Investigation of phase morphology,thermal behavior,and impact properties of polyamide-1010/polystyrene blends compatibilized by lightly sulfonated polystyrene ionomers

The phase morphology, thermal behavior, and impact properties of polyamide-1010 (PA)/polystyrene (PS) blends compatibilized by sulfonated polystyrene (HSPS) and their zinc salts (ZnSPS) were investigated, using a dynamic mechanical analyzer (DMA), a scanning electron microscope (SEM), a differential scanning calorimetry (DSC), and a pendulum impact tester. It was found that the addition of the ionomer had an improved effect on the phase morphology of the resulting blends, where the HSPS was a more effective compatibilizer than was the ZnSPS due to its low melt viscosity and less self-agglomeration in the PA matrix. DSC results showed that with increasing the ionomer content the amount of the less perfect crystals of PA increased in these blends and, hence, led to a small increase in the crystallinity of the PA phase. The crystallization rate of the PA in the resulting blends was accelerated slightly by the ZnSPS but was decreased by the HSPS, which was probably due to the nucleation effect of ZnSPS for PA but no nucleation of HSPS. The best improvement in the notched impact strength of the blends was achieved with the content of the ionomer up to 20 wt % based on the amount of PS. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 61–69, 1998     

羧化聚苯乙烯增容PA1010/PS共混体系的形态及相容性研究

采用扫描电镜、动态粘弹谱和偏光显微镜等方法研究了羧化度的摩尔分数为３．２％时羧化聚苯然增容ＰＡ１０１０／ＰＳ共混体系的形态及相容性。结果表明,在ＰＡ１０１０／ＰＳ体系中ＣＰＳ的加入能有效地改善体系的相容性,这表现在加入ＣＰＳ后分散相与基体间的界面变得模糊。     

Co-continuous and encapsulated three phase morphologies in uncompatibilized and reactively compatibilized polyamide 6/polypropylene/polystyrene ternary blends using two reactive precursors

Phase morphology development in ternary uncompatibilized and reactively compatibilized blends based on polyamide 6 (PA6), polypropylene (PP) and polystyrene (PS) has been investigated. Reactive compatibilization of the blends has been performed using two reactive precursors; maleic anhydride grafted polypropylene (PP-g-MA) and styrene maleic anhydride copolymer (SMA) for PA6/PP and PA6/PS pairs, respectively. For comparison purposes, uncompatibilized and reactively compatibilized PA6/PP and PA6/PS binary blends, were first investigated. All the blends were melt-blended using a co-rotating twin-screw extruder. The phase morphology investigated using scanning electron microscope (SEM) and selective solvent extraction tests revealed that PA6/PP/PS blends having a weight percent composition of 70/15/15 is constituted from polyamide 6 matrix in which are dispersed composite droplets of PP core encapsulated by PS phase. Whereas, a co-continuous three-phase morphology was formed in the blends having a composition of 40/30/30. This morphology has been significantly affected by the reactive compatibilization. In the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends, PA6 phase was no more continuous but gets finely dispersed in the PS continuous phase. The DSC measurements confirmed the dispersed character of the PA6 phase. Indeed, in the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends where the PA6 particle size was smaller than 1 μm, the bulk crystallization temperature of PA6 (188 °C) was completely suppressed and a new crystallization peak emerges at a lower temperature of 93 °C as a result of homogeneous nucleation of PA6.     

Blends of polyamide1010 with unmodified and maleic‐anhydride‐grafted high‐impact polystyrene

