Hydrolytic degradation of biobased poly(butylene succinate‐co‐furandicarboxylate) and poly(butylene adipate‐co‐furandicarboxylate) copolyesters under mild conditions

It is indispensable to investigate hydrolytic degradation behavior to develop novel (bio)degradable polyesters. Biobased and biodegradable copolyesters poly(butylene adipate‐co ‐butylene furandicarboxylate) (PBAF) and poly(butylene succinate‐co ‐butylene furandicarboxylate) (PBSF) with BF molar fraction (?_BF) between 40 and 60% were synthesized in this study. The hydrolytic degradation of film samples was conducted in a pH 7.0 PBS buffer solution at 25 °C. Slight mass loss (1–2%) but significant decrease in intrinsic viscosity (35–44%) was observed after 22 weeks. The apparent hydrolytic degradation rate decreased with increasing ?_BF and initial crystallinity. Meanwhile, PBAFs degraded slightly faster than PBSFs with the same composition. The ?_BF and crystallinity increased slowly with degradation time, suggesting the aliphatic moiety and the amorphous region are more susceptible to hydrolysis. And high enough tensile properties were retained after hydrolysis degradation, indicating PBAF and PBSF copolyesters are hydrolytically degradable, with tunable hydrolytic degradation rate and good balance between hydrolytic degradability and durability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44674.     

Synthesis and characteristics of biodegradable copolyesters from the transesterification of poly(butylene adipate‐co‐succinate) and poly(ethylene terephthalate)

Poly(butylene adipate‐co‐succinate) (PBAS), an aliphatic polyester, is known for its excellent biodegradability, but its physical and mechanical properties are poor. To improve the physical properties, stiff aromatic rings were added to PBAS through transesterification with poly(ethylene terephthalate) (PET). New biodegradable copolyesters were prepared by the intermolecular ester‐exchange reactions between molten PBAS and PET. The transesterification reaction was carried out at 280°C without a catalyst. The newly synthesized copolyesters were characterized with ¹H‐NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The mechanical properties were measured with a universal test machine, and the biodegradability was also investigated. By the new peaks appearing in ¹H‐NMR spectra of the copolyesters, the occurrence of the transesterification reaction between PBAS and PET was confirmed. A reduction of the melting temperature was observed for the copolyesters. The elongations at break of the new copolyesters increased for all compositions and reaction times, in comparison with PBAS. However, the tensile strength decreased with the induction of terephthalate units in the copolyesters. The biodegradability of the copolyesters also depended on the number of terephthalate units. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3266–3274, 2004     

Biodegradable poly (butylene succinate‐co‐cyclohexanedimethylene succinate): Synthesis,crystallization, morphology,and rheology

Poly (butylene succinate‐co‐cyclohexanedimethylene succinate) (PBCSs), which are composed of various amounts of cyclohexanedimethylene succinate (CS) with butylene succinate (BS) were synthesized via polycondensation. The composition of PBCSs was analyzed by a ¹H‐nuclear magnetic resonance (¹H‐NMR). Crystallization, morphology, and rheological properties of PBCSs were investigated by a polarized optical microscopy (POM), a differential scanning calorimetry (DSC), a X‐ray diffraction (XRD), and a parallel‐plate rheometer (PPR). The studies revealed that the composition of PBCSs played an important role in controlling their properties. Only one T_g can be seen for PBCSs by DSC, which demonstrate they are miscible copolymers. PBCSs exhibited lower crystallization capacity than its homopolyesters either Poly (butylene succinate) (PBS) or poly (cyclohexanedimethylene succinate) (PCS). It also proved that the cyclohexyl group of CHDM not only affected the crystalline formation, but also changed spherulitic morphology during crystallization. The spherulitic size gradually decreased with an increase of CS content. When CS content approached 50 wt %, the crystallization ability reached minimum. By comparing the effect of temperature with shear rate, it concluded that the viscosities of PBCSs were more sensitive to temperature rather than shear rate, and flow activation energies of PBCSs linearly increased with an increase of CS content. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40103.     

