Miscibility and rheological properties of poly(vinyl chloride)/styrene–acrylonitrile blends prepared by melt extrusion

Styrene–acrylonitrile (SAN) with acrylonitrile (AN) concentrations of 11.6–26 wt % and α‐methylstyrene acrylonitrile (αMSAN) with a wide range of AN concentrations are miscible with poly(vinyl chloride) (PVC) through solution blending. Here we examine the rheological properties and miscibility of PVC/SAN and PVC/αMSAN blends prepared by melt extrusion for commercial applications. We have investigated the rheological properties of the blends with a rheometer and a melt indexer. The PVC/SAN and PVC/αMSAN blends have a low melting torque, a long degradation time, and a high melt index, and this means that they have better processability than pure PVC. The miscibility of the blends has been characterized with differential scanning calorimetry, dynamic mechanical thermal analysis, and advanced rheometrics expansion system analysis. The miscibility of the blends has also been characterized with scanning electron microscopy. The SAN series with AN concentrations of 24–31 wt % is immiscible with PVC by melt extrusion, whereas αMSAN with 31 wt % AN is miscible with PVC, even when they are blended by melt extrusion, because of the strong interaction between PVC and αMSAN. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanical and thermal properties of (acrylonitrile‐styrene‐acrylic)/(α‐methylstyrene‐acrylonitrile) binary blends

In this work, (acrylonitrile‐styrene‐acrylic)/(α‐methylstyrene‐acrylonitrile) copolymer (ASA/α‐MSAN) binary alloy was prepared with different composition ratios via melt blending. This work mainly focused on improving the heat resistance of ASA. According to the results of dynamic mechanical thermal analysis, the binary blends exhibited three glass transition temperatures (T_gs) and the shift of the T_gs indicated the partial miscibility of binary blends. This partial miscibility maintained the high T_g of α‐MSAN, which led to the outstanding heat resistance of binary blends. Furthermore, heat distortion temperature also showed that the heat resistance of binary blends was significantly enhanced with the addition of α‐MSAN. However, the introduction of this highly rigid polymer also brought with it the sharp decrease of the impact strength and elongation at break, which is reflected in the morphologies of the blend system obtained via scanning electron microscopy. In addition, the incorporation of α‐MSAN increased the tensile strength, flexural strength, and modulus. There were no new groups observed from Fourier‐transform infrared spectra, which means no strong specific intermolecular interactions existed between ASA and α‐MSAN. Moreover, the processibility of the blend system was obviously improved from the results of melt flow rate. J. VINYL ADDIT. TECHNOL., 22:156–162, 2016. © 2014 Society of Plastics Engineers     

Melt miscibility and mechanical properties of metallocene linear low‐density polyethylene blends with high‐density polyethylene: influence of comonomer type

In this paper, the implications of melt miscibility on the thermal and mechanical properties of linear low‐density polyethylene (LLDPE)/high‐density polyethylene (HDPE) blends were assessed with respect to the influence of the comonomer type. The influence of the latter was examined by selecting one butene LLDPE and one octene LLDPE of very similar weight‐average molecular weight (M_w), molecular‐weight distribution (MWD) and branch content, keeping the comonomer type as the only primary molecular variable. Each of the two metallocene LLDPEs was melt‐blended with the same HDPE at 190 °C in a Haake melt‐blender. The rheological, thermal and mechanical properties were measured by the use of an ARES rheometer, differential scanning calorimeter and Instron machine, respectively. The rheological measurements, made over the linear viscoelastic range, suggested no significant influence of the branch type on the melt miscibility. The rheology results are in agreement with those obtained from previous transmission electron microscopy (TEM) and small‐angle neutron scattering (SANS) studies. The dynamic shear viscosity and total crystallinity of the metallocene (m)‐LLDPE blends with HDPE followed linear additivity. At small strains, the branch type has little or no influence on the melt miscibility and solid‐state properties of the blends. Even the large‐strain mechanical properties, such as tensile strength and elongation at break, were not influenced by the comonomer type. However, the ultimate tensile properties of the HDPE‐rich blends were poor. Incompatibility of the HDPE‐rich blends, as a result of the weak interfaces between the blend components, is suggested to develop at large strains. Copyright © 2005 Society of Chemical Industry     

