thermal stability than pure PLA/PBAT. In the ternary composite system of PLA/PBAT/AT, AT acted as a heterogeneous nucleating agent and was able to increase the crystallization temperature. When the AT content was low (≤2.5 wt%), AT nanoparticles could uniformly disperse in the PLA/PBAT matrix. In general, AT was an effective filler to reinforce and toughen PLA/PBAT blend simultaneously, and the PLA/PBAT/AT nanocomposite with 2.5 wt% AT exhibited a good combination of strength and toughness.     

In situ polymerized poly(butylene succinate)/silica nanocomposites: Physical properties and biodegradation

A series of poly(butylene succinate)/silica (PBS/silica) nanocomposites were prepared by in situ polymerization. Solid-state ²⁹Si NMR and FTIR analysis indicated that silanol-bonded carbonyl groups are established within PBS/silica nanocomposite materials. Rheological effects inherent to the silica filler were evaluated by melt rheological analysis as a function of shear force in the molten state. Despite high shear force, PBS/silica nanocomposites maintained a relatively high melt viscosity, attributable to a network structure resulting from covalent bonding between silica and the polymer chain. Nanocomposite material containing 3.5 wt% silica exhibited greatly improved mechanical properties. The tensile strength at break and elongation were ca. 38.6 MPa and 515%, while those of the parent PBS were 26.3 MPa and 96%, respectively. PBS/silica nanocomposites showed composition dependency on biodegradation ascribable to reduced crystallinity and preferential microbial attack.     

Protecting enzymes against heat inactivation by temperature-sensitive polymer in confined space

At high temperature, many enzymes are inactivated by aggregations at hydrophobic sites which are exposed on denaturation. Isolating denatured enzymes via hydrophobic interactions with other material is a significant method to prevent enzymes from aggregation. But the temperature-sensitive polymer poly(N-isopropylacrylamide) (PNIPAAm), supposed to protect enzymes spontaneously at high temperatures, can not efficiently complex denatured carbonic anhydrase B (CAB, as a model enzyme) in bulk aqueous solution due to different phase transition speeds. Here, we present a novel method for protecting enzymes against heat inactivation, in which PNIPAAm and CAB are encapsulated in a confined space constructed by reverse microemulsion. At high temperatures, PNIPAAm forms nanoscale aggregates possessing both large specific surface areas and hydrophobic surfaces, and then adsorbs denatured CAB via hydrophobic interactions to avoid intermolecular aggregation of CAB. With cooling, CAB is released spontaneously and recovers its activity. The assays for enzymatic activity demonstrate that CAB is effectively protected against heat inactivation through this method (protection efficiency is up to 83.2%).     

Enhancement of mechanical and thermal properties of oil palm empty fruit bunch fiber poly(butylene adipate-co-terephtalate) biocomposites by matrix esterification using succinic anhydride

In this work, the oil palm empty fruit bunch (EFB) fiber was used as a source of lignocellulosic filler to fabricate a novel type of cost effective biodegradable composite, based on the aliphatic aromatic co-polyester poly(butylene adipate-co-terephtalate) PBAT (Ecoflex?), as a fully biodegradable thermoplastic polymer matrix. The aim of this research was to improve the new biocomposites' performance by chemical modification using succinic anhydride (SAH) as a coupling agent in the presence and absence of dicumyl peroxide (DCP) and benzoyl peroxide (BPO) as initiators. For the composite preparation, several blends were prepared with varying ratios of filler and matrix using the melt blending technique. The composites were prepared at various fiber contents of 10, 20, 30, 40 and 50 (wt %) and characterized. The effects of fiber loading and coupling agent loading on the thermal properties of biodegradable polymer composites were evaluated using thermal gravimetric analysis (TGA). Scanning Electron Microscopy (SEM) was used for morphological studies. The chemical structure of the new biocomposites was also analyzed using the Fourier Transform Infrared (FTIR) spectroscopy technique. The PBAT biocomposite reinforced with 40 (wt %) of EFB fiber showed the best mechanical properties compared to the other PBAT/EFB fiber biocomposites. Biocomposite treatment with 4 (wt %) succinic anhydride (SAH) and 1 (wt %) dicumyl peroxide (DCP) improved both tensile and flexural strength as well as tensile and flexural modulus. The FTIR analyses proved the mechanical test results by presenting the evidence of successful esterification using SAH/DCP in the biocomposites' spectra. The SEM micrograph of the tensile fractured surfaces showed the improvement of fiber-matrix adhesion after using SAH. The TGA results showed that chemical modification using SAH/DCP improved the thermal stability of the PBAT/EFB biocomposite.     

