Miscibility, properties and morphology of biodegradable blends of UHMW-PPC/PVA/EVOH

Thermally stable and biodegradable blends of ultrahigh molecular weight poly(propylene carbonate) (UHMW-PPC), poly(vinyl alcohol) (PVA) and poly(ethylene-co-vinyl alcohol) (EVOH) were melt compounded in a batch mixer followed by compression molding. The miscibility, mechanical properties, thermal behavior, and morphologies of the blends were investigated by torque rheometer, Fourier transform infrared spectroscopy, tensile strength test, thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The experimental results showed well interfacial miscibility among phases of PVA, EVOH and PPC. The hydrogen bonding interaction between PPC with PVA and/or EVOH can also be confirmed by Fourier transform infrared spectroscopy spectra. The study on the mechanical properties and thermal behavior demonstrated that PVA/EVOH content can enhance the tensile strength, thermal stability and crystallinity of the blends dramatically. Further, scanning electron microscopic observation revealed a three-phase structure with good interfacial adhesion.     

Control and development of crystallinity and morphology in poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)/poly(propylene carbonate) blends

Two different methodologies (reactive blending and mechanical blending) for preparing blends of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) and poly(propylene carbonate) (PPC) were used. The miscibility, chemical structure, thermal behavior, crystallinity, morphology, and mechanical properties of the blends were investigated with Fourier transform infrared spectroscopy, differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and tensile tests. A certain extent of hydrogen‐bonding interactions between PHBV and PPC took place in the blends. The graft copolymerization was confirmed in the reactive system. The incorporation of PPC hampered the crystallization process of PHBV and evidently altered the morphology, and the effect was enhanced in the reactive blend. The mechanical properties of PHBV could be changed by 1–2 orders of magnitude by blending modification. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1427–1436, 2005     

Blends of poly(propylene) and polyacetal compatibilized by ethylene vinyl alcohol copolymers

Polymer blends of poly(propylene) (PP) and polyacetal (polyoxymethylene, POM) with ethylene vinyl alcohol (EVOH) copolymers were investigated by differential scanning calorimetry (DSC), rheological, tensile, and impact measurements, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The PP–POM–EVOH blends were extruded with a co‐rotating twin‐screw extruder. The ethylene group in the EVOH is partially miscible with PP, whereas the hydroxyl group in the EVOH can form hydrogen bonding with POM. The EVOH tends to reside along the interface, acting as a surfactant to reduce the interfacial tension and to increase the interfacial adhesion between the blends. Results from SEM and mechanical tests indicate that a small quantity of the EVOH copolymer or a smaller vinyl alcohol content in the EVOH copolymer results in a better compatibilized blend in terms of finer phase domains and better mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1471–1477, 2003     

Biobased blends of poly(propylene carbonate) and poly(hydroxybutyrate‐co‐hydroxyvalerate): Fabrication and characterization

Poly(propylene carbonate) (PPC), a CO₂‐based bioplastic and poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were melt blended followed by injection molding. Fourier transform infrared spectroscopy detected an interaction between the macromolecules from the reduction in the OH peak and a shift in the C?O peak. The onset degradation temperature of the polymer blends was improved by 5% and 19% in comparison to PHBV and PPC, respectively. Blending PPC with PHBV reduced the melting and crystallization temperatures and crystallinity of the latter as observed through differential scanning calorimetry. The amorphous nature of PPC affected the thermal properties of PHBV by hindering the spherulitic growth and diluting the crystalline region. Scanning electron micrographs presented a uniform dispersion and morphology of the blends, which lead to balanced mechanical properties. Incorporating PHBV, a stiff semi‐crystalline polymer improved the dimensional stability of PPC by restricting the motion of its polymer chains. © 2016 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44420.     

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.     

