Toughening of recycled polystyrene used for TV backset

The recycled polystyrene (rPS) was toughened with ethylene‐octylene copolymer thermoplastic elastomer (POE) and high‐density polyethylene (HDPE) with various melt flow index (MFI), compatibilized by styrene‐butadiene‐styrene copolymer (SBS) to enhance the toughness of rPS for use as TV backset. The rPS/POE binary blends exhibited an increased impact strength with 5–10 wt % POE content followed by a decrease with the POE content up to 20 wt %, which could be due to poor compatibility between POE and rPS. For rPS/POE/SBS ternary blends with 20 wt % of POE content, the impact strength increased dramatically and a sharp brittle‐ductile transition was observed as the SBS content was around 3–5 wt %. Rheological study indicated a possible formation of network structure by adding of SBS, which could be a new mechanism for rPS toughening. In rPS/POE/HDPE/SBS (70/20/5/5) quaternary blends, a fibril‐like structure was observed as the molecular weight of HDPE was higher (with lower MFI). The presence of HDPE fibers in the blends could not enhance the network structure, but could stop the crack propagation during fracture process, resulting in a further increase of the toughness. The prepared quaternary blend showed an impact strength of 9.3 kJ/m² and a tensile strength of 25 MPa, which can be well used for TV backset to substitute HIPS because this system is economical and environmental friendly. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The influence of matrix viscosity and composition on the morphology,rheology, and mechanical properties of thermoplastic elastomer nanocomposites based on EPDM/PP

The morphological and rheological properties of thermoplastic elastomer nanocomposites (TPE nanocomposites) were studied using different viscosities of polypropylene (PP) and ethylene‐propylene‐diene monomer (EPDM) rubber content (20, 40, 60 wt%). The components, namely EPDM, PP, Cloisite 15A, and maleic anhydride‐modified PP as compatibilizer, were compounded by a one‐step melt mixing process in a laboratory internal mixer. The structure of the nanocomposites was characterized with X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and rheometry in small amplitude oscillatory shear. The distribution state of the clay between the two phases (PP and EPDM) was found to be dependent on the viscosity ratio of PP to EPDM. In the nanocomposites prepared based on low viscosity PP (LVP) and EPDM, the clay was mostly dispersed into the PP phase and the size of the dispersed rubber particles decreased in comparison with unfilled but otherwise similar blends. However, the dispersed elastomer droplet size in the high viscosity PP (HVP) blends containing 40 and 60% EPDM increased with the introduction of the clay. For TPE nanocomposites, the dependence of the storage modulus (G′) on angular frequency (ω) followed a clear nonterminal behavior. The increase in the storage modulus and the decrease in the terminal zone slope of the elastic modulus curve were found to be larger in the LVP nanocomposite in comparison with the HVP sample. The yield stress of nanoclay‐filled blends prepared with LVP increased more than that of HVP samples. The tensile modulus improved for all nanocomposites but a higher percentage of increase was observed in the case of LVP samples. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Evolution of rheological properties and morphology development during crosslinking of polyolefin elastomers and their TPV blends with polypropylene

This work investigates the evolution of the rheological properties of elastomeric dynamically vulcanized ethylene‐α‐olefin copolymers (ECs) and their blends with polypropylene (PP), during peroxide initiated crosslinking. Rheological techniques are used in conjunction with gel content measurements to determine the onset of gelation during static crosslinking. The complex viscosity and moduli follow power‐law dependence with respect to frequency at the gel point. The relaxation exponent and corresponding values of tan δ at the gel point are determined from the complex viscosity versus frequency curves and used as criteria for the determination of the instance of gelation. The evolution of morphology of thermoplastic vulcanizate (TPV) blends consisting of EC and PP during dynamic crosslinking is discussed in the context of the evolving rheological properties of the matrix and the dispersed phase that take place upon peroxide modification. TPVs having the crosslinked EC as the matrix present a very fine morphology, whereas the blends containing crosslinked EC particles, present a coarser morphology. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Polypropylene-elastomer (TPO) nanocomposites: 1. Morphology

