Comparison of some butadiene-based impact modifiers for polycarbonate

The relationship of blend morphology to deformation mechanisms and notched Izod impact strength was studied with three butadiene-based impact modifiers for polycarbonate (PC). The impact modifiers were a linear polybutadiene (PB), a styrene–butadiene–styrene block copolymer (SBS), and a structured latex particle having a PB core and methyl methacrylate/styrene shell (MBS). The particle-size distribution in the blends was determined from transmission electron micrographs (TEM). Fractographic analysis combined with TEM examination of thin sections from impacted specimens provided insight into the failure mechanisms. Good impact was achieved with PC/MBS blends when cavitation of the core–shell particles relieved triaxiality and enabled the matrix to fracture by the plane stress ductile tearing mode that is characteristic of thin PC. The best impact properties were obtained with PC/SBS blends when the modifier was dispersed as aggregates of small particles. Cavitation at the weak internal boundaries relieved triaxiality, but subsequent coalescence of cavitated particles during ductile drawing of the matrix created critical size voids and the resulting secondary cracks reduced the toughness of the blend. In general, PB did not significantly enhance the impact strength of PC. © 1994 John Wiley & Sons, Inc.     

聚苯乙烯／聚乙烯共混体系的研究

讨论了不同第三组分和不同种聚乙烯对以聚苯乙烯为基质的ＰＳ／ＰＥ共混体系结构和性能的影响，发现苯乙烯－丁二烯－苯乙烯嵌段共聚物和苯乙烯－氢化丁二烯－苯乙烯嵌段共聚物作为第三组分对ＰＳ／ＰＥ共混体系均具有增容作用，用ＳＢＳ的效果比ＳＥＢＳ好，而ＳＢＳ的结构对增韧效果的影响不大。在ＳＢＳ存在下，ＬＬＤＰＥ对ＰＳ增韧效果最好，ＨＤＰＥ次之，ＬＤＰＥ最差。     

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 characterization of the core–shell latex particle by transmission electron microscopy and image analysis

To describe the morphology of the core–shell latex particle of methyl methacrylate–butadiene–styrene graft copolymer (MBS) quantitatively, we propose four parameters, that is, the diameter of the core, the shell thickness (TH), the roundness of the core, and the eccentricity (E); we calculated these parameters with geometrical parameters determined by the analysis of transmission electron microscope images. The mean values and distributions of the four parameters based on a certain amount of particles were used for quantitative characterization of MBS latex samples. With increasing monomer‐to‐polymer ratios of the graft polymerization, both the MBS TH and the numbers of homopolymer particles increased, and the core–shell morphology tended to be irregular. For the MBS latices derived from poly(styrene–butadiene) latex with a wide distribution of particle sizes, the core–shell structures of the larger particles were different from those of smaller ones to a certain extent, and both the TH and the E decreased with increasing core size. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 855–861, 2003     

Distribution of MBS emulsion particles in immiscible polystyrene/SAN blends

The effect of mixing technique and sequence on the distribution of methacrylated-butadienestyrene (MBS) emulsion particles in immiscible blends of polystyrene (PS) and a styrene/acrylonitrile copolymer (SAN) was examined using transmission electron microscopy. The shell of the emulsion particle is essentially poly(methyl methacrylate) (PMMA), which is miscible with SAN but immiscible with PS. In simple thermodynamic terms, the MBS particle should have an affinity for SAN over PS. It was found, however, that the sequence of mixing had a strong influence on the location of the MBS particles. If the PS-SAN interface is established before the addition of the MBS particles, the MBS particles are located exclusively in the SAN phase. If the MBS particles are present at the time the PS-SAN interface is formed, then the particles line up at the interface.     

