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1.
Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by To = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was Tp = 0.91B + 320, and the temperature at which degradation was completed was Tf = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), To = 0.96B + 308, Tp = 0.99B + 320, and Tf = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), To = 1.11B + 305, Tp = 1.10B + 319, and Tf = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures To, Tp, and Tf relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001  相似文献   

2.
Hsiu-Jung Chiu 《Polymer》2005,46(11):3906-3913
Segregation morphology of poly(3-hydroxybutyrate) (PHB)/poly(vinyl acetate) (PVAc) and poly(3-hydroxybutyrate-co-10% 3-hydroxyvalerate) (P(HB-co-10% HV)/PVAc blends crystallized at 70 °C have been investigated by means of small angle X-ray scattering (SAXS). Morphological parameters including the crystal thickness (lc) and the amorphous layer thickness (la) were deduced from the one-dimensional correlation function (γ(z)). Blending with PVAc thickened the PHB crystals but not the P(HB-co-10% HV) crystals. On the basis of the composition variation of la, and the volume fraction of lamellar stacks (?s) revealed that PHB/PVAc blends created the interlamellar segregation morphology when the weight fraction of PVAc (wPVAc)≤0.2 and the interlamellar and interfibrillar segregation coexisted when wPVAc>0.2, while P(HB-co-10% HV)/PVAc blends yielded the interfibrillar segregation morphology at all blend compositions. For both PHB/PVAc and P(HB-co-10% HV)/PVAc blends, the distance of PVAc segregation was promoted by increasing PVAc composition and the distance of PVAc segregation in P(HB-co-10% HV)/PVAc blends was greater than in PHB/PVAc at a given PVAc composition. The crystal growth rate played a key role in controlling the segregation of PVAc.  相似文献   

3.
Yan ChenGuang Yang  Qun Chen 《Polymer》2002,43(7):2095-2099
The noncrystalline structures of poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) copolymers were studied by variable temperature solid-state wide-line 1H NMR and solid-state high-resolution 13C NMR spectroscopy. It is found that at room temperature there exists a rich and rigid component in the noncrystalline region of PHB and PHBV. The content of this component decreases with the increase in 3-hydroxyvalerate content in PHBV and with the increase in temperature. The brittleness of PHB may be partly attributed to the rigidness of the noncrystalline region at room temperature, while the improvement of the properties of PHBV may come from the enhanced mobility of the noncrystalline region.  相似文献   

4.
A. González  M. Iriarte  J.J. Iruin 《Polymer》2004,45(12):4139-4147
This work summarizes the miscibility and transport properties of different polymer blends obtained by mixing a bacterial, isotactic poly(3-hydroxybutyrate) (iPHB) with copolymers of styrene and vinyl phenol (Sty-co-VPh copolymers). Given that iPHB and pure commodity poly(styrene) (PS) form immiscible blends, PS has been modified by copolymerizing it with vinyl phenol (VPh) units, in an attempt to promote blend miscibility. VPh units have appropriate functional groups that interact with iPHB ester moieties. The potential miscibility was investigated by differential scanning calorimetry (DSC) measuring the glass transition temperatures of blends of different compositions. As an additional test, the interaction parameter between the two components, using the iPHB melting point depression caused by the second component, was also measured. Copolymers containing less than 90% styrene showed miscibility with iPHB.Given the remarkable barrier properties of iPHB to gases and vapours, the study has been completed by measuring transport properties of carbon dioxide through different iPHB/Sty-co-VPh copolymer blends, using gravimetric sorptions in a Cahn electrobalance. A clear difference was observed between the behaviour of rubbery blends and those that exhibit a glassy behaviour at the selected experimental temperature (303 K).  相似文献   

5.
Relationships between composition- and temperature-dependent intermolecular interactions and cold crystallization behaviors of poly(3-hydroxybutyrate) (PHB)/ cellulose acetate butyrate (CAB) blends have been investigated mainly by infrared (IR) spectroscopy, together with differential scanning calorimetry, and wide-angle X-ray diffraction (WAXD). Weak intermolecular hydrogen bondings between OH groups in CAB and CO groups in amorphous part of PHB define as inter were detected in OH stretching bands of the blends. These interactions occur in the blends with high CAB content (wCAB) and highly depend on temperature. For all the blends having 0.2 ≤ wCAB ≤ 0.7, when temperature is raised (e.g., above 90 °C for the blend with wCAB = 0.5) the cold crystallization of PHB was discerned, as evidenced by an increase of the absorbance of the band due to CO stretching in the crystal field. The crystallization was found to involve the dissociation of inter and transformation of inter into intramolecular hydrogen bondings within PHB and within CAB as summarized in Table 2 in this text, which promotes the crystallization and enhances stabilization of the crystals. Consequently, the crystallization of the PHB is influenced by exchanges of the hydrogen bondings as described above with raising temperatures. X-ray diffraction from PHB crystals in the blends show a remarkable decrease of crystallinity with wCAB and eventually disappear when wCAB ≥ 0.8.  相似文献   

