Crystallization behavior of partially crosslinked poly(β‐hydroxyalkonates)/poly(butylene succinate) blends

Partially crosslinked poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)/poly(butylene succinate) (PHBV/PBS) and poly(β‐hydroxybutyrate)/poly(butylene succinate) (PHB/PBS) blends were prepared by melt compounding with dicumyl peroxide. The effect of partial crosslinking on crystallization of the PHBV/PBS and PHB/PBS blends was investigated systematically. Differential scanning calorimetry results showed that the overall crystallization rates of both PHBV and PBS in their blends were enhanced considerably by the partial crosslinking. Similar results were also detected in the PHB/PBS blends. The polarized optical microscope observation displayed that the nuclei density of PHBV was increased while the spherulitic morphology did not change much. Conversely, the PBS spherulites turned into cloud‐like morphology after the partial crosslinking which is a result of the decrease in spherulite size, the reduction in interspherulite distance and the interconnection of fine PBS domains. Wide angle X‐ray diffraction patterns confirmed the enhancement in crystallization of the PHBV/PBS blends after the partial crosslinking without modification on crystalline forms of the PHBV and PBS components. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41020.     

PBS/PHB共混合金的制备及其性能

采用双螺杆挤出机将聚羟基丁酸酯(PHB)与聚丁二酸丁二酯(PBS)熔融共混,制备了PBS/PHB合金,并研究了其性能.结果表明:PBS与PHB组成了热力学互容体系;随着PHB用量的增加,PBS/PHB合金的晶体形态为尺寸逐渐减小的环带球晶,合金的拉伸强度与韧性显著增加;PBS/PHB合金在紫外光老化后的抗冲击性能下降,...     

Mechanical and thermal properties of poly(butylene succinate)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) biodegradable blends

Biodegradable polymer blends of poly(butylene succinate) (PBS) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) were prepared with different compositions. The mechanical properties of the blends were studied through tensile testing and dynamic mechanical thermal analysis. The dependence of the elastic modulus and strength data on the blend composition was modeled on the basis of the equivalent box model. The fitting parameters indicated complete immiscibility between PBS and PHBV and a moderate adhesion level between them. The immiscibility of the parent phases was also evidenced by scanning electron observation of the prepared blends. The thermal properties of the blends were studied through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DSC results showed an enhancement of the crystallization behavior of PBS after it was blended with PHBV, whereas the thermal stability of PBS was reduced in the blends, as shown by the TGA thermograms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42815.     

Mechanical properties, morphology, and crystallization behavior of blends of poly(l-lactide) with poly(butylene succinate-co-l-lactate) and poly(butylene succinate)

The blends of poly(l-lactide) (PLLA) with poly(butylene succinate) (PBS) and poly(butylene succinate-co-l-lactate) (PBSL) containing the lactate unit of ca. 3 mol% were prepared by melt-mixing and subsequent injection molding, and their mechanical properties, morphology, and crystallization behavior have been compared. Dynamic viscoelasticity and SEM measurements of the blends revealed that the extent of the compatibility of PBSL and PBS with PLLA is almost the same, and that the PBSL and PBS components in the blends with a low content of PBSL or PBS (5-20 wt%) are homogenously dispersed as 0.1−0.4 μm particles. The tensile strength and modulus of the blends approximately followed the rule of mixtures over the whole composition range except that those of PLLA/PBS 99/1 blend were exceptionally higher than those of pure PLLA. All the blends showed considerably higher elongation at break than pure PLLA, PBSL, and PBS. Differential scanning calorimetric analysis of the blends revealed that the isothermal and non-isothermal crystallization of the PLLA component is promoted by the addition of a small amount of PBSL, while the addition of PBS was much less effective.     