Influences of compatibilization and compounding process on electrical conduction and thermal stabilities of carbon black‐filled immiscible polypropylene/polystyrene blends

The influences of styrene–butadiene–styrene (SBS) copolymer compatibilizer and compounding process on the electrical conduction and thermal stabilities of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) (1/1) blends were investigated. The immiscible CB/PP/PS composite with CB homogeneously located in the PS phase exhibited the highest resistivity and the fastest variation amplitudes of electrical resistivity (ρ) and rheological parameters upon annealing. An optimal content of 5 vol% SBS could significantly lower ρ of the composites by partially trapping CB particles in the PP/PS interfacial region and by reducing the phase size. The compatibilizer markedly slowed down the variation amplitudes of ρ and rheological parameters and the phase coalescence of the composites submitted to thermal annealing. The (SBS/CB)/PP/PS composite with CB located at the PP/PS interface and in the PP phase prepared by blending a (SBS/CB) masterbatch with PP and PS exhibited lower ρ and better thermal stability in comparison with the CB/SBS/PP/PS composite with CB mainly within the PS phase and partially at the PP/PS interface prepared by direct blending. Spreading and wetting coefficients were used to explain the CB distribution and the phase morphology of the composites. © 2012 Society of Chemical Industry     

苯乙烯在MBS中的结合方式对PVC/MBS性能的影响

以乳液聚合法合成了化学组成恒定的具有核-壳结构的(甲基丙烯酸甲酯/丁二烯/苯乙烯)共聚物(MBS),通过改变原料及其配比,使苯乙烯(St)在MBS中以共聚或接枝方式结合,用动态力学热分析仪研究了MBS内耗与温度的关系。将MBS与聚氯乙烯(PVC)共混,研究了St结合方式对共混物冲击韧性及增韧机理的影响,结果表明,随着MBS核中St含量的增加,PVC/MBS共混物的脆-韧转变向高温移动;当St仅以接枝的方式结合时,橡胶粒子的空洞化及剪切屈服是主要的增韧机理,当St仅以共聚方式结合时,剪切屈服是主要的增韧机理。     

Blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 toughened by maleated polystyrene‐based copolymers: Mechanical properties,morphology, and rheology

Poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6 30/70) blends were impact modified by addition of three kinds of maleated polystyrene‐based copolymers, i.e., maleated styrene‐ethylene‐butylene‐styrene copolymer (SEBS‐g‐MA), maleated methyl methacrylate‐butadiene‐styrene copolymer (MBS‐g‐MA), and maleated acrylonitrile‐butadiene‐styrene copolymer (ABS‐g‐MA). The mechanical properties, morphology and rheological behavior of the impact modified PPO/PA6 blends were investigated. The selective location of the maleated copolymers in one phase or at interface accounted for the different toughening effects of the maleated copolymer, which is closely related to their molecular structure and composition. SEBS‐g‐MA was uniformly dispersed in PPO phase and greatly toughened PPO/PA6 blends even at low temperature. MBS‐g‐MA particles were mainly dispersed in the PA6 phase and around the PPO phase, resulting in a significant enhancement of the notched Izod impact strength of PPO/PA6 blends from 45 J/m to 281 J/m at the MBS‐g‐MA content of 20 phr. In comparison, the ABS‐g‐MA was mainly dispersed in PA6 phase without much influencing the original mechanical properties of the PPO/PA6 blend. The different molecule structure and selective location of the maleated copolymers in the blends were reflected by the change of rheological behavior as well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Relationship between structure and properties in high‐performance PA6/SEBS‐g‐MA/(PPO/PS) blends: The role of PPO and PS

This work aimed at studying the role of poly(phenylene oxide) (PPO) and polystyrene (PS) in toughening polyamide‐6 (PA6)/styrene‐ethylene‐butadiene‐styrene block copolymer grafted with maleic anhydride (SEBS‐g‐MA) blends. The effects of weight ratio and content of PPO/PS on the morphology and mechanical behaviors of PA6/SEBS‐g‐MA/(PPO/PS) blends were studied by scanning electron microscope and mechanical tests. Driving by the interfacial tension and the spreading coefficient, the “core–shell” particles formed by PPO/PS (core) and SEBS‐g‐MA (shell) played the key role in toughening the PA6 blends. As PS improved the distribution of the “core–shell” particles due to its low viscosity, and PPO guaranteed the entanglement density of the PPO/PS phase, the 3/1 weight ratio of PPO/PS supplied the blends optimal mechanical properties. Within certain range, the increased content of PPO/PS could supply more efficient toughening particles and bring better mechanical properties. Thus, by adjusting the weight ratio and content of PPO and PS, the PA6/SEBS‐g‐MA/(PPO/PS) blends with excellent impact strength, high tensile strength, and good heat deflection temperature were obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45281.     