Synergistic effect of compatibilizer and cloisite 30B on the functional properties of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/polylactide blends

Blends of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and polylactide (PLA) with different PHBV/PLA weight ratios (100/0, 75/25, 50/50, 25/75, 0/100) were prepared by melt compounding. To improve the miscibility between the two components of the blend, low amount of compatibilizing agent (5 wt%), obtained by grafting maleic anhydride onto PHBV, was used. When compared with the uncompatibilized blends, the compatibilizer presence induces a greater interfacial adhesion. The effect of Cloisite 30B (C30B) on the blend morphology and the blend properties was also investigated. The morphology of the different blends as well as the evolution of their material properties were discussed in terms of the nanoclay and compatibilizing agent contents. A synergistic effect of compatibilizer and C30B was highlighted leading to an improved miscibility of the two blend components. The resulting properties were correlated with the morphology observed for the different blends. POLYM. ENG. SCI., 54:2239–2251, 2014. © 2013 Society of Plastics Engineers     

Evaluation of mechanical properties and physical interactions of a ternary blend of poly(ethylene‐co‐octene)/poly(ethylene‐co‐vinyl acetate)/poly(vinyl chloride) in the molten state

In this work, ethylene‐co‐vinyl acetate (EVA), poly(ethylene‐co‐octene) (POE), and poly(vinyl chloride) (PVC) blends were processed in a molten state process using a corotating twin‐screw extruder to assess both the balance of mechanical properties and physical interactions in the melt state. Tensile measurements, scanning electron microscopy, and oscillatory rheometry were performed. By means of flow curves, the parameters of the power law as well as the distribution of relaxation times were assessed with the aid of a nonlinear regularization method. The mechanical properties for the EVA‐POE blend approximated the values for POE, while inclusion of PVC shifted the modulus values to those of neat EVA. The rise in modulus was corroborated by the PVC phase dispersion as solid particles that act as a reinforcement for the ternary blend. The rheological properties in the molten state show that the POE does not present molecular entanglement effects and so tends both to diminish the EVA mechanical properties and increase the fluidity of the blend. However, the addition of PVC both restored the EVA typical pseudoplastic feature and promoted the increase in the viscosity and the mechanical properties of the ternary blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improvement in the heat resistance of poly(vinyl chloride) profile with styrenic polymers

The styrenic polymers poly(α‐methylstyrene‐acrylonitrile) (α‐MSAN) and poly(acrylonitrile‐butadiene‐styrene) (ABS) and (three types) were used to improve the heat resistance of poly(vinyl chloride) (PVC). The glass transition temperature (T_g) and miscibility were analyzed by dynamic mechanical thermal analysis (DMTA). Effects of composition on heat distortion temperature (HDT) were investigated with the different styrenic polymers. Other physical properties such as mechanical properties and melt flow rate (MFR) were also determined. Morphology was observed by scanning electron microscopy (SEM) in order to support the mechanical property results. The PVC was miscible with α‐MSAN but partially miscible with the ABS series, and α‐MSAN was much more effective in enhancing the T_g and HDT of rigid PVC than the ABS series as for mechanical properties, the addition of α‐MSAN could improve the tensile strength, bending strength, and bending modulus but decrease the impact strength of the materials compared with the addition of the ABS series. Improvement in processability was observed in the MFR results with the addition of the styrenic polymers. On the basis of all the properties, the formulation with an α‐MSAN content of 30 phr (parts per hundred parts of resin) was superior for heat‐resistant PVC profile. The HDT of PVC could be increased from 76.9°C to 85.4°C (measured under the maximum bending stress of 0.45 MPa) and combined with good mechanical properties and processability by the addition of 30 phr of α‐MSAN. Also, a heat‐resistant PVC profile was successfully fabricated. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Miscibility and thermal and mechanical properties of melt‐mixed poly(lactic acid)/poly(trimethylene terephthalate)/(methyl methacrylate)‐butadiene‐styrene copolymer blends