Miscibility and crystallization of biodegradable poly(butylene succinate-co-butylene adipate)/poly(vinyl phenol) blends

Miscibility, crystallization kinetics, crystal structure, and microstructure of biodegradable poly(butylene succinate-co-butylene adipate) (PBSA)/poly(vinyl phenol) (PVPh) blends were studied by differential scanning calorimetry, optical microscopy, wide angle X-ray diffraction, and small angle X-ray scattering in detail in this work. PBSA and PVPh are miscible as evidenced by the single composition dependent glass transition temperature and the negative polymer-polymer interaction parameter. Isothermal crystallization kinetics of PBSA/PVPh blends was investigated and analyzed by the Avrami equation. The overall crystallization rates of PBSA decrease with increasing crystallization temperature and the PVPh content in the PBSA/PVPh blends; however, the crystallization mechanism of PBSA does not change in the blends. Furthermore, blending with PVPh does not modify the crystal structure of PBSA. The microstructural parameters, including the long period, thickness of crystalline phase and thickness of amorphous phase, all become larger with increasing the PVPh content, indicating that PVPh mainly resides in the interlamellar region of PBSA spherulites in the blends.     

Morphology,rheology, crystallization behavior,and mechanical properties of poly(lactic acid)/poly(butylene succinate)/dicumyl peroxide reactive blends

The reactive blends were prepared by the blending of poly(lactic acid) (PLA) with poly(butylene succinate) (PBS) in the presence of dicumyl peroxide (DCP) as a radical initiator in the melt state. The gel fractions, morphologies, crystallization behaviors, and rheological and mechanical properties of the reactive blends were investigated. Some crosslinked/branched structures were formed according to the rheological measurement and gel fraction results, and the crosslinked/branched structures played the role of nucleation site for the reactive blends. The PLA–PBS copolymers of the reactive blends acted as a compatibilizer for the PLA and PBS phases and, hence, improved the compatibility between the two components. Moreover, it was found that the reactive blends showed the most excellent mechanical properties as the DCP contents were 0.2 and 0.3 phr. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39580.     

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     

Eco-friendly cellulose acetate butyrate/poly(butylene succinate) blends: crystallization,miscibility, thermostability,rheological and mechanical properties

In this work, the crystallization, miscibility, thermostability, rheological and mechanical properties of cellulose acetate butyrate (CAB)/poly(butylene succinate) (PBS) blends were investigated in detail. Differential scanning calorimetry analysis confirmed that PBS could form crystalline phase in the solution casted CAB/PBS blends with W_CAB?≤?60 wt.%. When the blends were crystallized from melt, the crystallization of PBS was found to be severely suppressed by the amorphous diluent of CAB. CAB and PBS were confirmed to be thermodynamic miscible in molten state by the negative value of Flory-Huggins interaction parameter (χ₁₂?=??0.89) between CAB and PBS. The rheological characterization results and thermogravimetric analysis revealed that the melt viscosity and thermostability of CAB were reduced and improved by blending CAB with PBS, respectively. Moreover, the rigid CAB became more flexible after incorporating with ductile PBS. The application of CAB is expected to be extended via blending the two species of eco-friendly polymers.     

Morphology and melt rheology of biodegradable poly(lactic acid)/poly(butylene succinate adipate) blends: effect of blend compositions

Effect of the blend ratios on the morphology and melt rheology of poly(lactic acid) (PLA)/poly(butylene succinate adipate) (PBSA) blends were investigated using scanning electron microscope, strain-controlled rheometer, and capillary rheometer techniques. The morphological analysis shows that the average radius of the dispersed droplets of PBSA particles increases with change in the blend composition, and a co-continuous structure was generated when PBSA content reached 40%. For the linear viscoelasticity, the increase in the storage modulus at low-frequency region was more distinct in PLA/PBSA blends than in their pure components. A second plateau is clearly observed when the PBSA content was 20% or higher. Weight relaxation spectra showed that there was a longer relaxation time for blend system. These relaxation times were considered to be the shape relaxation periods of the droplets, which increase with change in the blend composition. The interfacial tensions of the PLA/PBSA blends at different compositions were between 5.3 and 6.1?mN/m, calculated from the weighted relaxation spectra and slightly higher than those obtained from Palierne model. These values are relatively high, indicating the poor miscibility of the two polymers. Both pure PLA and PBSA follow the Cox?CMerz rule, in good manner. Though, the rule does not satisfy with the PLA/PBSA blends. In addition, PLA/PBSA blends show more non-Newtonian tendencies than their pure components.     