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     

Effects of the molecular structure of impact modifier and compatibilizer on the toughening of PBT/SBS/PS‐GMA blends

This work aims at studying the toughening process of poly(butylene terephthalate) (PBT) through its blends with styrene‐butadiene‐styrene block copolymers (SBS), in the presence of poly(styrene‐ran‐glicydil methacrylate) (PS‐GMA) as reactive compatibilizer. High values of impact strength were attained for PBT/SBS blends without the compatibilizer; however, this improvement is achieved for blends with SBS having similar viscosity compared to PBT, at high SBS content (40 wt %) and for blends prepared under specific processing conditions. The efficiency of the in situ compatibilization of PBT/SBS blends by PS‐GMA was found to be strongly dependent on the SBS and PS‐GMA molecular characteristics. Better compatibilizing results were observed through fine phase morphologies and lower ductile to brittle transition temperatures (DBTT) as the interfacial interaction and stability of the in situ formed compatibilizer are maximized, that is, when the miscibility between SBS and PS‐GMA and reaction degree between PBT and PS‐GMA are maximized. For the PBT/SBS/PS‐GMA blends under study, this was found when it is used the SBS with higher polystyrene content (38 wt %) and with longer PS blocks (M_w = 20,000 g mol^?1) and also the PS‐GMA with moderate GMA contents (4 wt %) and with molecular weight similar to the critical one for PS entanglements (M_c = 35,000 g mol^?1). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5795–5807, 2006     

Plasticization of nano‐CaCO3 in polystyrene/nano‐CaCO3 composites

The shear rheological properties of polystyrene (PS)/nano‐CaCO₃ composites were studied to determine the plasticization of nano‐CaCO₃ to PS. The composites were prepared by melt extrusion. A poly(styrene–butadiene–styrene) triblock copolymer (SBS), a poly(styrene–isoprene–styrene) triblock copolymer (SIS), SBS‐grafted maleic anhydride (SBS–MAH), and SIS‐grafted maleic anhydride were used as modifiers or compatibilizers. Because of the weak interaction between CaCO₃ and the PS matrix, the composites with 1 and 3 phr CaCO₃ loadings exhibited apparently higher melt shear rates under the same shear stress with respect to the matrix polymer. The storage moduli for the composites increased with low CaCO₃ concentrations. The results showed that CaCO₃ had some effects on the compatibility of PS/SBS (or SBS–MAH)/CaCO₃ composites, in which SBS could effectively retard the movement of PS chain segments. The improvement of compatibility, due to the chemical interaction between CaCO₃ and the grafted maleic anhydride, had obvious effects on the rheological behavior of the composites, the melt shear rate of the composites decreased greatly, and the results showed that nano‐CaCO₃ could plasticize the PS matrix to some extent. Rheological methods provided an indirect but useful characterization of the composite structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Blends of i‐PP and SBS. II. Influence of in situ compatibilization on the mechanical properties

This article concerns the in situ compatibilization of immiscible isotatic polypropylene/styrene–butadiene–styrene triblock copolymer blends (i‐PP/SBS) by use of a reactive mixture. For this purpose, maleated PP (PP–MAH) and SBS (SBS–MAH) were used as functionalized polymers and 4,4′‐diaminediphenylmethane was used as a coupling agent between maleated polymers, resulting in a graft copolymer. Binary blends of i‐PP/SBS, nonreactive ternary blends of i‐PP/PP–MAH/SBS, and reactive ternary blends of i‐PP/PP–MAH/SBS–MAH with varying diamine/anhydride molar ratios were prepared. The mechanical properties of the blends were determined by tensile and impact‐resistance tests. The optimum improvement in the mechanical properties was found when the diamine/anhydride molar ratio in the ternary reactive blends was 0.5/1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 516–522, 2003     

