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.     

Deformation mechanism of polystyrene toughened with sub‐micrometer monodisperse rubber particles

Core–shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core‐shell rubber particles were then blended with polystyrene to prepare PS/PB‐g‐PS blends with a constant rubber content of 20 wt%. PB‐g‐PS particles with a lower PB/PS ratio (≤70/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high‐impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1–3 µm rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub‐micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress‐whitening zone of blends with a PB/PS ratio of 70/30 in PB‐g‐PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation. Subsequently, a compression‐induced activation method was explored to compare the PS/PB‐g‐PS blends with commercial HIPS, and the result show that the toughening mechanisms of the two samples are different. Copyright © 2006 Society of Chemical Industry     

Poly(methyl methacrylate) toughening with refractive index‐controlled core–shell composite particles

Poly(butylacrylate‐co‐styrene)/poly(methyl methacrylate) (PMMA) core–shell composite particles having different refractive indexes were prepared by a two‐stage consecutive emulsion polymerization. The refractive index of the core phase was controlled by varying the incorporated amount of divinylbenzene (DVB) which acted as a crosslinking agent as well as a refractive index enhancer. The blends of these core–shell composite particles with PMMA showed an impact strength increment of about three times compared with that of the pure PMMA. However, as the amount DVB increased, the impact strength showed a tendency toward decreasing. This was caused by the loss of the elastic property of the core phase. The toughened PMMA blended with core–shell composite particles having the core crosslinked with 1 wt % DVB showed the best transparency. However, the transparency was rather decreased, as the difference of the refractive index between the core phase and the pure PMMA increased. This suggested that in the case of using the core–shell composite particles as a toughening agent for PMMA the matching of the refractive index of the core phase with that of the pure PMMA was one of key factors in maintaining the transparency of the toughened PMMA. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1607–1614, 1999     

Epoxy networks toughened by core–Shell particles: Influence of the particle structure and size on the rheological and mechanical properties

The core–shell particles considered were poly(butyl acrylate) core/epoxy groups functionalizing the poly(methyl methacrylate) shell. Physical and thermomechanical properties of benzyl dimethylamine (BDMA)‐catalyzed diglycidyl ether of bisphenol A (DGEBA)/dicyandiamine epoxy networks toughened with core–shell particles were studied. The blends were prepared under well‐defined processing conditions. The resulting properties were found to depend on the state of the dispersion of the particles in the prepolymer matrix before crosslinking. These particles were dispersed at different volume fractions in order to vary the interparticle distance. The relationships between the size of the core–shell particles and the level of toughening are reported. Static mechanical tests were performed in tension and compression modes on these core–shell polyepoxy blends. A slight decrease in the Young's modulus and an increase in the ability to plastic deformation were observed. Using linear fracture mechanics (LEFM), an improvement of the fracture properties (K_IC) was measured. By varying the volume fraction of core–shell particles, an optimum toughness improvement was found for an interparticle distance equal to 400 nm (with an average particle size of 600 nm). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 849–858, 1999     

Morphology and rheology relationships of epoxy/core‐shell particle blends

The morphological and rheological behaviors of toughened epoxy resins modified with core‐shell rubber particles (CSR) were studied. These rubber particles were based on a poly (butadiene‐co‐styrene) core and a crosslinked poly (methyl methacrylate) shell. The effect of functionalized groups was performed on two types of CSR particles: first, those containing carboxyl‐functionalized groups (CSf), and second, particles containing no carboxyl‐functionalized groups (CSnf) in the PMMA‐shell. For these blends, the correlations between the morphology, particle dispersion state and their rheological behaviors before curing were investigated. Preliminary work using TEM micrographs indicated that the blends modified with CSf and CSnf exhibited the same particle size but differed with respect to the dispersion state. Rheological behavior of these blends was assessed in steady shear flow and dynamic viscoelastic experiments. Yield viscosity near‐zero shear rate occurred in the DGEBA/CSf blend presenting non‐Newtonian behavior at the particle volume fraction of 20% vol. The rheological behavior was clearly related to the state of particle dispersion and analyzed taking into account interactions between the particles‐particles and the particles‐matrix. The Williams‐Landel‐Ferry (WLF) shift procedure was used to construct modulus master curves G′ and G″ from the elastic solid state to molten polymers. A secondary plateau existed at low frequencies and was related to the presence of interactions leading to a physical network‐type structure. The deviation between theoretical G′ (Paleirne's model) and experimental G′ values was evaluated and exhibited high elasticity at the terminal zone, which correlated well with available literature.     