Orientation microstructure and properties of poly(propylene carbonate)/poly(butylene succinate) blend films

The blends of high molecular weight poly(propylene carbonate) (PPC) and poly(butylene succinate) (PBS) were melt blended using triphenylmethane triisocyanate (TTI) as a reactive coupling agent. TTI also serves as a compatibilizer for the blends of PPC and PBS. The blend containing 0.36 wt % TTI showed that the optimal mechanical properties were, therefore, calendared into films with different degrees of orientation. The calendering condition, degree of orientation, morphologies, mechanical properties, crystallization, and thermal behaviors of the films were investigated using wide‐angle X‐ray diffraction, scanning electron microscopy, tensile testing, and differential scanning calorimetry (DSC) techniques. The result showed that the as‐made films exhibited obvious orientation in machine direction (MD). Both tensile strength in MD and the tear strength in transverse direction (TD) increased with increasing the degree of orientation. The orientation of the film also increased the crystallinity and improved the thermal properties of the PPC/PBS blend films. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Incorporating amylopectin in poly(lactic acid) by melt blending using poly(ethylene‐co‐vinyl alcohol) as a thermoplastic carrier. (I) morphological characterization

In this study, the possibility of using a biodegradable grade of thermoplastic poly(ethylene‐co‐vinyl alcohol) with high (71 mol %) vinyl alcohol (EVOH‐29), as a carrier to incorporate the renewable and biodegradable component amylopectin (AP) into poly(lactic acid) (PLA) through melt blending, was investigated. The effect of using a plasticizer/compatibilizer (glycerol) in the blend systems was also investigated. In a first step, the EVOH/AP blends were produced and thereafter, in a second step, these were mixed with PLA. In this first study, the blend morphology was investigated using optical microscopy, scanning electron microscopy and Raman imaging spectroscopy and the thermal properties were measured by differential scanning calorimetry. Despite the fact that EVOH and AP are both highly polar, their blends were immiscible. Still, the blends exhibited an excellent phase dispersion on a micron level, which was enhanced further by the addition of glycerol. A good phase dispersion was finally observed by incorporation of the latter blends in the PLA matrix, suggesting that the proposed blending route can be successfully applied for these systems. Finally, the Differential scanning calorimetry (DSC) data showed that the melting point of EVOH dropped in the EVOH/AP blends, but the properties of the PLA phase was still relatively unaffected as a result of blending with the above components. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Increasing the compatibility of poly(l‐lactide)/poly(para‐dioxanone) blends through the addition of poly(para‐dioxanone‐co‐l‐lactide)

To modify the mechanical properties of a poly(l ‐lactide) (PLLA)/poly(para‐dioxanone) (PPDO) 85/15 blend, poly(para‐dioxanone‐co‐l ‐lactide) (PDOLLA) was used as a compatibilizer. The 85/15 PLLA/PPDO blends containing 1–5 wt % of the random copolymer PDOLLA were prepared by solution coprecipitation. Then, the thermal, morphological, and mechanical properties of the blends with different contents of PDOLLA were studied via differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and tensile testing, respectively. The DSC result revealed that the addition of PDOLLA into the blends only slightly changed the thermal properties by inhibiting the crystallization degree of the poly(l ‐lactide) in the polymer blends. The SEM photos indicated that the addition of 3 wt % PDOLLA into the blend was ideal for making the interface between the PLLA and PPDO phases unclear. The tensile testing result demonstrated that the mechanical properties of the blends containing 3 wt % PDOLLA were much improved with a tensile strength of 48 MPa and a breaking elongation of 214%. Therefore, we concluded that the morphological and mechanical properties of the PLLA/PPDO 85/15 blends could be tailored by the addition of the PDOLLA as a compatibilizer and that the blend containing a proper content of PDOLLA had the potential to be used as a medical implant material. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41323.     