The morphological,mechanical, rheological,and thermal properties of PLA/PBAT blown films with chain extender

Biodegradable poly(lactic acid) (PLA)/poly(butylene adipate‐co‐terephthalate) (PBAT) blends and films were prepared using melt blending and blowing films technique in the presence of chain extender‐Joncryl ADR 4370F. The ADR contains epoxy functional groups and used as a compatibilizer. The morphological, mechanical, rheological, thermal, and crystalline properties of the PLA/PBAT/ADR blown films were studied. Scanning electron microscopy micrographs of the films revealed more ductile deformation with increasing PBAT content. The addition of PBAT enhanced the toughness of the PLA film. Tensile tests indicated that the elongation at break increased from 20.5% to 334.6% in the machine direction and from 7.1% to 715.9% in the transverse direction. The Young modulus increased from 2690.5 to 395.6 MPa in the machine direction and from 2623.5 to 154.0 MPa in the transverse direction. The sealing strength of 40/60/0.15 PLA/PBAT/ADR film was the highest among all the samples up to 9.4 N 15 mm⁻¹. These findings gave important implications for designing and manufacturing polymer packaging materials.     

Thermal properties and degradability of poly(propylene carbonate)/poly(β-hydroxybutyrate-co-β-hydroxyvalerate) (PPC/PHBV) blends

Poly(propylene carbonate)/poly(β-hydroxybutyrate-co-β-hydroxyvalerate) (PPC/PHBV) blends were prepared via the solution casting method at different proportions. Their thermal characteristics were studied by means of differential scanning calorimetry (DSC) and thermogravimetry (TG). The degradability of the blends was investigated in soil suspension cultivation and in vitro degradation testing. The changes of structure and molecular weight for blends were also studied by ¹H nuclear magnetic resonance spectroscopy (¹H NMR), scanning electron microscopy (SEM) and gel permeation chromatography (GPC) before and after degradation. Although the PPC/PHBV blends were immiscible, the addition of PHBV could improve the thermal stability of PPC. PHBV was degraded mainly by the action of microbial enzymes in the soil suspension, which biodegraded it more rapidly than PPC in a natural environment. PPC was degraded mainly by chemical hydrolysis and random hydrolytic scission of chains in the PBS solution in vitro, and degradation of PPC was more rapid than that of PHBV in a simulated physiological environment.     

Thermal stability of the PBAT biofilms with cellulose nanostructures/essential oils for active packaging

The primary objective of this study is to evaluate the thermal stability of the active films with the cellulose nanostructure (CNS, 5?mass%) treated with encapsulated essential oils (EOs), eugenol and linalool. CNS untreated and treated were incorporated in the poly(butylene adipate-co-terephthalate) (PBAT) polymer matrix prepared by casting. In this study, all samples were characterized by FTIR, DRX, TG, DSC and SEM, elucidating the contribution of each component in the final films. CNS untreated and treated with EOs were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis (TGA), confirming the interaction between these components. The active biofilms were analyzed by TGA and DSC analyses (differential scanning calorimetry), confirming that their thermal stability was maintained similar to the neat PBAT film, without loss of properties. The CI (crystallinity index, %) of the polymeric films was calculated from heat fusion (ΔH) values, indicating that the incorporation of the nanostructures into the PBAT matrix increases the crystallinity of the biofilms, from 11.5 (neat PBAT) to 13.8% (PBAT/CNS-E), acting as a nucleating agent in the polymeric matrix. The presence of the EOs did not decrease the CNS stability, as well of the biocomposite films. Moreover, the thermal analysis confirmed that the EO was well involved by the CNS, before and after the incorporation in the PBAT polymer, as observed in the SEM images.

     

Valorization of olive husk flour as a filler for biocomposites based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate): Effects of silane treatment

The paper deals with the influence of surface treatment of olive husk flour (OHF) by trimethoxyoctadecylsilane (TMOS) on the morphology and physical properties of bio-composites based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Biocomposites based on PHBV/OHF: 80/20 (w/w) before and after filler treatment were prepared by melt compounding, while the modification of OHF surface by TMOS was performed by thermo-chemical vapor deposition. Scanning electron microscopic observations showed that modification of OHF by TMOS led to homogeneous and finer dispersion of the filler particles in PHBV matrix, indicating improved compatibility between the two components. Further, TGA data revealed an increase in thermal stability of treated PHBV/OHF biocomposites. An increase in the crystalline index determined by DSC was also observed due to the nucleating effect of OHF in the polymer matrix, however more pronounced for the treated biocomposites. The latter exhibited better tensile properties, as confirmed by DMA results, showing higher reinforcing effect of OHF for the treated biocomposites. This study highlighted significant improvements of the properties of PHBV/OHF biocomposites through silane treatment of OHF.