The crystallization behaviors, dynamic mechanical properties, tensile, and morphology features of polyamide1010 (PA1010) blends with the high‐impact polystyrene (HIPS) were examined at a wide composition range. Both unmodified and maleic‐anhydride‐(MA)‐grafted HIPS (HIPS‐g‐MA) were used. It was found that the domain size of HIPS‐g‐MA was much smaller than that of HIPS at the same compositions in the blends. The mechanical performances of PA1010–HIPS‐g‐MA blends were enhanced much more than that of PA1010–HIPS blends. The crystallization temperature of PA1010 shifted towards higher temperature as HIPS‐g‐MA increased from 20 to 50% in the blends. For the blends with a dispersed PA phase (≤35 wt %), the T_c of PA1010 shifted towards lower temperature, from 178 to 83°C. An additional transition was detected at a temperature located between the T_g's of PA1010 and PS. It was associated with the interphase relaxation peak. Its intensity increased with increasing content of PA1010, and the maximum occurred at the composition of PA1010–HIPS‐g‐MA 80/20. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 857–865, 1999     

Effects of maleated styrene–(ethylene‐co‐butene)–styrene on the morphology and mechanical and thermal properties of polystyrene/polyamide 1212 blends

Polystyrene (PS)/polyamide 1212 (PA 1212) blends were compatibilized with a maleated triblock copolymer of styrene–(ethylene‐co‐butene)–styrene (SEBS‐g‐MA). Scanning electron microscopy revealed that the addition of SEBS‐g‐MA was beneficial to the dispersion of PA 1212 in the PS matrix because of the reaction between them. The variation of the fraction of SEBS‐g‐MA in the blends allowed the manipulation of the phase structure, which first formed a sheetlike structure and then formed a cocontinuous phase containing PA 1212/SEBS‐g‐MA core–shell morphologies. As a result, the mechanical properties, especially the Charpy notched impact resistance, were significantly improved with the addition of SEBS‐g‐MA. Differential scanning calorimetry (DSC) data indicated that the strong interaction between SEBS‐g‐MA and PA 1212 in the blends retarded the crystallization of PA 1212. The heat distortion temperature of the compatibilized blends was improved in comparison with that of the unmodified blend, probably because of the apparent increase in the glass‐transition temperature with an increasing concentration of SEBS‐g‐MA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1354–1360, 2005     

Effect of styrene–isoprene–styrene,styrene–butadiene–styrene,and styrene–butadiene–rubber on the mechanical,thermal, rheological,and morphological properties of polypropylene/polystyrene blends

The mechanical, thermal, rheological, and morphological properties of polypropylene (PP)/polystyrene (PS) blends compatibilized with styrene–isoprene–styrene (SIS), styrene–butadiene–styrene (SBS), and styrene–butadiene–rubber (SBR) were studied. The incompatible PP and PS phases were effectively dispersed by the addition of SIS, SBS, and SBR as compatibilizers. The PP/PS blends were mechanically evaluated in terms of the impact strength, ductility, and tensile yield stress to determine the influence of the compatibilizers on the performance properties of these materials. SIS‐ and SBS‐compatibilized blends showed significantly improved impact strength and ductility in comparison with SBR‐compatibilized blends over the entire range of compatibilizer concentrations. Differential scanning calorimetry indicated compatibility between the components upon the addition of SIS, SBS, and SBR by the appearance of shifts in the melt peak of PP toward the melting range of PS. The melt viscosity and storage modulus of the blends depended on the composition, type, and amount of compatibilizer. Scanning electron microscopy images confirmed the compatibility between the PP and PS components in the presence of SIS, SBS, and SBR by showing finer phase domains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 266–277, 2003     

Compatibilization of polypropylene/polystyrene blends with poly(styrene-b-butadiene-b-styrene) block copolymer

The compatibilizing effect of the triblock copolymer poly(styrene-b-butadiene-b-styrene) (SBS) on the morphology and mechanical properties of immiscible polypropylene/polystyrene (PP/PS) blends were studied. Blends with three different weight ratios of PP and PS were prepared and three different concentrations of SBS were used for investigations of its compatibilizing effects. Scanning electron microscopy (SEM) showed that SBS reduced the diameter of the PS-dispersed particles as well as improved the adhesion between the matrix and the dispersed phase. Transmission electron microscopy (TEM) revealed that in the PP matrix dispersed particles were complex “honeycomblike” aggregates of PS particles enveloped and joined together with the SBS compatibilizer. Wide-angle X-ray diffraction (WAXD) analysis showed that the degree of crystallinity of PP/PS/SBS slightly exceeded the values given by the addition rule. At the same time, addition of SBS to pure PP and to PP/PS blends changed the orientation parameters A₁₁₀ and C significantly, indicating an obvious SBS influence on the crystallization process in the PP matrix. SBS interactions with PP and PS influenced the mechanical properties of the compatibilized PP/PS/SBS blends. Addition of SBS decreased the yield stress and the Young's modulus and improved the elongation at yield as well as the notched impact strength in comparison to the binary PP/PS blends. Some theoretical models for the determination of the Young's modulus of binary PP/PS blends were used for comparison with the experimental results. The experimental line was closest to the series model line. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2625–2639, 1998     

