Polylactide/poly(butylene adipate‐co‐terephthalate)/rare earth complexes as biodegradable light conversion agricultural films

Rare earth europium(III) complex with α‐thenoyltrifluoroacetone and triphenylphosphine oxide (Eu (TTA)₃(TPPO)₂, shortened as EuTT) was synthesized in this paper, then blended with polylactide (PLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) to prepare the biodegradable agricultural films. Through the optical performance, mechanical properties, and other research, the results showed that the rare earth complex could convert the sun's ultraviolet light to red light when doped polymer. Moreover, the relative intensity ratio of ⁵D₀/⁷F₂ to ⁵D₀/⁷F₁ of PLA/PBAT/EuTT film could reach 3.79, which implied that the film had strong fluorescence intensity and high color purity. The highest tensile strength of the film could reach 36.7/25.2 MPa, and the elongation at break was 462.8/483.0% in the machine and in the transverse direction when the added amount of Eu (TTA)₃(TPPO)₂ was 0.1 wt%. The tensile strength of the film was 33.3/20.1 MPa, and the elongation at break could reach 535.8/413.6% when the added amount of Eu (TTA)₃(TPPO)₂ was increased up to 0.3 wt%. Gel permeation chromatography showed that the Eu (TTA)₃(TPPO)₂ could cause depolymerization of polylactide, resulting in a decrease in the molecular weight of PLA. Furthermore, the crystallization ability of PLA was also improved. In this paper, the biodegradable films exhibited excellent ultraviolet light conversion ability and mechanical properties.     

Morphology and thermal properties of poly(L‐lactide)/poly(butylene succinate‐co‐butylene adipate) compounded with twice functionalized clay

Poly(L ‐lactide) (PLLA)/poly(butylene succinate‐co‐butylene adipate) (PBSA) blends were compounded with Cloisite 25A® (C25A) and C25A functionalized with epoxy groups, respectively. Epoxy groups on the surface of C25A were introduced by treating C25A with (glycidoxypropyl)trimethoxy silane (GPS) to produce so called Twice Functionalized Organoclay (TFC). Variation of morphology and properties of PLLA/PBSA/C25A composites was investigated before and after the treatment with GPS. The morphological structure of the composites was analyzed by using X‐ray diffractometry (XRD) and transmission electron microscopy (TEM). The silicate layers of PLLA/PBSA/TFC were exfoliated to a larger extent than PLLA/PBSA/C25A. Incorporation of the epoxy groups on C25A improved significantly elongation at break as well as tensile modulus and tensile strength of PLLA/PBSA/C25A. The larger amount of exfoliation of the silicate layers in PLLA/PBSA/TFC as compared with that in PLLA/PBSA/C25A was attributed to the increased interfacial interaction between the polyesters and the clay due to chemical reaction. Thermo gravimetric analysis revealed that both T_5%, which was the temperature corresponding to 5% weight loss, and activation energy of thermal decomposition of PLLA/PBSA/TFC were far superior to those of PLLA/PBSA/C25A as well as to those of PLLA/PBSA, indicating that the composites with exfoliated silicate layers were more thermally stable than those with intercalated silicate layers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 478–487, 2005     

Synthesis and Characterization of Poly（butylene adipate-co-terephthalate） Catalyzed by Rare Earth Stearates

Rare earth （Nd, Y, La, Dy） stearates have been synthesized and used as single component catalysts for the polycondensation of dimethyl terephthalate, adipic acid and 1,4-butanediol for the first time preparing biodegradable poly（butylene adipate-co-terephthalate） （PBAT） with high molecular weight, The microstructures of PBAT were characterized by ^1H NMR spectra. The PBAT exhibits good mechanical properties such as high tensile strength （ca. 20 MPa） and long break elongation （〉700%）.     