PP/PP-g-MA/MMT/elastomer nanocomposites were prepared in a twin-screw extruder at fixed 30 wt% elastomer and 0-7 wt% MMT content. The ratio of maleated polypropylene, PP-g-MA and organoclay was maintained at 1. Elastomer particle size and shape in the presence of MMT were evaluated for three different molecular weight grades of polypropylene (PP) and five different ethylene-co-octene elastomers (EOR) with different melt flow index (MFI) and octene contents. The MMT particles are located exclusively in the PP phase in the PP/PP-g-MA/MMT/EOR nanocomposites as seen from TEM images. Injection molded nanocomposite samples show significant decreases in elastomer particle size and increases in elastomer aspect ratio and particle density compared to as-extruded or pelletized samples. The elastomer particle size decreased significantly with increased MMT content and the molecular weight of PP. Low molecular weight PP based nanocomposite showed a greater reduction in elastomer particle size compared to medium and high molecular weight PP based nanocomposites. Elastomers having MFI in the range of 0.5-1.0 gave minimum elastomer particle sizes in the PP/PP-g-MA/MMT/EOR nanocomposite. The elastomer particles were deformed during injection molding leading to an increase in their aspect ratio. The nanocomposites containing high octene content elastomer gave smaller elastomer particle size and higher elastomer aspect ratios compared to nanocomposites containing low octene content elastomer.     

NR-g-(MAH-co-St)对纳米SiO2改性NR/PP共混型热塑性弹性体的影响

研究了马来酸酐／苯乙烯(MAH／St)多单体熔融接枝NR[NR-g-(MAH-CO-St)]对纳米SiO2改性天然橡胶／聚丙烯动态硫化共混型热塑性弹性体(NR／PPTPV)力学性能的影响；采用SEM分析了TPV的断面形貌。结果表明：纳米SiO2的质量分数为0.03时，NR-g-(MAH-CO-St)通过改善纳米SiO2分散的均匀性和细化交联NR分散相，使NR与PP两相的相容性得到明显改善，两相界面结合强度明显提高，NR／PP／纳米SiO2 TPV的力学性能提高。     

茂金属聚烯烃弹性体/聚丙烯热塑性硫化胶的制备与性能研究

采用双螺杆挤出机制备茂金属聚烯烃弹性体(POE)/聚丙烯(PP)热塑性硫化胶(TPV),考察硫化剂双25用量、助硫化剂TAIC用量和POE/PP共混比对TPV微观结构、动态力学性能、物理性能和耐热空气老化性能的影响。结果表明,硫化剂双25用量为2份、助硫化剂TAIC用量为5份、POE/PP共混比为60/40~70/30时,在保证POE/PP TPV顺利挤出的前提下,POE/PP TPV的综合性能较优。     

Rubber‐toughened polypropylene nanocomposite: Effect of polyethylene octene copolymer on mechanical properties and phase morphology

Rubber‐toughened polypropylene (PP)/org‐Montmorillonite (org‐MMT) nanocomposite with polyethylene octene (POE) copolymer were compounded in a twin‐screw extruder at 230°C and injection‐molded. The POE used had 25 wt % 1‐octene content and the weight fraction of POE in the blend was varied in the range of 0–20 wt %. X‐ray diffraction analysis (XRD) revealed that an intercalation org‐MMT silicate layer structure was formed in rubber‐toughened polypropylene nanocomposites (RTPPNC). Izod impact measurements indicated that the addition of POE led to a significant improvement in the impact strength of the RTPPNC, from 6.2 kJ/m² in untoughened PP nanocomposites to 17.8 kJ/m² in RTPPNC containing 20 wt % POE. This shows that the POE elastomer was very effective in converting brittle PP nanocomposites into tough nanocomposites. However, the Young's modulus, tensile strength, flexural modulus, and flexural strength of the blends decreased with respect to the PP nanocomposites, as the weight fraction of POE was increased to 20 wt %. Scanning electron microscopy (SEM) was used for the investigation of the phase morphology and rubber particles size. SEM study revealed a two‐phase morphology where POE, as droplets was dispersed finely and uniformly in the PP matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3441–3450, 2006     

Effects of blend composition and dynamic vulcanization on the morphology and dynamic viscoelastic properties of PP/EPDM blends

The morphology and dynamic viscoelastic properties of isotactic polypropylene (PP) blended with oil-free/oil-extended ethylene–propylene–diene (EPDM) rubbers were studied. Unvulcanized and dynamically vulcanized blends with the compositions PP/EPDM = 50/50 and = 30/70 were investigated. The morphology was observed by phase contrasted atomic force microscopy. The dynamic viscoelastic properties were determined with a rheometer of plate–plate configuration. It was shown that the rheological behavior was strongly affected by both the composition and the morphology of the blends. Significant improvement in the flowability of the dynamically vulcanized blends was observed when oil-extended EPDM was used instead of the oil-free version. It was demonstrated that the rheological properties are mostly controlled by the elastomer phase at low frequencies, while in the high-frequency range the influence of PP becomes dominant. The peculiarities in the rheological behavior of the thermoplastic elastomers (uncured blends, TPE) and thermoplastic dynamic vulcanizates (TPV, dynamically cured blends) containing oil-extended EPDMs were traced to a limited compatibility between the PP and EPDM components in the melt. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