Rheological and mechanical properties of compatibilized polystyrene/ethylene vinyl acetate blends

In this study, a blend of polystyrene (PS)/ethylene vinyl acetate (EVA) (PS/EVA, 90 : 10 wt %) was compatibilized with three different block copolymers, in which their end blocks were compatible with either styrene or EVA. The compatibilized blends with different compositions were prepared using a twin‐screw extruder and injection molded into the required test specimens. Mechanical properties of the blends, such as tensile properties and Charpy impact strength, morphology of tensile fractured surfaces, rheological properties, and thermal properties, were investigated. The results show that the interaction between the dispersed and continuous phase can be improved by the addition of a compatibilizer. Appreciable improvement in the impact strength of the blend with 15 wt % of compatibilizer C (polystyrene‐block‐polybutadiene) was observed. Its mechanical properties are comparable to those of the commercial high‐impact polystyrene, STYRON 470. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2071–2082, 2004     

Effects of maleated syndiotactic polystyrene on the morphology,mechanical properties,and crystallization behavior of syndiotactic polystyrene/polyamide 6 blends

The compatibilization of syndiotactic polystyrene (sPS)/polyamide 6 (PA‐6) blends with maleic anhydride grafted syndiotactic polystyrene (sPS‐g‐MA) as a reactive compatibilizer was investigated. The sPS/PA‐6 blends were in situ compatibilized by a reaction between the maleic anhydride (MA) of sPS‐g‐MA and the amine end group of PA‐6. The occurrence of the chemical reaction was substantiated by the disappearance of a characteristic MA peak from the Fourier transform infrared spectrum. Morphology observations showed that the size of the dispersed PA‐6 domains was significantly reduced and that the interfacial adhesion was much improved by the addition of sPS‐g‐MA. As a result of reactive compatibilization, the impact strengths of the sPS/PA‐6 blends increased with an increase in the sPS‐g‐MA content. The crystallization behaviors of the blends were affected by the compatibilization effect of sPS‐g‐MA. A single melting peak of sPS in the noncompatibilized blend was gradually split into two peaks as the amount of the compatibilizer increased. A single crystallization peak of PA‐6 in the noncompatibilized blend became two peaks with the addition of 3 wt % sPS‐g‐MA. The new peak was a result of the fractionation crystallization. As the amount of sPS‐g‐MA increased, the intensity of the new peak increased, and the original peak nearly disappeared. Finally, the crystallization peak of PA‐6 disappeared with 20 wt % sPS‐g‐MA in the blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2502–2506, 2003     

Stress‐relaxation behavior of natural rubber/polystyrene and natural rubber/polystyrene/natural rubber‐graft‐polystyrene blends

We studied the stress‐relaxation behavior of natural rubber (NR)/polystyrene (PS) blends in tension. The effects of strain level, composition, compatibilizer loading, and aging on the stress‐relaxation behavior were investigated in detail. The dispersed/matrix phase morphology always showed a two‐stage mechanism. On the other hand, the cocontinuos morphology showed a single‐stage mechanism. The addition of a compatibilizer (NR‐g‐PS) into 50/50 blends changed the blend morphology to a matrix/dispersed phase structure. As a result, a two‐step relaxation mechanism was found in the compatibilized blends. A three‐stage mechanism was observed at very high loadings of the compatibilizer (above the critical micelle concentration), where the compatibilizer formed micelles in the continuous phase. The aged samples showed a two‐stage relaxation mechanism. The rate of relaxation increased with strain levels. The aging produced interesting effects on the relaxation pattern. The rate of relaxation increased with temperature due to the degradation of the samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