Effect of mixing conditions on the rheological and optical properties of chemically modified poly(ethylene terephthalate‐co‐ethylene isophthalate)

The optical properties and rheological properties were studied for binary reactive blends composed of poly(ethylene terephthalate‐co‐ethylene isophthalate) [P(ET–EI)] and a styrene–acrylate based copolymer with glycidyl functionality. The blade rotation speed in the internal mixer greatly affected the structure and properties for the blend system. Intensive mixing at a high rotation speed enhanced the optical transparency because of the reduced particle size of the dispersed phase. The graft copolymer generated by the reaction between P(ET–EI) and the modifier was responsible for the fine morphology. Furthermore, the copolymer also enhanced the elastic nature in the molten state because it acted as a long‐chain branched polymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of poly(ethylene isophthalate‐co‐ethylene terephthalate) copolyesters

Poly(ethylene isophthalate‐co‐ethylene terephthalate) (PEIPET) copolymers of various compositions and molecular weights were synthesized by melt polycondensation and characterized in terms of chemical structure and thermal and rheological properties. At room temperature, all copolymers were amorphous and thermally stable up to about 400°C. The main effect of copolymerization was a monotonic increase of glass transition temperature (T_g) as the content of ethylene terephthalate units increased. The Fox equation accurately describes the T_g–composition data. The presence of ethylene terephthalate units was found to influence rheological behavior in the melt, with the Newtonian viscosity increasing as the content of ethylene terephthalate units increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 186–193, 2004     

Synthesis and characterization of biodegradable poly(butylene succinate‐co‐propylene succinate)s

Biodegradable polyesters such as poly(butylene succinate) (PBS), poly(propylene succinate) (PPS), and poly(butylene succinate‐co‐propylene succinate)s (PBSPSs) were synthesized respectively, from 1,4‐succinic acid with 1,4‐butanediol and 1,3‐propanediol through a two‐step process of esterification and polycondensation in this article. The composition and physical properties of both homopolyesters and copolyesters were investigated via ¹H NMR, DSC, TGA, POM, AFM, and WAXD. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), crystallinity (X), and thermal decomposition temperature (T_d) of these polyesters decreased gradually as the content of propylene succinate unit increased. PBSPS copolyesters showed the same crystal structure as the PBS homopolyester. Besides the normal extinction crosses under the polarizing optical microscope, the double‐banded extinction patterns with periodic distance along the radial direction were also observed in the spherulites of PBS and PBSPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nanocomposites based on poly(butylene adipate‐co‐terephthalate) and montmorillonite

Nanocomposites based on biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) and layered silicates were prepared by the melt intercalation method. Nonmodified montmorillonite (MMT) and organo‐modified MMTs (DA‐M, ODA‐M, and LEA‐M) by the protonated ammonium cations of dodecylamine, octadecylamine, and N‐lauryldiethanolamine, respectively, were used as the layered silicates. The comparison of interlayer spacing between clay and PBAT composites with inorganic content 3 wt % measured by X‐ray diffraction (XRD) revealed the formation of intercalated nanocomposites in DA‐M and LEA‐M. In case of PBAT/ODA‐M (3 wt %), no clear peak related to interlayer spacing was observed. From morphological studies using transmission electron microscopy, the ODA‐M was found to be finely and homogeneously dispersed in the matrix polymer, indicating the formation of exfoliated nanocomposite. When ODA‐M content was increased, the XRD peak related to intercalated clay increased. Although the exfoliated ODA‐M (3 wt %) nanocomposite showed a lower tensile modulus than the intercalated DA‐M and LEA‐M (3 wt %) composites, the PBAT/ODA‐M composite with inorganic content 5 wt % showed the highest tensile modulus, strength, and elongation at break among the PBAT composites with inorganic content 5 wt %. Their tensile properties are discussed in relation to the degree of crystallinity of the injection molded samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 386–392, 2005     

Structure–properties relationship in toughening of poly(butylene terephthalate) with core–shell modifier

The performance of acrylonitrile–butadiene–styrene (ABS) core–shell modifier with different grafting degree, acrylonitrile (AN) content, and core–shell ratio in toughening of poly(butylene terephthalate) (PBT) matrix was investigated. Results show PBT/ABS blends fracture in ductile mode when the grafting degree is high, and with the decrease of grafting degree PBT/ABS blends fracture in a brittle way. The surface of rubber particles cannot be covered perfectly for ABS with low grafting degree and agglomeration will take place; on the other hand, the entanglement density between SAN and PBT matrix decreases because of the low grafting degree, inducing poor interfacial adhesion. The compatibility between PBT and ABS results from the strong interaction between PBT and SAN copolymer and the interaction is influenced by AN content. Results show ABS cannot disperse in PBT matrix uniformly when AN content is zero and PBT/ABS fractures in a brittle way. With the addition of AN in ABS, PBT/ABS blends fracture in ductile mode. The core–shell ratio of ABS copolymers has important effect on PBT/ABS blends. When the core–shell ratio is higher than 60/40 or lower than 50/50, agglomeration or cocontinuous structure occurs and PBT/ABS blends display lower impact strength. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 5363–5371, 2006     