Influence of biodegradation on crystallization of poly (butylene adipate‐co‐terephthalate)

The biodegradation of aromatic‐aliphatic biodegradable polyester poly (butylene adipate‐co‐terephthalate) (PBAT) was studied under mesophilic (37°C) and thermophilic (55°C) anaerobic conditions. Anaerobic sludge from municipal wastewater treatment plant was utilized as an inoculum. Non‐isothermal crystallization kinetics of PBAT before and after biodegradation was explored by differential scanning calorimetry. Under mesophilic anaerobic conditions (37°C), the biodegradation after 126 days was only 2.2%, molecular weight changed from 93 000 to 25 500 g/mol, and the crystallization behavior was changed only slightly. However, biodegradation under thermophilic anaerobic conditions (55°C) caused much bigger changes: biodegradation according to biogas production reached after 126 days 8.3%, molecular weight changed from 93 000 to 9430 g/mol, and the crystallization behavior was changed significantly. While T_m increased only slightly, T_c on the other hand increased significantly for the sample after biodegradation at 55°C. Also, the crystallization rate was slower (particularly at lower cooling rates), but crystallinity was slightly higher. The diffraction pattern was observed by X‐ray diffraction.     

Effects of comonomer sequential structure on thermal and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate)s

In this work, new investigations on the effect of comonomer sequential structure on the thermal and crystallization behaviors and biodegradability have been implemented for the biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST) as well as aliphatic poly(butylene succinate) (PBS). At first, these copolyesters were efficiently synthesized from dimethyl succinate and/or dimethyl terephthalate and 1,4‐butanediol via condensation polymerization in bulk. Subsequently, their molecular weights and macromolecular chain structures were analyzed by gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. By means of differential scanning calorimeter (DSC) and wide‐angle X‐ray diffractometer (WAXD), thermal and crystallization behaviors of these synthesized aromatic–aliphatic copolyesters were further explored. It was demonstrated that the synthesized copolyesters were revealed to have random comonomer sequential structures with thermal and crystallization properties strongly depending on their comonomer molar compositions, and that crystal lattice structures of the new crystallizable copolyesters shifted from the monoclinic crystal of semicrystalline PBS to triclinic lattice of the poly(butylene terephthalate) (PBT) with increasing the terephthalate comonomer composition, and the minor comonomer components were suggested to be trapped in the crystallizable component domains as defects. In addition, the enzymatic degradability was also characterized for the copolyesters film samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1635–1644, 2006     

Impact of cellulose nanocrystal aspect ratio on crystallization and reinforcement of poly(butylene adipate‐co‐terephthalate)

Cellulose nanocrystals (CNCs) are appealing nanomaterials for the reinforcement of polymeric materials. It is now well established that high mechanical properties are obtained when preparing the nanocomposite by casting/evaporation methods and using CNC contents above the percolation threshold. This phenomenon results from the formation of a stiff CNC network within the matrix meaning that the properties of the matrix play only a limited role on the mechanical properties of the material when the matrix is in the rubbery state. In subpercolation concentration or when using a different processing technique, the level of understanding is less clear, mainly when the CNC‐induced crystallization of the matrix interferes with the reinforcing mechanism. In this study, we used CNCs with different aspect ratios to prepare nanocomposites by extrusion with polybutyrate adipate terephthalate as matrix. The impact of CNC on the crystallinity of the matrix and mechanical properties of the nanocomposite has been investigated. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2284–2297     

Nonisothermal crystallization behavior of poly(butylene adipate‐co‐terephthalate)/clay nano‐biocomposites

The study of the nonisothermal crystallization behavior of layered silicates micro‐ and nano‐biocomposites based on poly(butylene adipate‐co‐terephthalate) (PBAT), a biodegradable copolyester, has been carried out with different theoretical models. They were applied and developed with the aim to describe and better understand the influence of the layered silicates dispersion on crystallization. The nucleation efficiency of the layered silicates has been demonstrated with the use of the “Modified Avrami model,” thanks to the higher crystallization rate parameter, Z_c, and of the lower crystallization half‐time, t_1/2, compared to the neat matrix. The crystallization activation energies, E_a, calculated from “Kissinger's model” have shown that layered silicates have a negative effect on the crystallite growth process. Thus, these analyses have shown that layered silicates have a double effect on the crystallization process. These two opposites' phenomena depend on the dispersion quality and are more pronounced for the intercalated nano‐biocomposites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1503–1510, 2007     

TiO2 nanoparticles/poly(butylene adipate‐co‐terephthalate) bionanocomposite films for packaging applications