Study of miscibility,crystallization, mechanical properties,and thermal stability of blends of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)

Natural amorphous polymer poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3HB4HB) containing 41 mol % of 4HB was blended with poly(3‐hydroxybutyrate) (PHB) with an aim to improve the properties of PHB. The influence of P3HB4HB contents on thermal and mechanical properties of the blends was evaluated with differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, stress–strain measurement and thermo gravimetric analyzer. Miscibility of PHB/P3HB4HB blends was mainly decided by the contents of P3HB4HB. When P3HB4HB exceeded 50 wt %, the two polymer phases separated and showed immiscibility. The addition of P3HB4HB did not alter the crystallinity of PHB, yet it diluted the PHB crystalline phase as revealed by DSC studies. DSC and FTIR results showed that the overall crystallinity of the blends decreased remarkably with increasing of P3HB4HB contents. Decreased glass transition temperature and crystallinity imparted desired flexibility for the blends. The ductility of the blends increased progressively with increasing of P3HB4HB content. Thus, the PHB mechanical properties can be modulated by changing the blend composition. P3HB4HB did not significantly improve the thermal stability of PHB, yet it is possible to melt process PHB without much molecular weights loss via blending it with suitable amounts of P3HB4HB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of the mixing time on the phase structure and glass‐transition behavior of poly(ethylene terephthalate)/poly(ethylene‐2,6‐naphthalate) blends

Blends of poly(ethylene terephthalate) and poly(ethylene‐2,6‐naphthalate) (70 : 30 w/w) were prepared via a melt‐mixing process at 280°C with various mixing times. The melt‐mixed blends were analyzed by magnetic resonance spectroscopy, differential scanning calorimetry, dynamic mechanical measurements, transmission electron microscopy, and tensile tests. The results indicate that the blends mixed for short times had lower extents of transesterification and were miscible to a limited extent. The blends initially show two glass transitions, which approached more closely and merged gradually with increasing mixing time. A mechanical model was used to help understand the glass‐transition behavior. With increasing mixing time, the phase structure of the blends improved, and this led to an increase in the tensile strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Special interaction between poly (propylene carbonate) and corn starch

Poly (propylene carbonate) (PPC) has been blended with corn starch granule by melt mixing. The properties of blends were evaluated using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), Instron tensile testing, and Fourier transform infrared (FTIR). FTIR indicates the presence of a specific interaction, hydrogen bonding, between the oxygen functional groups of PPC and the hydroxyl groups of starch. From DMA and DSC analysis, it is found that with the increase of starch content in PPC/starch blends, the glass transition temperature of PPC in blends increases a little due to hydrogen bonding. Tensile properties also proved that there is good interfacial adhesion in PPC filled with starch. POLYM. COMPOS., 26:37–41, 2005. © 2004 Society of Plastics Engineers.     

Preparation and characterization of konjac glucomannan/poly(diallydimethylammonium chloride) blend films

A novel preservative film was prepared by blending konjac glucomannan (KGM) and poly (diallydimethylammonium chloride) (PDADMAC) in aqueous system. The effects of PDADMAC content on the miscibility, morphology, thermal stability, and mechanical properties of the blend films were investigated by density determination, scanning electron microscopy (SEM), attenuated total reflection infrared spectroscopy (ATR‐IR), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile tests. The results of the density determination predicted that the blends of KGM and PDADMAC were miscible when the PDADMAC content was less than 70 wt %. Moreover, SEM and XRD confirmed the result. ATR‐IR showed that strong intermolecular hydrogen bonds interaction occurred between the negative charge groups of KGM and the quaternary ammonium groups of PDADMAC in the blends. The tensile strength and the break elongation of the blends were improved largely to 106.5 MPa and 32.04%, when the PDADMAC content was 20 wt %. The thermal stability of the blends was higher than pure KGM. Results from the film‐coating preservation experiments with lichi and grapes showed that the blend film had excellent water‐holding and preservative ability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Evidence of compatibility and thermal stability improvement of poly(propylene carbonate) and polyoxymethylene blends