This study examined the miscibility and mechanical properties of melt‐mixed poly(lactic acid) (PLA), poly (trimethylene terephthalate) (PTT), and PLA/PTT blend with 5–10 phr of methyl methacrylate‐butadiene‐styrene copolymer (MBS). The isothermal crystallization kinetics of the PTT blends were analyzed by using the Avrami equation. The Differential Scanning Calorimetry (DSC) and scanning electron microscope results indicated that the miscibility of the PLA/PTT blends was improved by adding 5–10 phr of MBS. Although PLA, with the addition of 10 phr of MBS, had lower tensile strength at yield and higher breaking elongation and impact strength than pure PLA, no improvement in these mechanical properties could be observed in PLA/PTT blends. This result is explained by assuming that the crystallization of PTT at the interface favors the disentanglement of MBS from the PTT domain. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Thermal,mechanical, and morphological characterization studies of poly(2,6‐dimethyl‐1,4‐phenylene oxide) blends with polystyrene and brominated polystyrene

The miscibility of the binary and ternary blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide), brominated polystyrene, and polystyrene was investigated using a differential scanning calorimeter. The morphology of these blends was characterized by scanning electron microscopy. These studies revealed a close relation between the blend structure and its mechanical properties. The compatibilizing effect of poly(2,6‐dimethyl‐1,4‐phenylene oxide) on the miscibility of the polystyrene/brominated polystyrene blends was examined. It was found that poly(2,6‐dimethyl‐1,4‐phenylene oxide), which was miscible with polystyrene and partially miscible with brominated polystyrene, compatibilizes these two immiscible polymers if its contention exceeds 33 wt %. Upon the addition of poly(2,6‐dimethyl‐1,4‐phenylene oxide) to the immiscible blends of polystyrene/brominated polystyrene, we observed a change in the morphology of the mixtures. An improvement in the mechanical properties was noticed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 225–231, 2000     

Effect of a small amount of poly(3‐hydroxybutyrate) on the crystallization behavior of poly(l‐lactic acid) in their immiscible and miscible blends during physical aging

The miscibility and effect of physical aging on the crystallization behavior of poly(l ‐lactic acid) (PLLA)/poly(3‐hydroxybutyrate) (PHB) blends with a small amount of PHB (≤10 wt%) have been investigated using differential scanning calorimetry and Fourier transform infrared spectroscopy. It is found that the miscibility of PLLA/PHB blends with a very small percentage of PHB can be modulated by varying the molecular weight of the PHB. That is, a PLLA/PHB blend with low‐molecular‐weight PHB is miscible, whereas that with high‐molecular‐weight PHB is immiscible. It is found that physical aging at temperatures far below the glass transition temperature can promote the cold crystallization kinetics of PLLA in PLLA/PHB blends with high‐molecular‐weight PHB rather than in those with low‐molecular‐weight PHB. These findings suggest that the effect of physical aging on the crystallization behavior of the main component in a crystalline/crystalline blend with a small percentage of the second component is strongly dependent on the miscibility of the blend system. Enhanced chain mobility of PLLA in the interface region of PLLA matrix and PHB micro‐domains is proposed to explain the physical aging‐enhanced crystallization rate in immiscible PLLA/PHB blends with high‐molecular‐weight PHB. © 2013 Society of Chemical Industry     

Phase behavior of blends of poly(vinyl chloride) with an α-methyl styrene/acrylonitrile copolymer

Poly(vinyl chloride), PVC, is shown to be miscible with an α-methyl styrene/acrylonitrile copolymer, αMSAN, containing 30 percent AN by weight using differential scanning calorimetry for blends prepared by several methods. Melt blending gave single T_g mixtures; whereas, solution techniques gave results that depended on the solvent choice and the manner in which it was removed. These blends do not phase separate on heating prior to significant PVC decomposition (～250°C) in contrast to PVC/SAN blends which have much lower cloud points. Repulsion between α-methyl styrene and acrylonitrile units in the copolymer is the principal cause for miscibility of this system as shown by an analysis based on a binary interaction model using calorimetry data for low molecular weight liquid analog compounds.     