PP/POE热塑性弹性体的动态流变性能研究

研究了聚丙烯/乙烯-辛烯共聚物(PP/POE)动态硫化热塑性弹性体的动态流变性能。结果表明:2,5-二甲基-2,5-双(过氧化叔丁基)己烷(DBPH)交联的材料弹性较好,随着过氧化物用量的增加,PP/POE体系的能量损耗减少,弹性增加。TAIC交联材料的内耗较小,加入TAIC抑制了PP的降解,并使材料的内耗减少,含量越多内耗越少。在不同比例的PP/POE体系中,较低的振动频率下POE控制材料的弹性模量,较高的振动频率下PP控制材料的弹性模量。     

轮胎胶应力诱导脱硫及其对PP热塑性弹性体力学性能的影响

在轮胎胶粉熔融挤出过程中添加不同品种的热塑性弹性体作为溶胀剂和承载流体,并通过提高挤出机螺杆转速的高剪切应力诱导方法,研究了螺杆转速和挤出反应温度对脱硫轮胎胶共混物的凝胶含量、溶胶红外吸收光谱及聚丙烯（PP）/脱硫轮胎胶共混物热塑性弹性体力学性能的影响。结果表明,以乙烯-辛烯共聚物为承载流体时,所制备的PP动态交联热塑性弹性体的性能最好;仲丁醇、多烷基苯酚二硫化物或仲丁醇与多烷基苯酚二硫化物复合使用,均能促进脱硫反应的进行,并引起脱硫共混物中凝胶含量的减少、双键结构含量的增加和PP动态交联热塑性弹性体力学性能的明显增大;在转速为1000 r/min、温度为240 ℃的脱硫条件下,PP/脱硫轮胎胶共混物热塑性弹性体的拉伸强度和断裂伸长率分别达到11.2 MPa和123.2 %。     

Phase morphology and melt rheological behavior of uncrosslinked and dynamically crosslinked polyolefin blends: role of macromolecular structure

Thermoplastic vulcanizates (TPVs) based on polypropylene (PP) with ethylene–octene copolymer (EOC) and ethylene propylene diene rubber (EPDM) have been prepared by co-agent-assisted peroxide crosslinking system. The study was pursued to explore the influence of two dissimilar polyolefin polymers having different molecular architecture on the state and mode of dispersion of the blend components and their influence on melt rheological properties. The effects of dynamic crosslinking of the PP/EOC and PP/EPDM have been compared with special reference to the concentration of crosslinking agent and ratio of blend components. Morphological analyses show that, irrespective of blend ratio, dynamic vulcanization exhibits a dispersed phase morphology with crosslinked EOC or EPDM particles in the continuous PP matrix. It was found that viscosity ratio plays a crucial role in determining the state and mode of dispersion of blend components in the uncrosslinked system. The lower viscosity and torque values of uncrosslinked and dynamically crosslinked blends of PP/EOC in the melt state indicates that they exhibit better processing characteristics when compared to corresponding PP/EPDM blends.     

Effect of filler partitioning on the mechanical properties of TPO/nanosilica composites

Nanosilica (SiO₂) is used as a reinforcing filler in PP/elastomer thermoplastic polyolefin (TPO) blends containing ethylene‐octene polyolefin elastomer (POE), ethylene‐propylene rubber (EPR), and maleated EPR. The localization and dispersion of the filler are controlled by adding maleated derivatives to the matrix or the dispersed phase. A separated morphology, consisting of SiO₂ residing in the PP matrix, is necessary to achieve improvements in modulus. Filled TPOs containing POE have the best performance and exhibit improved moduli while retaining high values of elongation. J. VINYL ADDIT. TECHNOL., 13:147–150, 2007. © 2007 Society of Plastics Engineers     

Highly transparent thermoplastic elastomer from isotactic polypropylene and styrene/ethylene‐butylene/styrene triblock copolymer: Structure‐property correlations