Physical and mechanical properties of photopolymerized SBS–methacrylic monomer systems

An exploratory study on physical and mechanical properties—transmittance, pendulum hardness, dynamic‐mechanical, and tensile—of photopolymerized styrene–butadiene–styrene block copolymer (SBS)–methacrylic monomer systems at different compositions was carried out. The insoluble and crosslinked polymerized systems prepared exhibit a high transmittance along the visible light region and retain the regular structure corresponding to the matrix (SBS), that is, the dynamic‐mechanical spectra show the two peaks corresponding to the PS and PB phases in the tan δ–temperature plot. Trapped radicals remain in the photopoymerized SBS–methacrylic monomer (tetra or hexafunctional) system, so when these systems are heated above their vitreous transition temperature, a postpolymerization reaction is produced that gives rise to an increase of both the crosslinking density and the storage modulus. The modulus and ultimate tensile strength of the polymerized SBS–hexanediol dimethacrylate (HDDMA) systems increase with increasing initial proportions of the dimethacrylate monomer; on the contrary, the percent elongation at break and toughness decrease with increasing proportions of initial dimethacrylate monomer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2857–2864, 2003     

Rubber toughened and optically transparent blends of cyclic olefin copolymers

A study is presented of increasing the toughness of Cyclic Olefin Copolymer (COC) while maintaining its optical transparency. The COC consists of a random copolymer of ethylene and norbornene, and the impact modifiers consist of thermoplastic elastomers. It is shown that several requirements must be satisfied, namely: for toughening there is an optimum finite particle size, but in order to minimize light scattering the particles have to be as small as possible. In addition, the refractive index of the elastomer must be closely matched to COC over the visible wavelength range and use temperature. Also for toughening, there are additional requirements of the adhesion of the elastomer to COC and high molecular weight. It is found that styrene butadiene styrene (SBS) is the most effective elastomer in toughening COC while maintaining optical transparency. It is also found that the addition of an index matched styrene‐ethylene‐butylene‐styrene (SEBS) copolymer as a compatibilizer to the SBS elastomer is beneficial in increasing the toughness and lowering the optical haze. Finally, light scattering calculations are presented based on the Rayleigh Debye model to calculate the optical haze and transmission of these blends. These calculations take into account the refractive index of COC and the elastomer, the particle size distribution and volume fraction of the elastomer. It is shown that there is reasonable agreement between calculation and experimental results. It is possible to increase the toughness of COC to greater than 50 J/m (Notched Izod) while keeping the optical haze to below 5% with an elastomer loading of 5% (w/w). We also identify opaque blends of COC with a toughness of greater than 500 J/m with an elastomer loading of 20% (w/w).     

Mechanical properties and morphology of LCP/ABS blends compatibilized with a styrene–maleic anhydride copolymer

A co‐polyester liquid crystalline polymer (LCP) was melt blended with an acrylonitrile–butadiene–styrene copolymer (ABS). LCP fibrils are formed and a distinct skin/core morphology is observed in the injection moulded samples. At higher LCP concentration (50 wt%), phase inversion occurs, where the dispersed LCP phase becomes a co‐continuous phase. While the tensile strength and Young's modulus remain unchanged with increasing LCP content up to 30 wt% LCP, a significant enhancement of the modulus at 50 wt% LCP is observed due to the formation of co‐continuous morphology. The blend modulus is lower than the values predicted by the rule of mixtures, suggesting a poor interface between the LCP droplets and ABS matrix. A copolymer of styrene and maleic anhydride (SMA) was added in the LCP/ABS blends during melt blending. It is observed that SMA has a compatibilizing effect on the blend system and an optimum SMA content exists for mechanical properties enhancement. SMA improves the interfacial adhesion, whereas excess of SMA reduces the LCP fibrillation. Copyright © 2003 Society of Chemical Industry     

Amphiphilic styrene–butadiene–styrene triblock copolymer grafted with polyoxyethylene