Biodegradable poly(L‐lactic acid)/poly(butylene succinate‐co‐adipate) blends: Miscibility,morphology, and thermal behavior

Blends of two biodegradable and semicrystalline polymers, poly(L ‐lactic acid) (PLLA) and poly(butylene succinate‐co‐adipate) (PBSA), were prepared by solvent casting in different compositions. The miscibility, morphology, and thermal behavior of the blends were investigated using differential scanning calorimetry and optical microscopy. PLLA was found to be immiscible with PBSA as evidenced by two independent glass transitions and biphasic melt. Nonisothermal crystallization measurements showed that fractionated crystallization behavior occurred when PBSA was dispersed as droplets, evidenced by multiple crystallization peaks at different supercooling levels. Crystallization and morphology of the blends were also investigated through two‐step isothermal crystallization. For blends where PLLA was the major component, different content of PBSA did not make a significant difference in the crystallization mechanism and rate of PLLA. For blends where PBSA was the major component, the crystallization rate of PBSA decreased with increasing PLLA content, while the crystallization mechanism did not change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Evaluation of poly(methylsilane‐carbosilane) synthesized from methyl‐dichlorosilane and chloromethyldichloromethylsilane as a precursor for SiC

A new poly(methylsilane‐carbosilane) (PMSCS) for silicon carbide precursor was synthesized by Wurtz‐type copolycondensation of methyldichlorosilane (MeHSiCl₂) with chloromethyldichloromethylsilane (ClCH₂MeSiCl₂) and terminated with vinylmagnesium chloride (ViMgCl). The use of insufficient sodium made the reaction more economic and safe. By changing the ratios of two monomers and the end‐block agent, the properties of the obtained PMSCS and the C/Si ratio of its derived ceramic could be tuned. Upon pyrolysis at 1000 °C under argon, silicon carbide with nearly stoichiometric C/Si ratio and low oxygen content was obtained in 64% of ceramic yield. PMSCS showed high potential as an economical SiC ceramic precursor for the fabrication of SiC matrix, coating, and adhesives. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46610.     

Poly(butylene succinate‐co‐butylene adipate)/polyethylene oxide blends for controlled release materials: A morphological study

Varying the formulation and processing conditions of polymer blends allows the design of materials with a large range of morphologies. Active materials embedding active compounds in a devoted phase are promising applications of such blends, offering possible various transport properties. In this study, 13 poly(butylene succinate‐co‐butylene adipate) (PBSA)/polyethylene oxide (PEO) blends were extruded in a slit die. Their morphologies were characterized by water extraction (selective PEO dissolution), FTIR spectroscopy, and differential scanning calorimetry. Transport properties were assessed by water vapor permeation and fluorescein release as model migrant. Indeed, the desorption in water of fluorescein (previously entrapped in PEO) was monitored to preliminary investigate the release properties of these materials: two morphologies were obtained (i) pseudo multilayer films made of PEO‐rich layer/PBSA‐rich layer/PEO‐rich layer and (ii) PEO nodules dispersed in the PBSA‐rich matrix for the highest PBSA contents. The first systems were erodible ones with an uncontrolled fast delivery by PEO dissolution whereas the second ones showed a controlled release by permeation through the PBSA matrix from PEO nodules. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42874.     

Effect of a chain extender on the rheological and mechanical properties of biodegradable poly(lactic acid)/poly[(butylene succinate)‐co‐adipate] blends

Biodegradable polymer blends based on poly(lactic acid) (PLA) and poly[(butylene succinate)‐co‐adipate] (PBSA) were prepared with a laboratory internal mixer. An epoxy‐based, multifunctional chain extender was used to enhance the melt strength of the blends. The morphology of the blends was observed with field emission scanning electron microscopy. The elongational viscosities of the blends, with and without chain extender, were measured with a Sentmanat extensional rheometer universal testing platform. The blends with chain extender exhibited strong strain‐hardening behavior, whereas the blends without chain extender exhibited only weak strain‐hardening behavior. Measurements of the linear viscoelastic properties of the melts suggested that the chain extender promoted the development of chain branching. The results show that PBSA contributed to significant improvements in the ductility of the PLA/PBSA blends, whereas the chain extender did not have a significant effect on the elastic modulus and strain at break of the blends. The combined blending of PLA with PBSA and the incorporation of the chain extender imparted both ductility and melt strength to the system. Thus, such an approach yields a system with enhanced performance and processability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigation of thermal,rheological, and physical properties of amorphous poly(ethylene terephthalate)/organoclay nanocomposite films