Poly(propylene carbonate) (PPC) is a promising new sustainable polymer produced from carbon dioxide. PPC has inferior thermal stability which could be enhanced by synergistic blending with other polymers. Blends of PPC and the engineering thermoplastic polyoxymethylene are produced by melt compounding in various weight ratios. The compatibility of the blends is investigated using thermogravimetric analysis (TGA), differential scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), density measurements, and scanning electron microscopy (SEM). TGA reveals that thermal stability of the blends increases dramatically in comparison to the neat PPC. A small shift in the glass transition temperature demonstrates the immiscibility of the blends but also indicates some compatibility, attributed to potential dipole–dipole interactions which are also corroborated with the FTIR results. A deviation of the rule of mixtures for density is found for some of the blends. SEM analysis of the blends shows two phase morphology; however, the interfacial adhesion appeared to be enhanced with increasing PPC content. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45823.     

Tailoring the morphology and properties of poly(lactic acid)/poly(ethylene)‐co‐(vinyl acetate)/starch blends via reactive compatibilization

Poly(lactic acid)/poly(ethylene‐co‐vinyl acetate)/starch (PLA/EVA/starch) ternary blends were prepared by multi‐step melt processing (reactive extrusion) in the presence of maleic anhydride (MA), benzoyl peroxide and glycerol. The effects of MA and glycerol concentration on the morphology and properties of the PLA/EVA/starch blends were studied using scanning electron microscopy, transmission electron microscopy, atomic force microscopy, the Molau experiment, dynamic mechanical thermal analysis and differential scanning calorimetry etc. The plasticization and compatibilization provided a synergistic effect to these blends accompanied by a significant reduction in starch particle size and an increase in interfacial adhesion. Starch was finely dispersed in the ternary blends with a dimension of 0.5 ? 2 µm. Furthermore, EVA‐coated starch or a starch‐in‐EVA type of morphology was observed for the reactively compatibilized PLA/EVA/starch blends. The EVA with starch gradually changed into a co‐continuous phase with increasing MA concentration. Consequently, the toughness of the blends was improved. Since property stability of starch is an issue, the tensile properties of these blends were measured after different storage times and the blends showed good property stability. Copyright © 2012 Society of Chemical Industry     

Miscibility and intermolecular hydrogen‐bonding interactions in poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)/poly(4‐vinyl phenol) binary blends

The miscibility and hydrogen bonding interaction in the poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)/poly(4‐vinyl phenol) [P(3HB‐co‐3HH)/PVPh] binary blends were investigated by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The DSC results indicate that P(3HB‐co‐3HH) with 20 mol % 3HH unit content is fully miscible with PVPh, and FTIR studies reveal the existence of hydrogen bonding interaction between the carbonyl groups of P(3HB‐co‐3HH) and the hydroxyl groups of PVPh. The effect of blending of PVPh on the mechanical properties of P(3HB‐co‐3HH) were studied by tensile testing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Reactive compatibilization of poly(l‐lactic acid)/poly(propylene carbonate) blends: Thermal,thermomechanical, and morphological properties

Poly(l ‐lactic acid) (PLLA) was blended with poly(propylene carbonate) (PPC) with various compositions by a melt‐blending process to evaluate their general properties for a potential flexible packaging field. The mechanical properties, including the tensile strength and modulus, revealed a tendency to decrease with the addition of ductile PPC; this was induced by the poor interfacial adhesion between PLLA and PPC with the cavities and clear edges and was observed through morphological observation. Reactive compatibilization was applied to improve the interfacial adhesion between PLLA and PPC, and the elongation at break was profoundly enhanced because of the improved interfacial adhesion between the two phases. The compatibilized PLLA/PPC blends showed considerable improvements in the storage modulus in the transition region with stable thermal stability; this could be a benefit for thermal processing. The addition of PPC had a great effect on the solidlike behavior and increased the elasticity of the PLLA/PPC blends. Up to 2.0 phr maleic anhydride showed a great efficiency in enhancing the dynamic storage modulus and complex viscosity of the PLLA/PPC blends. We also confirmed that it was feasible to fabricate PLLA/PPC blends with controllable barrier properties with combination of PLLA and PPC under reactive compatibilization while retaining the biodegradability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43388.     