Preparation and properties of core [poly(styrene‐n‐butyl acrylate)]–shell [poly(styrene–methyl methacrylate–vinyl triethoxide silane)] structured latex particles with self‐crosslinking characteristics

Structured latex particles with a slightly crosslinked poly(styrene‐n‐butyl acrylate) (PSB) core and a poly(styrene–methacrylate–vinyl triethoxide silane) (PSMV) shell were prepared by seed emulsion polymerization, and the latex particle structures were investigated with Fourier transform infrared, thermogravimetric analysis, differential scanning calorimetry, transmission electron microscopy, and dynamic light scattering. The films that were formed from the structured core (PSB)–shell (PSMV) particles under ambient conditions had good water repellency and good tensile strength in comparison with films from structured core (PSB)–shell [poly(styrene–methyl methyacrylate)] latex particles; this was attributed to the self‐crosslinking of CH₂?CH? Si(OCH₂CH₃)₃ in the outer shell structure. The relationship between the particle structure and the film properties was also investigated in this work. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1824–1830, 2006     

Core-shell structured latex particles. III. Structure–properties relationship in toughening of polycarbonate with poly(n-butyl acrylate)/poly(benzyl methacrylate–styrene) structured latex particles

The performance of the designed structured core-shell latex particles in toughening polycarbonate (PC) matrix was examined. Izod impact testing of the PC-core-shell latex blends were used to evaluate the influence of parameters related to the core-shell latex particles on toughening polycarbonate. Among these parameters are the particle size and levels of crosslinking of the core rubber particles, composition and molecular weight of the shell polymer, and weight ratio of shell to core polymers as well as the particle morphology. In this work, core-shell structured latex particles with thinner shells of higher molecular weight polymers were found to improve the impact resistance of polycarbonate. The role of chain entanglements in increased adhesion between the discrete rubbery phase and the continuous glassy matrix and the importance of surface-to-surface interparticle distance for toughening at various temperatures are discussed. © 1995 John Wiley & Sons, Inc.     

Toughening and brittle‐tough transition in blends of an amorphous polyamide with a modified styrene/ethylene‐butylene/styrene triblock copolymer

Amorphous polyamide (aPA)/maleated styrene/ethylene‐butylene/styrene triblock copolymer (mSEBS) blends with a mSEBS content up to 25% were obtained in the melt state with the aim of toughening the notch sensitive pseudoductile matrix, and of studying the parameters that influence the morphology that leads to the brittle/tough transition. The increase in the T_g of the rubbery phase, which depended on the maleinized copolymer content, indicated the presence of reacted copolymers. These copolymers should decrease the interfacial tension, thus allowing the presence of a fine dispersed particle size. The impressive (27‐fold) toughness increase observed, which is among the largest observed in toughened blends, took place at 15% mSEBS content. The critical interparticle distance (τ_c) of the blends was smaller than that of polyamide 6 (PA6)/mSEBS blends tested at the same conditions. Having ruled out the possible influence of other parameters, the lower τ_c of the aPA/mSEBS blends of this study is attributed to their higher interfacial adhesion that was inferred by the calculation of the solubility parameters and by the measured interfacial toughness. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Tough polyamide 6/core–shell blends prepared via in situ anionic polymerization of ε‐caprolactam by reactive extrusion

In this study, the molten ε‐caprolactam (CL) solution of maleated styrene‐ethylene/butylene‐styrene block copolymer (SEBS‐g‐MA) and polystyrene (PS) containing catalyst and activator were introduced into a twin screw extruder, and polyamide 6 (PA6)/SEBS/PS blends were successfully prepared via anionic polymerization of CL by reactive extrusion. The mechanical properties measurements indicated that both the elongation at break and notched Izod impact strength of PA6/SEBS/PS (85/10/5) blends were improved distinctly with slight loss of tensile and flexural strength as compared to that of pure PA6. The images of transmission electron microscopy showed that a core–shell structure with PS core and poly (ethene‐co‐1‐butene) (PEB) shell was formed within the PA6 matrix. Fourier transform infrared was used to investigate the formation mechanisms of the core–shell structure. POLYM. ENG. SCI., 53:2705–2710, 2013. © 2013 Society of Plastics Engineers     