A styrene–butadiene–styrene triblock copolymer (SBS) was grafted with polyoxyethylene via a ring‐opening reaction of an epoxidized styrene–butadiene– styrene triblock copolymer (ESBS) with monocarboxylic‐group‐terminated methoxypoly(ethylene glycol) (CMPEG). The latter was prepared through the esterification of methoxypoly(ethylene glycol) with maleic anhydride. The optimum conditions for the preparation of the graft copolymer were studied. The graft copolymer was characterized with Fourier transform infrared spectrophotometry. Its water absorbency, oil absorbency, emulsifying property, phase‐transfer catalysis property in the Williamson solid–liquid reaction, and use as a compatibilizer in the blending of SBS with oil‐resistant chlorohydrin rubber (CHR) were also studied. The optimum conditions were a CMPEG/epoxy group molar ratio of 1.5, an N,N‐dimethyl aniline/ESBS concentration of 5 wt %, and an ESBS concentration of 12–14 g/100 mL at 75–80°C for 10 h. The polyoxyethylene content could reach 0.27 mmol/g. The graft copolymer absorbed a certain amount of water, fairly resisted kerosene, and possessed good emulsifying and phase‐transfer catalysis properties, both of which were enhanced with increasing polyoxyethylene graft content. The graft copolymer could be used as a compatibilizer for a blend of SBS and CHR. A 3 wt % concentration of the graft copolymer based on a 50/50 blend could increase both the tensile strength and ultimate elongation of the blend about 1.7 times. The blend behaved like an oil‐resistant thermoplastic elastomer. Scanning electron microscopy demonstrated the improved compatibility of the two components by the graft copolymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

SBS and SEBS block copolymers as impact modifiers for polypropylene compounds

Blends of polypropylene (PP) and thermoplastic elastomers (TPE), namely SBS (styrene‐butadiene‐styrene) and SEBS (styrene‐ethylene/1‐butene‐styrene) block copolymers, were prepared to evaluate the effectiveness of the TPE type as an impact modifier for PP and influence of the concentration of elastomer on the polymer properties. Polypropylene homopolymer (PP‐H) and ethylene–propylene random copolymer (PP‐R) were evaluated as the PP matrix. Results showed that TPEs had a nucleating effect that caused the PP crystallization temperature to increase, with SBS being more effective than SEBS. Microstructure characterization tests showed that in most cases PP/SEBS blends showed the smallest rubber droplets regardless of the matrix used. It was seen that SEBS is a more effective toughening agent for PP than SBS. At 0°C the Izod impact strength of the PP‐H/SEBS 30% b/w blend was twofold higher than the SBS strength, with the PP‐R/SEBS 30% b/w blend showing no break. A similar behavior on tensile properties and flexural modulus were observed in both PP/TPE blends. Yield stress and tensile strength decreased and elongation at break increased by expanding the dispersed elastomeric phase in the PP matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 254–263, 2005     

The toughness and morphology of (chlorinated poly[vinyl chloride])/(methyl methacrylate‐butadiene‐styrene) blends

A series of methyl methacrylate‐butadiene‐styrene (MBS) graft copolymers were synthesized via seeded emulsion polymerization techniques by grafting styrene and methyl methacrylate on poly(butadiene‐co‐styrene) (SBR) particles. The chlorinated poly(vinyl chloride) (CPVC)/MBS blends were obtained by melting MBS graft copolymers with CPVC resin, and the effect of the core/shell ratio of MBS graft copolymer and SBR content of CPVC/MBS blends on the mechanical properties and morphology of CPVC/MBS blends was studied. The results showed that, with the increase in the core/shell ratio, the impact strength of the blend increased and then decreased. It was found that, when the core/shell ratio was 50/50, the impact strength was about 155 J/m, and the tensile strength evidently increased. The toughness of the CPVC/MBS blend was closely related to the SBR content of the blend, and with the increasing of SBR content of blend, the impact strength of the blend increased. The morphology of CPVC/MBS blends was observed via scanning electron microscopy. Scanning electron microscopy indicated that the toughness of CPVC/MBS blend was consistence with the dispersion of MBS graft copolymers in the CPVC matrix. J. VINYL ADDIT. TECHNOL., 22:501–505, 2016. © 2015 Society of Plastics Engineers