Miscibility,thermal behaviour,morphology and mechanical properties of binary blends of poly[(R)‐3‐hydroxybutyrate] with poly(γ‐benzyl‐L‐glutamate)+

The miscibility, thermal behaviour, morphology and mechanical properties of poly[(R)‐3‐hydroxybutyrate] (PHB) with poly(γ‐benzyl‐L ‐glutamate) (PBLG) are investigated by means of differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile tests. The DSC results show that PHB and PBLG are immiscible in the melt state. Such immiscibility also exists in the amorphous state due to a clear two‐phase separated structure observed by SEM measurements. The blend samples with different thermal history, namely as original and melt samples separately, display differences in thermal behaviour such as the DSC scan profile, the crystallinity and the melting temperature of PHB. The crystallization of PHB both from the molten state and the amorphous state is retarded on addition of the second component. The SEM measurements reveal that a phase inversion occurs between the PHB/PBLG (60/40) and PHB/PBLG (40/60) blends. Except for the PHB/PBLG (40/60) blend, a microphase separated structure is observed for all blend compositions. The mechanical properties vary considerably with blend composition. Compared with pure components, the PHB/PBLG (20/80) blend shows a certain improvement in mechanical properties. © 2001 Society of Chemical Industry     

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     

PVC/α-MSAN共混物的性能研究

采用机械共混法制备了PVC与α-甲基苯乙烯类-丙烯腈共聚物(α-MSAN)共混材料,探讨了α-MSAN用量对共混材料的力学性能、耐热性能和加工性能的影响。结果表明:α-MSAN可以改善共混材料的耐热性能和加工性能;随着α-MSAN用量的增多,共混材料的热变形温度(最大弯曲正应力分别为1.80 MPa和0.45MPa)、拉伸强度、弯曲强度、弯曲模量和熔体流动速率上升,而冲击强度、断裂伸长率下降。综合考虑性能与成本等因素,α-MSAN用量为30份最佳,此时,共混材料的热变形温度由72.4℃提高至81.6℃(最大弯曲正应力为1.80 MPa)。     

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     

Miscibility of segmented polyurethane/poly(vinyl chloride) blends

Miscibilities of segmented polyurethanes (SPUs) and poly(vinyl chloride) (PVC) or functionalized poly(vinyl chloride) (FPVC) were studied with dynamic mechanical analysis, differential scanning calorimetry, and X‐ray diffraction. Mechanical properties of the blends were also studied with tensile measurements. The miscibility of the blends depended greatly on the hard‐segment content of SPU and the existence of the functional groups. The combination of SPU with a low hard‐segment content and PVC with functional groups made the blend system miscible. Moreover, controlling the blend composition of SPU/FPVC allowed us to modify the mechanical properties of SPU, where the elongation at break was multiplied without a significant change in its tensile strength. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3022–3029, 2001     

Miscibility of poly(α-methyl siyrene-co-acrylonitrile) with polyacrylates and polymethacrylates

A copolymer formed from 30 percent acrylonitrile and 70 percent α methyl styrene by weight, or αMSAN, has been examined for miscibility in blends with various polyacrylates and polymethacrylates. None of the polyacrylates or poly(vinyl acetate) were miscible with α-MSAN at room temperature or above. The methyl and ethyl esters of the polymethacrylate series (PMMA, PEMA) proved to be miscible with α MSAN, but none of the higher homologues were miscible under these conditions. Blends of both PMMA and PEMA with α MSAN exhibited lower critical solution temperatures. The observed cloud points decreased as PMMA molecular weight increased up to 10⁵ where kinetic effects caused an apparent reversal of this trend. Atactic PMMA interacts more strongly with αMSAN than does either isotactic PMMA or atactic PEMA. These structural effects are compared with similar trends found in other systems.     