Thermal, rheological, and physical properties of amorphous poly(ethylene terephthalate) (PET)/organoclay nanocomposite films which were successfully prepared with melt processing method using a PET/organoclay masterbatch were studied in detail. Structural and physical properties of the films were characterized by the UV–Vis spectroscopy, XRD and SEM analysis, DSC, DMA, and rheological tests and gas permeability measurements. Cold‐crystallization behavior of the samples was analyzed by the DSC and DMA methods. Aspect ratio of the organoclay layers were determined with the Nielsen and Halpin‐Tsai models based on the gas permeability and DMA data, respectively. It was found that the organoclay reduced the nonisothermal cold‐crystallization rate of PET chains by restricting the segmental motion of the polymer in the solid state. On the other hand, the organoclay enhanced the nonisothermal melt‐crystallization of PET due to the nucleation effect. Aspect ratio (A_f) of the clay layers were found to be about 20 by using the gas permeability and DMA data. Aspect ratio value was also confirmed by the analysis of SEM images of the samples. A physical model for the sample microstructure was offered that the stacks with the thickness of 20–30 nm and the lateral size of 400–600 nm, probably consisting of 5–8 layers, were uniformly dispersed in the PET structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and properties of emulsifier‐/solvent‐free polyurethane‐acrylic hybrid emulsions for binder materials: Effect of the glycidyl methacrylate/acrylonitrile content

To obtain binder materials, emulsions of emulsifier‐/solvent‐free waterborne polyurethane‐acrylic hybrids with a fixed acrylic monomer content (30 wt %) were prepared in this study. This study focused on the effect of glycidyl methacrylate (GMA)/acrylonitrile (AN) wt % on the shelf stability, mean particle size and viscosity of hybrid emulsion samples, water swelling %/dynamic mechanical thermal properties/mechanical properties of hybrid film samples, and the failure mode and adhesive strength of binder materials prepared in this study. Characterization of the chemical structures of prepolymers, hybrid materials (binder materials), and atmospheric pressure plasma‐treated polyethylene (PE) has been performed by means of Fourier transformed infrared spectroscopy to determine the presence/disappearance/peak intensity change of functional groups. Various properties such as mean particle size, viscosity, T_g, water swelling %, hardness and mechanical properties, and failure mode and adhesive strength for leather/leather, control PE/leather, and plasma‐treated PE/leather were found to be significantly dependent on the weight ratio of GMA/AN. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44497.     

Structure−property relationships of halogen‐free flame‐retarded poly(butylene terephthalate) and glass fiber reinforced PBT

Flame retardancy for thermoplastics is a challenging task where chemists and engineers work together to find solutions to improve the burning behavior without strongly influencing other key properties of the material. In this work, the halogen‐free additives aluminum diethylphosphinate (AlPi‐Et) and a mixture of aluminum phosphinate (AlPi) and resorcinol‐bis(di‐2,6‐xylyl phosphate) (AlPi‐H + RXP) are employed in neat and reinforced poly(butylene terephthalate) (PBT), and the morphology, mechanical performance, rheological behavior, and flammability of these materials are compared. Both additives show submicron dimensions but differ in terms of particle and agglomerate sizes und shapes. The overall mechanical performance of the PBT flame‐retarded with AlPi‐Et is lower than that with AlPi‐H‐RXP, due to the presence of larger agglomerates. Moreover, the flow behavior of the AlPi‐Et/PBT materials is dramatically changed as the larger rod‐like primary particles build a percolation threshold. In terms of flammability, both additives perform similar in the UL 94 test and under forced‐flaming combustion. Nevertheless, AlPi‐Et performs better than AlPi‐H + RXP in the LOI test. The concentration required to achieve acceptable flame retardancy ranges above 15 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Strain rate dependent mechanical properties of a high‐strength poly(methyl methacrylate)

Strain rate dependency is an important issue for the mechanical response of materials in impact events. Dynamic mechanical properties of a high‐strength poly(methyl methacrylate) (PMMA) were studied by using split Hopkinson pressure bar technology. The maximum stress is enhanced with the increase of strain rate, and then keeps a constant with the further increase of strain rate, which is accompanied with a linear increase of fracture energy density. The critical data of strain rate and maximum stress were determined. Eyring's equation was applied for analyzing the influence factors, which relate to the hardening induced by strain rate and softening caused by adiabatic temperature rise. Inherent physical mechanisms were clarified and the strategies for designing advanced impact‐resistant polymers were proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46189.     