Toughening of poly(propylene carbonate) by hyperbranched poly(ester‐amide) via hydrogen bonding interaction

Poly(propylene carbonate) (PPC) is a biodegradable alternative copolymer of propylene oxide and carbon dioxide. As an amorphous polymer with lower glass transition temperature around 35 °C, PPC shows poor mechanical performance in that it becomes brittle below 20 °C and its dimensional stability deteriorates above 40 °C; thus toughening of PPC is urgently needed. Here we describe a biodegradable hyperbranched poly(ester‐amide) (HBP) that is suitable for this purpose. Compared with pure PPC, the PPC/HBP blend with 2.5 wt% HBP loading showed a 51 °C increase in thermal decomposition temperature and a 100% increase in elongation at break, whilst the corresponding tensile strength remained as high as 45 MPa and tensile modulus showed no obvious decrease. Crazing as well as cavitation was observed in the scanning electron microscopy images of the blends, which provided good evidence for the toughening mechanism of PPC. The intermolecular hydrogen bonding interaction confirmed by Fourier transform infrared spectral analysis proved to be the reason for the toughening phenomenon. Copyright © 2011 Society of Chemical Industry     

Blends of poly(vinyl chloride) with α‐methylstyrene‐acrylonitrile‐butadiene‐styrene copolymer: Thermal properties,mechanical properties,and morphology

Binary blends of poly(vinyl chloride) (PVC) with α‐methylstyrene‐acrylonitrile‐butadiene‐styrene copolymer (AMS‐ABS) were prepared via melt blending. A single glass transition temperature (T_g) was observed by differential scanning calorimetry, thus indicating that PVC is miscible with the α‐methylstyrene‐acrylonitrile‐styrene in AMS‐ABS. The results from attenuated total reflection Fourier transform infrared spectra indicated that specific strong interactions were not available in the blends. With increasing amounts of AMS‐ABS, both heat distortion temperature and thermal stability were increased considerably. With regard to mechanical properties, flexural and tensile properties decreased with increasing AMS‐ABS content. A synergism was observed in impact strength. The morphology of both impact‐fractured and tensile‐fractured surfaces, observed by scanning electron microscopy, correlated well with the mechanical properties. It is suggested that there was a transition of fracture mechanisms with the changing composition of the binary blends—from shear yielding for blends rich in PVC to cavitation for blends rich in AMS‐ABS. J. VINYL ADDIT. TECHNOL., 19:1–10, 2013. © 2013 Society of Plastics Engineers     

Compatibilization of poly(lactic acid)/high impact polystyrene interface using copolymer poly(stylene‐ran‐methyl acrylate)

In this work, a surfactant‐free emulsion polymerization method was utilized to synthesize poly(styrene‐ran‐methyl acrylate) (PSMA) at a styrene/(methyl acrylate) mole ratio of 75/25 with the aim to compatibilize high impact polystyrene (HIPS)/poly(lactic acid) (PLA) interface. HIPS/PLA blends with different PSMA contents were prepared. Their phase morphologies, mechanical properties, and rheological and crystallization behaviors were investigated using scanning electron microscopy, tensile tests, rotational rheometry, and differential scanning calorimetry. The rheological results showed that the complex viscosity, storage moduli, and loss moduli of PLA/HIPS blends were enhanced with increasing PSMA content. A decrease in the degree of crystallinity of PLA in PLA/HIPS blends with the addition of PSMA was observed in the differential scanning calorimetry results. It was also revealed that the addition of a small amount of PSMA can effectively improve the compatibility and thus the interfacial adhesion of the PLA/HIPS blends, thereby reducing the size of the HIPS dispersion phase. When 1 wt % of PSMA was used, compared with the PLA/HIPS blends without PSMA, the tensile strength and notched Charpy impact strength of PLA/HIPS blends were improved by 95.3% and 104.8%, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45799.