PP-g-（DMC-co-St）增容PP／PVC共混体系的研究

利用合成的多单体接枝物[PP-g-（DMC-co-St）]增容PP／PVC共混体系,研究了其用量对共混物力学性能以及流变性能的影响,并通过扫描电镜（SEM）分析了共混物的亚微观相结构。结果表明：①在试验条件下,共混物熔体具有典型的假塑性流体特征,在PP-g-（DMC-co-St）用量为6份时,熔体的表观黏流活化能和非牛顿指数最大;②PP-g-（DMC-co-St）对PP／PVC共混体系有较好的增容效果,增容后在PP-g-（DMC-co-St）用量为6份时,试样的拉伸强度、缺口冲击强度出现最大值,与扫描电镜照片的分析结果一致。     

Blends of SBS triblock copolymer with poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polystyrene mixture

Blends of styrene–butadiene–styrene (SBS) or styrene–ethylene/1‐butene–styrene (SEBS) triblock copolymers with a commercial mixture of polystyrene (PS) and poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) were prepared in the melt at different temperatures according to the chemical kind of the copolymer. Although solution‐cast SBS/PPO and SBS/PS blends were already known in the literature, a general and systematic study of the miscibility of the PS/PPO blend with a styrene‐based triblock copolymer in the melt was still missing. The thermal and mechanical behavior of SBS/(PPO/PS) blends was investigated by means of DSC and dynamic thermomechanical analysis (DMTA). The results were then compared to analogous SEBS/(PPO/PS) blends, for which the presence of a saturated olefinic block allowed processing at higher temperatures (220°C instead of 180°C). All the blends were further characterized by SEM and TGA to tentatively relate the observed properties with the blends' morphology and degradation temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2698–2705, 2003     

Morphological,thermal, and mechanical properties of poly(vinyl chloride)/acrylonitrile butadiene rubber blend using CuSO4·5H2O as cross‐linking agent

Novel rigid poly(vinyl chloride) (PVC)/cross‐linked acrylonitrile butadiene rubber (NBR) blend using copper (II) sulfate pentahydrate (CuSO₄·5H₂O) as cross‐linking agent was prepared by melt mixing. Fourier transform infrared analysis showed that the coordination cross‐linking occurred between NBR and CuSO₄·5H₂O in the PVC matrix, in which a novel morphology was first observed by scanning electron microscopy analysis. The thermal stability and degradation behavior of the PVC/NBR/CuSO₄·5H₂O blend were examined by means of dynamic mechanical thermal analysis and thermogravimetric analysis. It was found that the glass‐transition temperature (T_g) of the PVC/NBR/CuSO₄·5H₂O blend was enhanced by adding the coordination cross‐linked NBR into the PVC matrix. In spite of the onset decomposition temperature and the first rapidest decomposition temperature of the resultant blends reduced in comparison to neat PVC, the second rapidest decomposition temperature and the residues of the resultant blends were significantly enhanced. In addition, the thermal degradation kinetics and mechanical properties of the resultant blends were also investigated. POLYM. ENG. SCI., 54:1864–1870, 2014. © 2013 Society of Plastics Engineers     

Melt‐state miscibility of poly(ethylene‐co‐1‐octene) and linear polyethylene

On purpose to examine the effect of branch length on the miscibility of polyolefin blends, miscibility behavior of linear polyethylene/poly(ethylene‐co‐1‐octene) blend was studied and compared to that of linear polyethylene/poly(ethylene‐co‐1‐butene) blend. Miscibility of the blend was determined by observing the morphology quenched from the melt, and by using the relation between interaction parameter and copolymer composition. When the weight composition and molecular weight was the same, poly(ethylene‐co‐1‐octene) was slightly more miscible with linear polyethylene than poly(ethylene‐co‐1‐butene) was. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008