Polypropylene (PP) is one of the most useful general purpose plastics. However, the poor transparency and brittleness of PP restricts its applications in the field of medical and personal care where silicone and polyvinyl chloride (PVC) are presently used. This work concentrates on developing highly transparent elastomeric PP blends and also thermoplastic elastomer by blending isotactic polypropylene (I‐PP) with styrene/ethylene‐butylene/styrene (SEBS) triblock copolymer. PP/SEBS blend derived from high melt flow index (MFI) PP and high MFI SEBS exhibit remarkable transparency (haze value as low as 6%) along with good percentage of elongation and processability. The reduction in difference of refractive index (RI) between PP and SEBS has been observed by blending SEBS with PP. The wide angle X‐ray diffraction studies show that there is significant reduction in the percentage crystallinity of PP by the addition of SEBS block copolymer. Temperature‐dependent polarized light microscopy studies reveal the reduction in spherulites size by the addition of SEBS block copolymer. Transmission electron micrographs show that the SEBS polymer forms a fine lamellar structure throughout the PP matrix with phase inversion at higher SEBS concentration. Development of phase morphology, crystalline morphology, and crystallinity in different blends has been analyzed and microstructure‐haze correlations have been developed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

In situ reactive compatibilization and reinforcement of peroxide dynamically vulcanized polypropylene/ethylene‐propylene‐diene monomer tpv by zinc dimethacrylate

This work demonstrates an approach of in situ reactive compatibilization between polypropylene (PP) and ethylene‐propylene‐diene monomer (EPDM) by using ZDMA as a compatibilizer and, simultaneously, as a very strong reinforcing agent. With 7phr ZDMA in the PP/EPDM (30/70, w/w) thermoplastic vulcanizate (TPV), the tensile strength and elongation at break were increased from 5.3 MPa and 222% up to 11.2 MPa and 396%, respectively. Increasing the PP concentration further improved mechanical properties of the TPVs with ZDMA. This tremendous reinforcing as well as the compatibilization effect of the ZDMA was understood by polymerization of ZDMA and ZDMA reacting with EPDM and PP during peroxide induced dynamic vulcanization. A peculiar nano‐composite structure that the crosslinked rubber particles were “bonded” by a transition zone which containing numerous of nano‐particles with dimensions of about 20–30 nm was observed from transmission electron microscopy (TEM). Scanning electron microscopy (SEM) results showed that increase of PP/EPDM ratio reduced the size of crosslinked EPDM particles. Moreover, we found that the ZDMA reinforced EPDM particles resulted in a higher tan δ peak temperature for EPDM phase and built “filler‐filler”‐like networking in the PP melt. POLYM. COMPOS. 34:1357–1366, 2013. © 2013 Society of Plastics Engineers     

聚丙烯/聚烯烃弹性体共混物的制备与性能研究

通过熔融共混法制备了一系列聚丙烯(PP)/聚烯烃弹性体(POE)共混物,采用热重分析、示差扫描量热分析和拉伸测试对所得样品进行了热性能及力学性能的表征。结果表明,随着POE含量的增加,PP的抗拉强度和断裂伸长率均呈现先增加后减小的趋势。而当POE的含量低于5%时,样品的熔融温度明显低于纯PP的熔融温度;而当其含量超过5%时,样品的熔融温度与纯样基本一致。另外,POE的引入导致PP的热降解温度降低。     

Effect of the compatibilizer on the morphology and properties of dynamically cured PP/POE/epoxy blends

Dynamic vulcanization was successfully applied to epoxy resin reinforced polypropylene (PP)/ethylene‐octene copolymer (POE) blends, and the effects of different compatibilizers on the morphology and properties of dynamically cured PP/POE/epoxy blends were studied. The results show that dynamically cured PP/POE/epoxy blends compatibilized with maleic anhydride‐grafted polypropylene (MAH‐g‐PP) have a three‐phase structure consisting of POE and epoxy particles dispersed in the PP continuous phase, and these blends had improved tensile strength and flexural modulus. While using maleic anhydride‐grafted POE (MAH‐g‐POE) as a compatibilizer, the structure of the core‐shell complex phase and the PP continuous phase showed that epoxy particles could be embedded in MAH‐g‐POE in the blends, and gave rise to an increase in impact strength, while retaining a certain strength and modulus. DSC analysis showed that the epoxy particles in the blends compatibilized with MAH‐g‐PP were more efficient nucleating agents for PP than they were in the blends compatibilized with MAH‐g‐POE. WAXD analysis shows that compatibilization do not disturb the crystalline structure of PP in the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Compatibilization and toughening of poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 alloy with poly(ethylene 1‐octene): Mechanical properties,morphology, and rheology