6.
Limin Zhang  Guangjin Hou  Feng Deng 《Polymer》2007,48(10):2928-2938
Solid-state NMR techniques have been employed to investigate the domain structure and mobility of the bacterial biopolymeric metabolites such as poly(3-hydroxybutyrate) (PHB) and its copolymers poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) containing 2.7 mol% (PHBV2.7) and 6.5 mol% (PHBV6.5) 3-hydroxyvalerate. Both single-pulse excitation with magic-angle spinning (SPEMAS) and cross-polarization magic-angle spinning (CPMAS) 13C NMR results showed that these biopolymers were composed of amorphous and crystalline regions having distinct molecular dynamics. Under magic-angle spinning, 1H T1ρ and 13C T1 showed two processes for each carbon. Proton relaxation-induced spectral editing (PRISE) techniques allowed the neat separation of the 13C resonances in the crystalline regions from those in the amorphous ones. The proton spin-lattice relaxation time in the tilted rotating frame, , measured using the Lee-Goldburg sequence with frequency modulation (LGFM) as the spin-locking scheme, was also double exponential and significantly longer than 1H T1ρ. The difference between for the amorphous and crystalline domains was greater than that of 1H T1ρ. Our results showed that the differences could be exploited in LGFM-CPMAS experiments to separate the signals from two distinct regions. 1H spin-diffusion results showed that the domain size of the mobile components in PHB, PHBV2.7 and PHBV6.5 were about 13, 24 and 36 nm whereas the ordered domain sizes were smaller than 76, 65 and 55 nm, respectively. The results indicated that the introduction of 3-hydroxyvalerate into PHB led to marked molecular mobility enhancement in the biopolymers.  相似文献   

7.
Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was blended with poly(lactic acid) (PLA) with various reactive processing agents to decrease its brittleness and enhance its processability. Three diisocyanates, namely, hexamethylene diisocyanate, poly(hexamethylene diisocyanate), and 1,4‐phenylene diisocyanate, were used as compatibilizing agents. The morphology, thermomechanical properties, and rheological behavior were investigated with scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, tensile testing, dynamomechanical thermal analysis in torsion mode (dynamic mechanical analysis), and oscillatory rheometry with a parallel‐plate setup. The presence of the diisocyanates resulted in an enhanced polymer blend compatibility; this led to an improvement in the overall mechanical performance but did not affect the thermal stability of the system. A slight reduction in the PHBV crystallinity was observed with the incorporation of the diisocyanates. The addition of diisocyanates to the PHBV–PLA blend resulted in a notable increase in the final complex viscosity at low frequencies when compared with the same system without compatibilizers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44806.  相似文献   

8.
Microbial synthesis of copolymers of [R]-3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB), P(3HB-co-4HB), by Alcaligenes eutrophus, Alcaligenes latus, and Comamonas acidovorans from various carbon sources has been studied. The copolyester compositions varied from 0 to 100 mol% 4HB, depending on the microorganism and the combination of carbon substrates supplied. The thermal and physical properties of compositions with 0–100 mol% 4HB were investigated. The copolyesters represented a wide variety of polymeric materials, from hard crystalline plastic to very elastic rubbers, depending on composition. The copolyester films with high 4HB fractions (64–100 mol% 4HB) exhibited the characteristics of a thermoplastic elastomer, and the tensile strength increased from 17 to 104 MPa as the 4HB fraction increased. The enzymatic degradation of P(3HB-co-4HB) films was studied in an aqueous solution of extracellular polyhydroxybutyrate (PHB) depolymerase from Alcaligenes faecalis or lipase from Rhizopus delemer. The erosion rate of P(3HB-co-4HB) films was strongly dependent on the copolymer composition. In addition, environmental degradation of P(3HB-co-4HB) films in sea water was investigated.  相似文献   