In this present study, biodegradable PBAT nanocomposites containing different weight percentages (1, 3, 5, 7, and 10% w/w) of TiO₂ nanoparticles were prepared by using solvent casting technique, chloroform as a solvent. The microstructure and morphology of the as‐synthesized poly(butylene adipate‐co‐terephthalate) (PBAT)/TiO₂ nanocomposite films were characterized by Fourier‐transform infrared, X‐ray diffraction, scanning electron microscopy, and transmission electron microscope. The thermal degradation of PBAT composites was studied by using thermogravimetric analysis. The mechanical strength of the films was improved by increasing TiO₂ concentration. Tensile strength increased from 32.60 to 63.26 MPa, respectively. Barrier properties of the PBAT/TiO₂ nanocomposites were investigated by using an oxygen permeability tester. The oxygen permeability (oxygen transmission rate) decreased with increasing the TiO₂ nanoparticle concentrations. The PBAT/TiO₂ nanocomposite films showed profound antimicrobial activity against both Gram‐positive and Gram‐negative foodborne pathogenic bacteria, namely, Escherichia coli and Staphylococcus aureus, to understand to the zone of inhibition. These results indicated that filler–polymer interaction is important and the role of the TiO₂ as a reinforcement in the nanocomposites was evident. Copyright © 2017 John Wiley & Sons, Ltd.     

Preparation and characterization of novel transparent plasticized poly(butylene terephthalate)‐co‐poly(alkylene glycol terephthalate) gel

Transparent plasticized gels with good mechanical, optical, and dielectric properties have important applications in various fields. We prepared a new gel using a poly(butylene terephthalate)‐co‐poly(alkylene glycol terephthalate) (PBT‐co‐PAGT) copolymer and a plasticizer, dibutyl adipate (DBA). This method improved the polymer crystallinity, and suppressed particle formation in cast‐films when the polymer was dissolved in 1,1,1,3,3,3‐hexafluoro‐2‐propanol, followed by solvent evaporation, and enabled uniform swelling of the polymer network by the plasticizer to form a transparent and flexible gel. The dielectric constants of the developed PBT‐co‐PAGT/DBA gels are much higher than those of PBT‐co‐PAGT films at low frequency. We believe that these PBT‐co‐PAGT/DBA gels could be used as photovoltaic, dielectric, and actuator materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 829–832     

Effect of PEO‐PPO‐PEO copolymer on the mechanical and thermal properties and morphological behavior of biodegradable poly (L‐lactic acid) (PLLA) and poly (butylene succinate‐co‐L‐lactate) (PBSL) blends

A blend of two biodegradable and semi‐crystalline polymers, poly (L‐lactic acid) (PLLA; 70 wt%) and poly (butylene succinate‐co‐L‐lactate) (PBSL; 30 wt%), was prepared in the presence of various polyethylene oxide‐polypropylene oxide‐polyethylene oxide (PEO‐PPO‐PEO) triblock copolymer contents (0.5, 1, 2 wt%). Mechanical, thermal properties, and Fourier transform infrared (FTIR) analysis of the blends were investigated. It was found that the addition of copolymer to PLLA/PBSL improved the fracture toughness of the blends as shown by mode I fracture energies. It was supported by morphological analysis where the brittle deformation behavior of PLLA changed to ductile deformation with the presence of elongated fibril structure in the blend with copolymer system. The glass transition temperature (T_g), melting temperature (T_m) of PLLA, and PBSL shift‐closed together indicated that some compatibility exists in the blends. In short, PEO‐PPO‐PEO could be used as compatibilizer to improve the toughness and compatibility of the PLLA/PBSL blends. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of high‐molecular‐weight aliphatic–aromatic copolyesters from poly(ethylene‐co‐1,6‐hexene terephthalate) and poly(L‐lactic acid) by chain extension

A series of aliphatic–aromatic multiblock copolyesters consisting of poly(ethylene‐co‐1,6‐hexene terephthalate) (PEHT) and poly(L ‐lactic acid) (PLLA) were synthesized successfully by chain‐extension reaction of dihydroxyl terminated PEHT‐OH prepolymer and dihydroxyl terminated PLLA‐OH prepolymer using toluene‐2,4‐diisoyanate as a chain extender. PEHT‐OH prepolymers were prepared by two step reactions using dimethyl terephthalate, ethylene glycol, and 1,6‐hexanediol as raw materials. PLLA‐OH prepolymers were prepared by direct polycondensation of L ‐lactic acid in the presence of 1,4‐butanediol. The chemical structures, the molecular weights and the thermal properties of PEHT‐OH, PLLA‐OH prepolymers, and PEHT‐PLLA copolymers were characterized by FTIR, ¹H NMR, GPC, TG, and DSC. This synthetic method has been proved to be very efficient for the synthesis of high‐molecular‐weight copolyesters (say, higher than M_w = 3 × 10⁵ g/mol). Only one glass transition temperature was found in the DSC curves of PEHT‐PLLA copolymers, indicating that the PLLA and PEHT segments had good miscibility. TG curves showed that all the copolyesters had good thermal stabilities. The resulting novel aromatic–aliphatic copolyesters are expected to find a potential application in the area of biodegradable polymer materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5898–5907, 2009     