用氯化钠－ 无水三氯化铝协同增容聚苯乙烯/三元乙丙橡胶共混物

在熔融状态下利用Friedel － Crafts 烷基化反应原位增容聚苯乙烯( PS) /三元乙丙橡胶( EPDM) 共混物,研究了不同的催化体系对PS /EPDM 共混物性能及动态流变行为的影响。结果表明,加入助催化剂氯化钠的催化体系有利于强化PS 与EPDM 间的接枝反应,同时降低EPDM 的交联反应,提高了PS /EPDM 共混物的力学性能; 动态力学分析结果表明加入助催化剂后PS /EPDM 共混物的储能模量和PS 的玻璃化转变温度均降低; 动态流变行为显示,在低频率区域,加入了助催化剂的共混物其动态储能模量、损耗模量和复数黏度均高于加入普通催化体系者,损耗因子低于普通催化体系; 从扫描电镜照片可以看出,加入助催化剂共混物的两相结合紧密,脆断面的橡胶粒子剥离空洞减少,相容性提高。     

离聚体增容PA1010／SBS共混物的研究

采用磺化丁基胶锌盐(ZnSIIR)离聚体作为PA1010/SBS共混物的增容剂,研究了共混体系的结构、形态、相容性及对材料冲击性能的影响。结果表明,ZnSIIR的加入有效改善了SBS在PA1010中的相容性;对PA1010结晶起成核作用,并加快其结晶速率;共混物缺口冲击强度得到提高,且在PA1010/SBS为90/10、ZnSIIR为SBS的10％左右时效果较佳。     

Phase morphologies and mechanical properties of high‐impact polystyrene (HIPS) and polycarbonate blends compatibilized with polystyrene and polyarylate block copolymer

Phasemorphology and mechanical properties of blends of high‐impact polystyrene (HIPS) and polycarbonate (PC) blends compatibilized with a polystyrene (PS) and polyarylate (PAr) (PS–PAr) block copolymer were investigated. Over a broad range of composition from 50/50 through 30/70, HIPS/PC blends formed cocontinuous structures induced by the flow during the extrusion or injection‐molding processes. These cocontinuous phases had heterogeneity between the parallel and perpendicular directions to the flow. The micromorphology in the parallel direction to the flow consisted of stringlike phases, which were highly elongated along the flow. Their longitudinal size was long enough to be longer than 180 μm, while their lateral size was shorter than 5 μm, whereas that in the perpendicular direction to the flow showed a cocontinuous phase with regular spacing due to interconnection or blanching among the stringlike phases. The PS–PAr block copolymer was found to successfully compatibilize the HIPS/PC blends. The lateral size of the stringlike phases could be controlled both by the amount of the PS–PAr block copolymer added and by the shear rate during the extrusion or injection‐molding process without changing their longitudinal size. The HIPS/PC blend compatibilized with 3 wt % of the PS–PAr block copolymer under an average shear rate of 675 s^?1 showed a stringlike phase whose lateral size was reduced almost equal to the rubber particle size in HIPS. The tensile modulus and yield stress of the HIPS/PC blends could be explained by the addition rule of each component, while the elongation at break was almost equal to that of PC. These mechanical properties of the HIPS/PC blends can be explained by a parallel connection model independent of the HIPS and PC phases. On the other hand, the toughness factor of the HIPS/PC blends strongly depended on the lateral size of the stringlike phases and the rubber particle size in the HIPS. It was found that the size of the string phases and the rubber particle should be smaller than 1.0 μm to attain a reasonable energy absorbency by blending HIPS and PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2347–2360, 2001     

Compatibilization and morphology development of immiscible ternary polymer blends