9.
In this work the miscibility and the carbon dioxide transport properties of a bacterial, isotactic poly(3-hydroxybutyrate) (iPHB) and its blends with a copolymer of epichlorohydrin and ethylene oxide (ECH-co-EO) have been studied. Blends were prepared by solution/precipitation. The aim to obtain miscible blends of iPHB with a rubbery second component (such as the ECH-co-EO copolymer) is to have mixtures with glass transition temperatures below room temperature. In these conditions, the iPHB chains not involved in the crystalline regions retain its mobility. This mobility seems to be necessary for the attack of microorganisms and the corresponding biodegradability.Miscibility is the general rule of these mixtures, as shown by the existence of a single glass transition temperature for each blend and by the depression of the iPHB melting point. The interaction energy density stabilising the mixtures, calculated using the Nishi-Wang treatment, was similar to those of other polymer mixtures involving different polyesters and poly(epichlorohydrin) (PECH) and ECH-co-EO copolymers. The so-called binary interaction model has been used in order to simulate the evolution of the interaction energy density with the ECH-co-EO copolymer composition. Previously reported experimental data on blends of iPHB with PECH and poly(ethylene oxide) (PEO) have been used to quantify the required segmental interaction energy densities.In the determination of the CO2 transport properties of the mixtures, only iPHB rich blends containing up to 40% of copolymer were considered. The effect of the ECH-co-EO copolymer is to increase the sorption and the diffusion of the penetrant (and, consequently, the permeability) with respect to the values of the pure iPHB. This is primarily due to the reduction of the global crystallinity of the blends and to the low barrier character of the ECH-co-EO copolymer. Sorption data can be reasonably reproduced using an extension of the Henry's law to ternary systems.  相似文献   

10.
The thermal and mechanical properties of the biodegradable blends of poly(L ‐lactic acid) (PLLA) and lignin prepared by manual mixing have been investigated. Both the results of DSC and FTIR spectral analyses indicated the existence of intermolecular interaction between PLLA and lignin. Furthermore, FTIR elucidated the existence of an intermolecular hydrogen‐bonding interaction. Study of the mechanical properties of the blends indicated that the maximum strength and the elongation of the material decreased and the Young's modulus remained almost constant when the lignin content reached 20%. Thermogravimetry indicated that lignin would accelerate the thermal degradation of PLLA when the content of lignin was more than 20%. Compared with some other biodegradable polymers, the blend of PLLA and lignin is thought to be a promising material, because the material properties, as well as the price, are at an acceptable level when the content of lignin is less than about 20%. Copyright © 2003 Society of Chemical Industry  相似文献   

11.
The transport properties of carbon dioxide, water, and different organic solvents in bacterial poly(3-hydroxybutyrate) (PHB) at 30°C were investigated. CO2 sorption was measured by the gravimetric method using a recording microbalance at subatmospheric pressures. Results were adequately interpreted in terms of Henry's law. Organic solvent and water permeabilities for both vapors and liquid were measured using a gravimetric cell. The data were interpreted in different terms depending on the units in which permeability was measured. Most of the solvent-polymer systems showed the typical time-lag plot, but in liquid permeation experiments, some anomalous behaviors were observed, with a transient period of rapid permeation at the beginning of the experiment before reaching the steady state. The transport properties of PHB were compared with those of other polymers, either from synthetic or biodegradable origin. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1849–1859, 1997  相似文献   

12.
The thermal behaviour and phase morphology of poly(3-hydroxybutyrate) (PHB) and starch acetate (SA) blends have been studied by differential scanning calorimetry, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy and polarizing optical microscopy. PHB/SA blends were immiscible. The melting temperatures of PHB in the blends showed some shift with increase of SA content. The melting enthalpy of the PHB phase in the blend was close to the value for pure PHB. The glass transition temperatures of PHB in the blends remained constant at 9°C. The FTIR absorptions of hydroxyl groups of SA and carbonyl groups of PHB in the blends were found to be independent of the second component at 3470cm-1 and 1724cm-1, respectively. The crystallization of PHB was affected by the addition of the SA component both from the melt on cooling and from the glassy state on heating. The temperature and enthalpy of non-isothermal crystallization of PHB in the blends were much lower than those of pure PHB. The crystalline morphology of PHB crystallized from the melt under isothermal conditions varied with SA content. The cold crystallization peaks of PHB in the blends shifted to higher temperatures compared with that of pure PHB. ©1997 SCI  相似文献   

13.
Conventionally, the chemically crosslinked shape memory polymer (SMP) blends are hard to recycle due to their network structure. Herein, the environmental SMP blends of olefin block copolymer (OBC), a unique thermoplastic elastomer, and poly(?‐caprolactone) (PCL) were physically crosslinked. Dicumyl peroxide was used as the compatibilizer to improve their miscibility, as evidenced by the reduced dispersed domain size of PCL in the OBC matrix and the increased complex viscosity. The peroxide modified OBC/PCL blend conferred enhanced tensile properties, increased dynamic storage modulus, increased crystallization temperature, and higher recovery stress. The shape memory behaviors of OBC/PCL blends predeformed under two different predeformation temperatures (30 and 65 °C) were investigated. The recovery stress showed respective maximum peak values corresponding to their predeformation temperatures. In addition, the modified blends gave the better shape memory performance at 65 °C. Besides the peroxide modification approach, a precycle training process via prestretching the samples and reducing the mechanical hysteresis was implemented to improve shape memory performance further. This is the first work on the OBC‐based SMP blends to enhance shape memory performance by combining the chemical modification using added peroxide compatibilizer and the process modification using a precycle training process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45475.  相似文献   