Crystallization kinetics and morphology of poly(butylene succinate‐co‐adipate)

The crystallization kinetics of biodegradable poly(butylene succinate‐co‐adipate) (PBS/A) copolyester was investigated by using differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The Avrami and Ozawa equations were used to analyze the isothermal and nonisothermal crystallization kinetics, respectively. By using wide‐angle X‐ray diffraction (WAXD), PBS/A was identified to have the same crystal structure with that of PBS. The spherulitic growth rates of PBS/A measured in isothermal conditions are very well comparable with those measured by nonisothermal procedures (cooling rates ranged from 0.5 to 15 °C/min). The kinetic data were examined with the Hoffman–Lauritzen nucleation theory. The observed spherulites of PBS/A with different shapes and textures strongly depend on the crystallization temperatures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3231–3241, 2005     

Morphology of poly(butylene terephthalate)–poly(ethylene terephthalate‐co‐isophthalate‐co‐sebacate) segmented copolyesters

Segmented copolyesters, namely, poly(butylene terephthalate)–poly(ethylene terephthalate‐co‐isophthalate‐co‐sebacate) (PBT‐PETIS), were synthesized with the melting transesterification processing in vacuo condition involving bulk polyester produced on a large scale (PBT) and ternary amorphous random copolyester (PETIS). Investigations on the morphology of segmented copolyesters were undertaken. The two‐phase morphology model was confirmed by transmission electron microscopy and dynamic mechanical thermal analysis. One of the phases was composed of crystallizable PBT, and the other was a homogeneous mixture of PETIS and noncrystallizable PBT. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2257–2263, 2003     

New super‐tough poly(butylene terephthalate) materials based on compatibilized blends with metallocenic poly(ethylene‐octene) copolymer

New super‐tough poly(butylene terephthalate) (PBT)/poly(ethylene‐octene) copolymer (PEO) blends containing 2 wt% poly(ethylene‐co‐glycidyl methacrylate) (EGMA) as a compatibilizer were obtained by extrusion and injection molding. The blends comprised of an amorphous PBT‐rich phase with some miscibilized EGMA, a pure PEO amorphous phase, and a crystalline PBT phase that was not influenced by the presence of either PEO or EGMA. The blends showed a fine particle size up to 20 wt% PEO content. Super‐tough blends were obtained with PEO contents equal to or higher than 10%. The maximum toughness was very high (above 710 J/m) and was attained with 20% PEO without chemical modification of the commercial components used. Copyright © 2003 John Wiley & Sons, Ltd.     

Hydrogen bonding interaction and crystallization behavior of poly (butylene succinate‐co‐butylene adipate)/thiodiphenol complexes

The poly (butylene succinate‐co‐butylene adipate) (PBSA)/thiodiphenol (TDP) complexes were prepared by melt blending. Intermolecular hydrogen bonding between carbonyl group of PBSA and hydroxyl group of TDP formed as verified by a combination FTIR and peak fitting technique. As a result, the crystallization temperature, melting temperature, crystallinity and crystallization rate of PBSA decreased with addition of TDP, implying impeded crystallization and reduced lamellar thickness. On the basis of Lauritzen–Hoffman analysis, the fold surface energy (σ_e) and work of chain folding (q) were increased by TDP incorporation. POM observation exhibited concentric ring‐banded spherulites for samples with 10 and 20 wt% TDP. A peculiar ring‐banded pattern with discrepant band spacing was obtained for the first time by addition of 30 wt% TDP, whose formation mechanism remains to be discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Crystallization kinetics and morphology of biodegradable poly(butylene succinate‐co‐propylene succinate)s