We report a novel and effective strategy that compatibilizes three immiscible polymers, polyolefins, styrene polymers, and engineering plastics, achieved by using a polyolefin-based multi-phase compatibilizer. Compatibilizing effect and morphology development are investigated in a model ternary immiscible polymer blends consisting of polypropylene (PP)/polystyrene(PS)/polyamide(PA6) and a multi-phase compatibilizer (PP-g-(MAH-co-St) as prepared by maleic anhydride (MAH) and styrene (St) dual monomers melt grafting PP. Scanning electron microscopy (SEM) results indicate that, as a multi-phase compatibilizer, PP-g-(MAH-co-St) shows effective compatibilization in the PP/PS/PA6 blends. The particle size of both PS and PA6 is greatly decreased due to the addition of multi-phase compatibilizer, while the interfacial adhesion in immiscible pairs is increased. This good compatibilizing effect is promising for developing a new, technologically attractive method for achieving compatibilization of immiscible multi-component polymer blends as well as for recycling and reusing of such blends. For phase morphology development, the morphology of PP/PS/PA6 (70/15/15) uncompatibilized blend reveals that the blend is constituted from PP matrix in which are dispersed composite droplets of PA6 core encapsulated by PS phase. Whereas, the compatibilized blend shows the three components strongly interact with each other, i.e. multi-phase compatibilizer has good compatibilization between the various immiscible pairs. For the 40/30/30 blend, the morphology changed from a three-phase co-continuous morphology (uncompatibilized) to the dispersed droplets of PA6 and PS in the PP matrix (compatibilized).     

Compatibilization of styrene–butadiene–styrene block copolymer in polypropylene/polystyrene blends by analysis of phase morphology

Effect of compatibilization of styrene–butadiene–styrene (SBS) block copolymer in polypropylene/polystyrene (PP/PS) blends was studied by means of small angle X‐ray scattering (SAXS) and scanning electron microscope (SEM). According to SAXS, a certain amount of SBS was located at the interface in all the analyzed samples, forming the relatively thicker interface layer penetrating into homopolymers, and the thickness of the interface layer was quantified in terms of Porod light scattering theory. The incorporation of SBS into PP/PS blends resulted in a decrease in domain size following an emulsification curve as well as an uniform size distribution, and consequently, a fine dispersion of PP domains in the PS matrix. This effect was more pronounced when the concentration of SBS was higher. A critical concentration of SBS of 15% above which the interface layer approaches to saturation and domain size attains a steady‐state was observed. Further, the morphology fluctuation of unetched fracture surface of umcompatibilized and compatibilized blends was analyzed using an integral constant Q based on Debye‐Bueche light scattering theories. Variation of Q as a function of the concentration of SBS showed that, due to the penetrating interface layer, adhesion between phases was improved, making it possible for applied stress to transfer between phases and leading to more uniform stress distribution when blends were broken; accordingly, a more complicated morphology fluctuation of fracture surface appeared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:365–370, 2007     

Effect of compatibilization on the properties of HIPS/PA1010 blends

Blends consisting of high‐impact polystyrene (HIPS) as the matrix and polyamide 1010 (PA1010) as the dispersed phase were prepared by mixing. The grafting copolymers of HIPS and maleic anhydride (MA), the compatibilizer precursors of the blends, were synthesized. The contents of the MA in the grafting copolymers are 4.7 wt % and 1.6 wt %, and were assigned as HAM and LMA, respectively. Different blend morphologies were observed by scanning electron microscopy (SEM); the domain size of the PA1010 dispersed phase in the HIPS matrix of compatibilized blends decreased comparing with that of uncompatibilized blends. For the blend with 25 wt % HIPS‐g‐MA component, the T_c of PA1010 shifts towards lower temperature, from 178 to 83°C. It is found that HIPS‐g‐MA used as the third component has profound effect on the mechanical properties of the resulting blends. This behavior has been attributed to the chemical reaction taking place in situ during the mixing between the two components of PA1010 and HIPS‐g‐MA. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 799–806, 2000     