Blends of a poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO)/polyamide 6 (PA 6) alloy toughened with a novel polyolefin elastomer poly(ethylene‐1‐octene) (POE) were prepared via melt extrusion. In order to improve the compatibilization between POE and the PPO/PA 6 alloy, POE was grafted with maleic anhydride (MA), which could react with the amine group of PA 6. The Izod impact strength of the blends exhibited an optimum when the extent of MA grafting of POE was changed, which is an order of magnitude higher than that of the untoughened blends. The morphology revealed that the size of the POE particles decreased with an increasing MA grafting ratio of POE. Studies on the tensile properties and rheology of the blends were also carried out. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3110–3116, 2003     

Cell coalescence suppressed by crosslinking structure in polypropylene microcellular foaming

A series of crosslinked polypropylene samples with increased melt strengths were prepared via a copolymerization reaction, followed by melt processing. These crosslinked PP samples (PP‐Cs) were foamed by a temperature rising process using supercritical CO₂ as the physical blowing agent. The introduction of crosslinking structure resulted in PP‐Cs foams with well‐defined closed cell structure, decreased cell size, and increased cell density in comparison with a linear PP, which were attributed to the suppressed cell coalescence due to the significant increase in melt strength of PP‐Cs. Further increasing the crosslinking degree tended to enhance the suppression effect on the cell coalescence, and hence increase the cell density of PP foams under the same foaming conditions, especially at the longer foaming times. The well‐defined closed cell structure was observed at the foaming temperature of 170–250°C and saturation pressure of 12–20 MPa. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Morphology and mechanical properties of impact modified polypropylene blends

Isotactic polypropylene (PP) has been reactively blended with various grades of an ethylene–octene copolymer (EOC) in a twin‐screw extruder. Free radical polymerization of styrene and a multifunctional acrylate during melt extrusion has resulted in an enhancement of mechanical properties over the binary blend. The reactive blend exhibits a notched Izod impact strength over 12 times that of pure polypropylene and greater than double the performance of the binary blend. Electron microscopy shows that by grafting onto the polymers, elastomer particle size and interparticle distance decrease, while particle shape becomes less spherical. The acrylate is crucial to achieve superior performance, as infrared spectra correlate an increase in graft yield to improvements in stress–strain behavior and impact strength. In addition, melt flow index (MFI) and melt strength data indicate a reduction in unwanted side reactions of polypropylene and the presence of long‐chain branching. Dynamic‐mechanical analysis reveals that the reaction promotes miscibility between polypropylene and the EOC and reduces molecular mobility at their glass‐transition temperatures. Mechanical properties, graft yield, and MFI are shown to be highly dependent upon the elastomer's concentration, density, and molecular weight, initiator and monomer concentration, as well as processing temperature. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Rheological behaviors of glass bead‐ and wollastonite‐filled polypropylene composites modified with thermoplastic elastomers

Steady‐ and oscillatory‐shear rheological behaviors of polypropylene/glass bead (PP/GB) and PP/wollastonite (PP/W) melts modified with thermoplastic elastomers, poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) copolymer (SEBS) and the corresponding block copolymer grafted with maleic anhydride (SEBS‐g‐MA), were examined by means of a parallel‐plate rheometer. With adding the elastomers (SEBS and SEBS‐g‐MA) and fillers (spherical GB and acicular W) to PP, viscosity especially at low shear rates and shear‐thinning flow behavior at high shear rates were pronounced as evidenced quantitatively by Carreau–Yasuda (CY) parameters, but Cox–Merz analogy became weakened. Besides, melt‐elasticity in terminal region and relaxation time (t_c) in crossing point increased, indicating an enhancement in quasi‐solid behavior of molten PP. Comparing with the elastomers, rheological behaviors of molten PP were more influenced with adding the rigid fillers, especially with W due to distinct acicular shape of W particles. SEBS‐g‐MA elastomer more affected rheological behaviors of the ternary composites than SEBS elastomer, implying that SEBS elastomer and the filler particles behaved individually (i.e., development of separate microstructure) in (PP/GB)/SEBS and (PP/W)/SEBS ternary composites, but core‐shell microstructure developed with strong interfacial adhesion by adding SEBS‐g‐MA elastomer, and the filler particles encapsulated with the thick SEBS‐g‐MA elastomer interlayer (i.e., core‐shell particles) acted like neither big elastomer particles nor like individual rigid particles in melt‐state. Moreover, effects of SEBS‐g‐MA elastomer reached a maximum on rheological behaviors of (PP/W)/SEBS‐g‐MA ternary composite, indicating a synergy between core‐shell microstructure and acicular W particles. Correlations between oscillatory‐shear flow properties and microstructures of the blends and composites were evaluated using Cole–Cole (CC), Han–Chuang (HC), and van Gurp–Palmen (vGP) plots. COMPOS., 2012. © 2012 Society of Plastics