The crystallization behavior of biodegradable poly(butylene succinate) and copolyesters poly(butylene succinate‐co‐propylene succinate)s (PBSPS) was investigated by using ¹H NMR, DSC and POM, respectively. Isothermal crystallization kinetics of the polyesters has been analyzed by the Avrami equation. The 2.2‐2.8 range of Avrami exponential n indicated that the crystallization mechanism was a heterogeneous nucleation with spherical growth geometry in the crystallization process of polyesters. Multiple melting peaks were observed during heating process after isothermal crystallization, and it could be explained by the melting and recrystallization model. PBSPS was identified to have the same crystal structure with that of PBS by using wide‐angle X‐ray diffraction (WAXD), suggesting that only BS unit crystallized while the PS unit was in an amorphous state. The crystal structure of polyesters was not affected by the crystallization temperatures, too. Besides the normal extinction crosses under the POM, the double‐banded extinction patterns with periodic distance along the radial direction were also observed in the spherulites of PBS and PBSPS. The morphology of spherulites strongly depended on the crystallization temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 420–428, 2007     

Morphological changes during heating in poly(L‐lactic acid)/poly(butylene succinate) blend systems as studied by synchrotron X‐ray scattering

Blends of poly(L ‐lactic acid) (PLA) and poly(butylene succinate) (PBS) were prepared in various compositions via melt mixing, and the morphological changes were investigated with differential scanning calorimetry and synchrotron wide‐angle and small‐angle X‐ray scattering techniques at a heating rate of 10 °C/min. Differential scanning calorimetry thermograms of PLA/PBS blends showed two distinct melting peaks over the entire composition range. The exothermal peak for PLA shifted significantly to a lower temperature and overlapped with that of PBS around 100 °C. A depression of the melting point of the PLA component via blending was observed. The synchrotron wide‐angle X‐ray scattering during heating revealed that there was no cocrystallization or crystal modification via blending. The synchrotron small‐angle X‐ray scattering data showed that well‐defined double‐scattering peaks (or peaks with a clear scattering shoulder) appeared during crystallization, indicating that this system possessed dual lamellar stacks. These peaks were deconvoluted into two components with a peak separation computer program, and then the morphological parameters of each component were obtained by means of the correlation function. The long period and average lamellar thickness of the two components before melting decreased with an increasing content of the other polymer component. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1931–1939, 2002     

Synthesis of star‐shaped poly(D,L‐lactic acid‐alt‐glycolic acid)‐b‐poly(L‐lactic acid) with the poly(D,L‐lactic acid‐alt‐glycolic acid) macroinitiator and stannous octoate catalyst

Two types of three‐arm and four‐arm, star‐shaped poly(D,L ‐lactic acid‐alt‐glycolic acid)‐b‐poly(L ‐lactic acid) (D,L ‐PLGA50‐b‐PLLA) were successfully synthesized via the sequential ring‐opening polymerization of D,L ‐3‐methylglycolide (MG) and L ‐lactide (L ‐LA) with a multifunctional initiator, such as trimethylolpropane and pentaerythritol, and stannous octoate (SnOct₂) as a catalyst. Star‐shaped, hydroxy‐terminated poly(D,L ‐lactic acid‐alt‐glycolic acid) (D,L ‐PLGA50) obtained from the polymerization of MG was used as a macroinitiator to initiate the block polymerization of L ‐LA with the SnOct₂ catalyst in bulk at 130 °C. For the polymerization of L ‐LA with the three‐arm, star‐shaped D,L ‐PLGA50 macroinitiator (number‐average molecular weight = 6800) and the SnOct₂ catalyst, the molecular weight of the resulting D,L ‐PLGA50‐b‐PLLA polymer linearly increased from 12,600 to 27,400 with the increasing molar ratio (1:1 to 3:1) of L ‐LA to MG, and the molecular weight distribution was rather narrow (weight‐average molecular weight/number‐average molecular weight = 1.09–1.15). The ¹H NMR spectrum of the D,L ‐PLGA50‐b‐PLLA block copolymer showed that the molecular weight and unit composition of the block copolymer were controlled by the molar ratio of L ‐LA to the macroinitiator. The ¹³C NMR spectrum of the block copolymer clearly showed its diblock structures, that is, D,L ‐PLGA50 as the first block and poly(L ‐lactic acid) as the second block. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 409–415, 2002