Macromolecular design of novel sulfur‐containing copolyesters with promising mechanical properties

The miscibility of poly(butylene succinate) (PBS)/poly(butylene thiodiglycolate) (PBTDG) blends was investigated by DSC technique. PBS and PBTDG were completely immiscible in as blended‐state, as evidenced by the presence of two T_gs at ?34 and ?48°C, respectively. The miscibility changes upon mixing at elevated temperature: the original two phases merged into a single one because of transesterification reactions. Poly(butylene succinate/thiodiglycolate) block copolymers, prepared by reactive blending of the parent homopolymers, were studied to investigate the effects of transesterification reactions on the molecular structure and solid‐state properties. ¹³C‐NMR analysis evidenced the formation of copolymers whose degree of randomness increased with mixing time. Thermal characterization results showed that all the samples were semicrystalline, with a soft rubbery amorphous phase and a rigid crystal phase whose amount decreased by introducing BTDG units into the PBS chain (20 ≤ χ_c ≤ 41). Lastly, the mechanical properties were found strictly related to crystallinity degree (χ_c), the random copolymer, exhibiting the lowest elastic modulus (E = 61 MPa) and the highest deformation at break (ε_b (%) = 713). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Blending Modification of PHBV/PBS/PEG and its Biodegradation

This study used poly(butylene succinate) and poly(ethylene glycol) to modify poly(3-hydroxybutyrate-co-3-hydroxyvalerate). The results showed that the incorporation of poly(butylene succinate) and poly(ethylene glycol) improved the mechanical properties of blends. The results showed that crystallinity of the poly(ethylene glycol)-containing blends decreased, so do the crystallization temperature and melting temperature of the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) component of blends. Poly(butylene succinate)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(ethylene glycol) ratio of 50:20:30 was chosen owing to its good properties. The poly(3-hydroxybutyrate-co-3-hydroxyvalerate) component of blends can be degraded completely by Pseudomonas mendocina DS04-T, whereas this strain cannot degrade poly(butylene succinate) and poly(ethylene glycol). Apart from poly(butylene succinate), Fusarium sp. FS1301 can also biodegrade poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(ethylene glycol).     

PHB/PLLA聚酯材料与PHB/PLLA/PEO聚酯材料的体外降解性

对聚β-羟基丁酸酯/聚乳酸（PHB/PLLA）及聚β-羟基丁酸酯/聚乳酸/聚氧乙烯（PHB/PLLA/PEO）膜状样品在37 ℃磷酸缓冲溶液（PBS）/溶菌酶中的降解行为进行了研究,通过定期观察质量损失、降解过程中的热力学性质及样品表面形态变化,发现PHB/PLLA共混未能提高PHB的降解速度,而PEO加入到PHB/PLLA体系中显著提高了PHB、PLLA的降解速度,进而提高了PHB/PLLA共混体系的降解速度。     

Unraveling the cause for the unusual processing behavior of commercial partially bio-based poly(butylene succinates) and their stabilization

The commercially available partially bio-based poly(butylene succinate) (PBS) and poly(butylene succinate-co-adipate) (PBSA) are subjected to prolonged and multiple extrusion cycles to investigate their thermal behavior. Empirically, both PBS and PBSA form branches at 190°C, with PBS possessing a higher tendency for branching than PBSA as studied by rheology and size exclusion chromatography (SEC). In each case, the branching is favored by fumaric acid moieties, making both PBS and PBSA susceptible to accelerated thermal oxidation. Indeed, the NMR signal attributed to fumaric acid disappears upon thermal processing of PBS and PBSA. Presumably, the bio-based succinic acid used contains minor quantities of fumaric acid, yet still sufficient to cause this surprising processing behavior. The branching of both polymers is suppressed by stabilizers such as phenolic antioxidants, as proven by rheology and SEC. This is complemented by nuclear magnetic resonance (NMR), revealing that the fumaric acid signal is still well-resolved in the stabilized processed samples.     