14.
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.  相似文献   

15.
介绍了生物可降解材料聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P(3HB-co-4HB))的性能及特点;综述了针对P(3HB-co-4HB)加工温度窄、脆性大、成本高等缺点而进行的增塑改性、扩链改性、共混改性的技术进展以及P(3HB-co-4HB)纺丝成纤技术;阐述了利用P(3HB-co-4HB)可塑性、生物降解性和生物相容性等在医疗领域的应用情况及发展前景;指出P(3HB-co-4HB)的研究将集中在其材料加工流动性、结晶性能的改善及其纤维加工技术与纤维表面整理技术等方面。  相似文献   

16.
The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997  相似文献   

17.
Porous poly(L ‐lactide) (PLLA) films were prepared by water extraction of poly(ethylene oxide) (PEO) from solution‐cast PLLA and PEO blend films. The dependence of blend ratio and molecular weight of PEO on the porosity and pore size of films was investigated by gravimetry and scanning electron microscopy. The film porosity and extracted weight ratio were in good agreement with the expected for porous films prepared using PEO of low molecular weight (Mw = 1 × 103), but shifted to lower values than expected when high molecular weight PEO (Mw = 1 × 105) was utilized. The maximum pore size was larger for porous films prepared from PEO having higher molecular weight, when compared at the same blending ratio of PLLA and PEO before water extraction. Differential scanning calorimetry of as‐cast PLLA and PEO blend films revealed that PLLA and PEO were phase‐separated at least after solvent evaporation. On the other hand, comparison of blend films before and after extraction suggested that a small amount of PEO was trapped in the amorphous region between PLLA crystallites even after water extraction and hindered PLLA crystallization during solvent evaporation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 629–637, 2000  相似文献   

18.
《Polymer》2014,55(26):6906-6914
Double ring-banded spherulites of biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV with 12 wt% 3HV) blending with 30 wt% amorphous poly(vinyl acetate) (PVAc) were examined using polarized light optical microscopy (POM), scanning electron microscopy (SEM), atomic-force microscopy (AFM) and micro-beam X-ray diffraction. A ring-banded spherulite of PHBV/PVAc 70/30 blend was linearly scanned across the bands in 5 μm steps by means of micro-beam X-ray diffraction. Solvent-etching and fracturing were utilized for probing the interior lamellar textures of the blend samples. Detail interior lamellar orientations in bulk film of PHBV three-dimensional ring-banded spherulites were revealed. SEM and micro-beam X-ray diffraction results suggest that the PHBV lamellar orientation gradually change along the radial growth direction with right-handed rotation sense. The blending effect in band pattern (width and regularity) of PHBV/PVAc blend was discussed.  相似文献   

19.
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a biodegradable polymer with significant potential for use in food packaging. However, its limited melt strength poses a challenge when employing film-blowing techniques to produce flexible packaging. To overcome this obstacle, we developed blends consisting of 70 wt% PHBV and 30 wt% poly(butylene-co-succinate-co-adipate) (PBSA). Organic peroxides such as dicumyl peroxide and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, were utilized as reactive compatibilizers to enhance the interfacial adhesion between the polymers. Additionally, acetyl tributyl citrate (ATBC) was employed as a plasticizer to improve processability and ductility. The inclusion of organic peroxides resulted in the formation of long-branched structures, as confirmed by the van-Gurp-Palmen plot. The melt flow index decreased from 30 to 9.8 g/10 min without ATBC and 15.5 g/10 min with ATBC. Successful production of blown PHBV/PBSA films was achieved on a pilot scale (bubble height 180 cm). These films exhibited heat-sealing capability and increased impact strength (7.7 kJ/m2). Moreover, the films maintained a maximum elongation at break of 4% during a 3-month storage experiment with frozen food. Food safety was assessed through overall migration experiments, and the non-plasticized films received approval. In conclusion, the compatibilized PHBV/PBSA blends demonstrate great potential as materials for manufacturing film-blown flexible packaging.  相似文献   

20.
Ternary blends containing polypropylene (PP), poly(1-butene) (PB), and hydrogenated oligo(cyclopentadiene) (HOCP) have been studied using microscopic calorimetric and dynamic mechanical techniques, with no phase separation having been observed in the melt for all the considered compositions. The morphology of the crystallized blends and spherulite growth rate of the PP component appeared to be influenced by the blend composition. The presence of one or two Tgs revealed by dynamic mechanical thermal analysis (DMTA) on quenched or crystallized blends has suggested that demixing phenomena can occur during the crystallization of the components. The blend composition has been found to affect the overall crystallization rate and the equilibrium melting temperature of the PP component. A parameter describing the enthalpic interactions between the PP component and the diluent fraction evidenced that the addition of HOCP to PP and PB increases the stability of the ternary blend. The above results suggest that the three components can form a miscible blend in the melt. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1659–1665, 1997  相似文献   

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