Mechanical and thermal properties of thermoplastic random copolyesters made from lipid‐derived Medium and long chain poly(ω‐hydroxyfatty acid)s

The physical properties of novel thermoplastic random copolyesters [‐(CH₂)_n‐COO‐/‐(CH₂)_n‐COO‐]_x made of long (n = 12) and medium (n = 8) chain length ω‐hydroxyfatty esters [HO‐(CH₂)_n‐COOCH₃] derived from bio‐based vegetable oil feedstock are described. Poly(ω‐hydroxy tridecanoate/ω‐hydroxy nonanoate) P(?Me13?/?Me9?) random copolyesters (M_n = 11,000–18,500 g/mol) with varying molar ratios were examined by TGA, DSC, DMA and tensile analysis, and WAXD. For the whole range of P(?Me13?/?Me9?) compositions, the WAXD data indicated an orthorhombic polyethylene‐like crystal packing. Their melting characteristics, determined by DSC, varied with composition suggesting an isomorphic cocrystallization behavior. TGA of the P(?Me13?/?Me9?)s indicated improved thermal stability determined by their molar compositions. The glass transition temperature, investigated by DMA, was also found to vary with composition. The crystallinities of P(?Me13?/?Me9?)s however, were unaffected by the composition. The stiffness (Young's modulus) of these materials was found to be related to their degrees of crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40492.     

Nonisothermal crystallization behavior of poly (butylene terephthalate)–poly (ethylene terephthalate‐co‐isophthalate‐co‐sebacate) segmented copolyesters

In this paper, two different analytical methods were applied to investigate nonisothermal crystallization behavior of copolyesters prepared by melting transesterification processing from bulk polyesters involving poly (butylene terephthalate) (PBT) and ternary amorphous random copolyester poly(ethylene terephthalate‐co‐isophthalate‐co‐sebacate) (PETIS). The results show that the half‐time of crystallization of copolyesters depended on the reaction time and decreased with the content of ternary polyesters in the amorphous segment. The modified Avrami model describes the nonisothermal crystallization kinetics very well. The values of the Avrami exponent range from 2.2503 to 3.7632, and the crystallization kinetics constant ranges from 0.0690 to 0.9358, presenting a mechanism of three‐dimensional spherulitic growth with heterogeneous nucleation. Ozawa analysis, however, failed to describe the nonisothermal crystallization behavior of copolyesters, especially at higher cooling rate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1232–1238, 2003     

Synthesis of poly(butylene succinate‐co‐butylene terephthalate) (PBST) copolyesters with high molecular weights via direct esterification and polycondensation

In this article, biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST) copolyesters with high molecular weights were synthesized by direct esterification and polycondensation route. The reaction conditions and catalytic systems were investigated in detail. Through balancing the reaction efficiency and the costs of reactants, the proper molar ratio of diol to diacid was determined. Titanium tetraisopropoxide (TTiPO) was found to be an effective catalyst both in esterification and polycondensation reaction, and its content was optimized based on the esterification ratio and amount of formed by‐products. The complex reaction was determined to be the dominant catalytic reaction mechanism. By importing the additives of metal oxides coupled with TTiPO, the weight‐average molecular weights of PBST increased sharply from 8.51 × 10⁴ to 14.38 × 10⁴, manifesting the additives promoted the polymerization reaction greatly. The enhancement of carbonyl polarization and provision of suitable reaction space arose from the metal oxides were the reasons for promoting the polymerization reaction. With respect to thermal properties, the same melting point and heat of fusion were found, while thermal stability increased with the import of additives. The result was prone to be interpreted by the higher molecular weights of PBST in the presence of additives. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the comonomer content on the solid‐state mechanical and viscoelastic properties of poly(propylene‐co‐1‐butene) films

In this study, we quantified the thermal and solid‐state mechanical and viscoelastic properties of isotactic polypropylene (i‐PP) homopolymer and poly(propylene‐1‐butene) copolymer films having a 1‐butene ratio of 8, 12, and 14 wt %, depending on the comonomer content. The uniaxial tensile creep and stress‐relaxation behaviors of the samples were studied in a dynamic mechanical analyzer at different temperatures. The creep behaviors of the samples were modeled with the four‐element Burger equation, and the long‐term creep strains were predicted with the time–temperature superposition method. The short‐term mechanical properties of the samples were also determined with tensile and impact testing at room temperature. We found that the Young's modulus and ultimate strength values of the samples decreased with increasing amount of 1‐butene in the copolymer structure. On the other hand, the strain at break and impact strength values of the samples improved with increasing amount of 1‐butene. Creep analysis showed that i‐PP exhibited a relatively lower creep strain than the poly(propylene‐co‐1‐butene)s at 30 °C. However, interestingly, we discovered that the temperature increase resulted in different effects on the creep behaviors. We also found that short‐chain branching improved the creep resistance of polypropylene at relatively high temperatures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46350.