Elongational rheology of biodegradable poly(lactic acid)/poly[(butylene succinate)‐co‐adipate] binary blends and poly(lactic acid)/poly[(butylene succinate)‐co‐adipate]/clay ternary nanocomposites

A series of blends based on poly(lactic acid) (PLA) and poly[(butylene succinate)‐co‐adipate] (PBSA) as well as their nanocomposites with nanoclay (PLA/PBSA/Clay ternary nanocomposites) were prepared using the twin‐screw extruder. The blends were prepared for PBSA contents ranging from 25 to 75 wt % and their corresponding nanocomposites were prepared at a single‐clay concentration. The morphology and structure of the blends and the nanocomposites were examined using field emission scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. Rheological properties (dynamic oscillatory shear measurements and elongational viscosities) of the blends, nanocomposites, and pure components were studied in detail. The strain hardening intensity of different blends and nanocomposites was compared with the behavior of the pure components. Strong strain hardening behavior was observed for blends composed of 50 wt % and higher PBSA content. However, the effect of PBSA content on the elongational viscosity was less pronounced in PLA/PBSA/Clay ternary nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Miscibility and properties of completely biodegradable blends of poly(propylene carbonate) and poly(butylene succinate)

Completely biodegradable blends of poly (propylene carbonate) (PPC) and poly(butylene succinate) (PBS) were melt‐prepared and then compression‐molded. The miscibilities of the two aliphatic polyesters, that is, PPC and PBS, were investigated by dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The static mechanical properties, thermal behaviors, crystalline behavior, and melt flowability of the blends were also studied. Static tensile tests showed that the yield strength and the strength at break increased remarkably up to 30.7 and 46.3 MPa, respectively, with the incorporation of PBS. The good ductility of the blends was maintained in view of the large elongation at break. SEM observation revealed a two‐phase structure with good interfacial adhesion. The immiscibility of the two components was verified by the two independent glass‐transition temperatures obtained from DMA tests. Moreover, thermogravimetric measurements indicated that the thermal decomposition temperatures (T_?5% and T_?10%) of the PPC/PBS blends increased dramatically by 30–60°C when compared with PPC matrix. The melt flow indices of the blends showed that the introduction of PBS improved the melt flowability of the blends. The blending of PPC with PBS provided a practical way to develop completely biodegradable blends with applicable comprehensive properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

不同天然色素对PBS性能的影响

将从石榴皮、大黄和黄芩中提取的3种色素以不同的质量比与可生物降解的聚丁二酸丁二醇酯(PBS)共混,制备了多种比例的PBS/色素复合材料,研究了上述3种PBS/色素材料的结晶性和热稳定性;同时研究了色素的添加对PBS力学性能和抗菌性的影响。结果表明,添加3种色素对PBS的结晶形态影响不大,但是使晶粒尺寸变小,结晶度增加;使PBS的热稳定性有所提高,但对综合力学性能影响不大;3种色素都使PBS材料具有良好的抗菌性。     

Miscibility,crystallization, and mechanical properties of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)/ poly(butylene succinate) blends

Naturally amorphous biopolyester poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3/4HB) containing 21 mol % of 4HB was blended with semi‐crystal poly(butylene succinate) (PBS) with an aim to improve the properties of aliphatic polyesters. The effect of PBS contents on miscibility, thermal properties, crystallization kinetics, and mechanical property of the blends was evaluated by DSC, TGA, FTIR, wide‐angle X‐ray diffractometer (WAXD), Scanning Electron Microscope (SEM), and universal material testing machine. The thermal stability of P3/4HB was enhanced by blending with PBS. When PBS content is less than 30 wt %, the two polymers show better miscibility and their crystallization trend was enhanced by each other. The optimum mechanical properties were observed at the 5–10 wt % PBS blends. However, when the PBS content is more than 30 wt %, phase inversion happened. And the two polymers give lower miscibility and poor mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Light-colored conductive nanorod-mediated co-continuous polypropylene/poly(butylene succinate) blends: Regulatory mechanism,morphology evolution,electrical, and optical properties