PP-g-GMA的制备及其增容PP/PA6共混物的性能

通过熔融接枝反应制备了甲基丙烯酸缩水甘油酯接枝聚丙烯（PP-g-GMA）,并将其作为聚丙烯/聚酰胺6（PP/PA6）共混物的相容剂,研究了PP-g-GMA对PP/PA6共混物的力学性能及形态结构的影响。结果表明,采用滴定法测得PP-g-GMA接枝率为3.35 %;当PP-g-GMA的添加量为4 %（质量分数,下同）和8 %时,PP/PA6/PP-g-GMA共混物的拉伸强度和缺口冲击强度分别较PP/PA6共混物提高了32.4 %和60.4 %;PP-g-GMA显著改善了PP/PA6 共混物的界面相容性,是PP/PA6共混物的有效增容剂。     

Investigation on particular phase morphology of immiscible polyamide 12 and polystyrene blends prepared via anionic ring‐opening polymerization

In this article, the particular phase morphology of immiscible polyamide 12/polystyrene (PA12/PS) blends prepared via in situ anionic ring‐opening polymerization of laurolactam (LL) in the presence of polystyrene (PS) was investigated. Scanning electron microscopy (SEM) and Fourier Transform infrared Spectroscopy (FTIR) were used to analyze the morphology of the blends. The results show that the PS is dispersed as small droplets in the continuous matrix of PA12 when PS content is 5 wt%. However, when the PS content is higher than 10 wt%, two particular phase morphologies appeared. Firstly, dispersed PS‐rich particles with the spherical inclusions of PA12 can be found when PS content is between 10 and 15 wt%. Then the phase inversion occurred (the phase morphology of the PA12/PS blends changed from the PS dispersed/PA12 matrix to PA12 dispersed/PS matrix system) when PS content is 20 wt% or higher, which is unusual for polymer blends prepared via conventional methods such as mixing, hydrolytic polycondensation and so on. The formation of this particular phase morphology development was simply elucidated via a phase inversion mechanism. Furthermore, the stability of the phase morphology of the PA12/PS blends after annealing at 230°C was also investigated via SEM. POLYM. ENG. SCI., 52:1831–1838, 2012. © 2012 Society of Plastics Engineers     

Reactive compatibilization of polystyrene/poly(ethylene–co–vinyl acetate) (EVA) blends

A reactive compatibilizer, mercapto‐functionalized EVA (EVASH), in combination with styrene‐butadiene block copolymer (SBS), was used to compatibilize the blends of polystyrene (PS) and ethylene–vinyl acetate copolymer (EVA). The reactive compatibilization was confirmed by the presence of insoluble material and from dynamic‐mechanical analysis. In addition to a more uniform morphology with small phase size, the compatibilization also provided excellent stabilization of the morphology, with an almost complete suppression of coarsening during annealing. As a consequence, a substantial increase on the elongation at break without significant influence on ultimate tensile strength was achieved for compatibilized blends with different compositions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 14–22, 2006     

Influences of component ratio of minor phases and charge sequence on the morphology and mechanical properties of PP/PS/PA6 ternary blends

In this study, influences of both component ratio of minor phases and charge sequence on the morphology and mechanical performance in typical ternary blends, polypropylene (PP)/polystyrene (PS)/polyamide-6 (PA6), have been studied. Reactive compatibilization of the blends has been carried out using multi-monomer melt grafted PP with anhydride groups and styrene segments. For uncompatibilized blends, scanning electron microscope (SEM) and selective solvent extraction showed that the blends presented a core–shell morphology with PS as shell and PA6 as core in the PP matrix, in spite of the component ratio and charge sequence. The shell thickened and droplet size decreased with increasing the PS/PA6 component ratio. While for compatibilized blends, the addition of compatibilizers resulted in a significant reduction of the dispersed droplet size and the phase structure of the dispersed phases was greatly dependent on the charge sequence. When the blending of PA6, g-PP, and PP are preceded, the encapsulation structure reversed into the structure of PS phase encapsulated by PA6 phase, which led to better tensile and flexural strength of the blends.