It is still a critical challenge to prepare engineering plastics with multi-functionalities and high-performances while considering their aesthetic properties and dyeing processes. In this study, a light-colored conductive nanorod (CNR) was employed to mediate the morphology of immiscible polypropylene/poly(butylene succinate) (PP/PBS) blends. The CNR could be only located in polar PBS phase to effectively control the viscoelasticity ratio between binary phases. By incorporating just 9 per hundred resins (phr) of CNR, the sea-island structure of PP/PBS (70/30) would transform a stable co-continuous morphology of PP/PBS/CNR (70/30/9). The addition of CNR led to a significant reduction in blends' surface resistivity and volume resistivity. Simultaneously, the mechanical properties and appearance colors of the ternary blends were improved. The effect of CNR in morphological mediation was further verified with PP/poly(butylene adipate terephthalate)/CNR (PP/PBAT/CNR) and PP/poly(ε-caprolactone)/CNR (PP/PCL/CNR) blends. In summary, this work provided a desirable engineering plastic, demonstrating permanent antistatic performance, improved mechanical properties and good colorability.     

Effects of the matrix crystallinity,dispersed phase,and processing type on the morphological,thermal, and mechanical properties of polylactide-based binary blends with poly[(butylene adipate)-co-terephthalate] and poly[(butylene succinate)-co-adipate]

In this study, we prepared immiscible blends of 75 wt % polylactide (PLA) with 25 wt % poly[(butylene adipate)-co-terephthalate] (PBAT) through an injection-molding (IM) process and a twin-screw extruder (TSE) followed by IM. An amorphous polylactide (A-PLA) and a semicrystalline polylactide (SC-PLA) were used as the matrixes to investigate the matrix crystallization effect on the morphology and property development of the blends with only IM. A blend of A-PLA with 25 wt % poly[(butylene succinate)-co-adipate] (PBSA) was also prepared through IM to compare its properties with those of the A-PLA–PBAT blends. The morphological, thermal, solid viscoelastic, tensile, and flexural properties of the blends were compared, and their dependency on the evolution of the blend morphology was analyzed. The tensile results show that when IM was used as the sole processing technique, the ductility and toughness were significantly improved only when SC-PLA was used as the matrix. Preprocessing through TSE also resulted in the enhancement of the blend ductility. In A-PLA–PBSA, the vitrification of PLA hindered the crystallization of PBSA to very low temperatures (<0°C) and resulted in a very nonuniform structure with weak intermolecular bonding between phases. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47636.     

Processability enhancement of poly(lactic acid-co-ethylene terephthalate) by blending with poly(ethylene-co-vinyl acetate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(butylene succinate)

Processability enhancement feasibility of an in-house synthesized poly(lactic acid-co-ethylene terephthalate), PLET, is investigated by blending with commercial poly(ethylene-co-vinyl acetate), EVA, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, and poly(butylene succinate), PBS. The three blend systems are prepared by varying PLET contents, and their properties are characterized. DSC, SEM, and FTIR results indicate that PLET/EVA blends are immiscible, while the corresponding PLET/PBS and PLET/PHBV blends are miscible and partially miscible, respectively. DMA results show that the three blend systems have storage modulus comparable to those of commercial EVA, PHBV, and PBS, when PLET content is kept lower than 50, 25, and 25 wt%, respectively. PLET/EVA blends show higher thermal stability, compared to those of the other two blend systems. Results on degradability tests indicate that PLET/PBS blends show highest hydrolytic degradability, compared to the other two blends, as both blend constituents are associated in the hydrolytic degradation.