Effect of the core‐shell impact modifier shell thickness on toughening PVC

The shell thickness of a core/shell impact modifier is found to be the single most important factor in the toughening of rigid polyvinyl chloride (PVC). When the shell thickness is greater than a critical value of 15.8 nm, these core‐shell elastomeric particles are able to remain structurally intact and well dispersed within the PVC matrix after melt blending. However, too thick a shell thickness results in a hard core (high modulus) of these core/shell particles and loss of the rubbery nature required of an efficient impact modifier. Therefore, these over‐thick particles can act only as rigid fillers, not as efficient rubbery modifiers. On the other hand, when the shell thickness is less than the critical value of 4.9 nm, too thin a shell layer is simply unable to fully protect and cover the inner rubbery core during vigorous processing conditions, and these core‐shell particles tend to connect with one another through the partially exposed core to form a cellular‐like structure, thus resulting in poor toughening efficiency. Regardless of the particle size, as long as the shell thickness of these core/shell elastomers is between these two critical values (15.8 nm and 4.9 nm), they all display high efficiency in toughening rigid PVC. Polym. Eng. Sci. 44:1885–1889, 2004. © 2004 Society of Plastics Engineers.     

Phenolic foams toughened with crosslinked poly (n‐butyl acrylate)/silica core‐shell nanocomposite particles

A new type of crosslinked poly (n‐butyl acrylate) (PBA)/silica core‐shell nanocomposite particles was adopted as toughening agent to improve the mechanical properties of phenolic foams. The effects of the nanocomposite particles on the structures and properties of lightweight phenolic foams were investigated. SEM result showed that the addition of a small quantity of the nanocomposite particles can significantly enhance the structural homogeneity of phenolic foams. Thermalgravimetric analysis result suggested that the incorporation of the nanocomposite particles did not affect the thermal stability of the toughened phenolic foams. The flexural strength, compressive strength, and elastic modulus of the phenolic foams increased distinctively after the addition of the nanocomposite particles, the maximum values of which increased by 36.0%, 42.9%, and 32.3%, respectively. In this study, the optimum dosage of the nanocomposite particles is 0.03 phr in the modified phenolic foams. Moreover, the influence on the flammability of phenolic foams by toughening can almost be neglected. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42590.     

Effect of seed characteristics on morphology development in poly(n‐butyl acrylate)‐poly(n‐butyl methacrylate) core‐shell dispersions

This article reports on the influence of synthesis characteristics such as seed cross linking, particle‐size distribution (PSD), and surfactant in the seeded emulsion polymerization of n‐butyl acrylate–butyl methacrylate core‐shell systems. These systems were studied using a combination of techniques such as light scattering (static and dynamic), asymmetric field flow fractionation coupled with multiangle laser light scattering and transmission electron microscopy. Complimentary data, obtained from static light scattering and electron microscopy studies, on the effect of seed crosslinking on morphology development reveals that the presence of a crosslinked seed favors the formation of nonequilibrium core‐shell morphology. For uncrosslinked seeds occluded structures were present with a diffuse boundary between the core and the shell. In both cases, i.e., with or without surfactant, a monomodal PSD was observed for the core‐shell systems and the relative size polydispersity and the shape of the seed PSD were retained. Use of surfactant was found to broaden the PSD but did not seem to affect the formation core‐shell morphology. The study also shows the influence of crosslinked seeds on the film properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Simultaneously improved toughness and dielectric properties of epoxy/core‐shell particle blends

Epoxy/core‐shell particle blends were prepared using a diglycidylether of bisphenol A epoxy and acrylics‐type core‐shell particles. The impact strength of the blends was tested, and the result showed that the epoxy was greatly toughened with optimum core‐shell particle content. Meanwhile, the dielectric properties of both epoxy and its blends were investigated using a broadband dielectric analyzer. It was found that the dielectric constant of the epoxy blends with lower core‐shell particle content were less than that of the epoxy in the investigated frequency range, while the dielectric loss was less than that of the neat epoxy over a low frequency range, even for the epoxy blends with the optimum core‐shell particle content. The dielectric breakdown strength of the epoxy blends at room and cryogenic temperature were also investigated. To identify the primary relationship of the above properties and structure of the epoxy blends, the microstructure of the core‐shell particle and the morphology of the samples were observed by transmission electron microscopy and scanning electron microscopy. It was considered that these epoxy/core‐shell particle blends with improved toughness and desirable dielectric properties could have a potential application in the insulation of electronic packaging system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Morphology of micron‐sized,monodisperse, nonspherical polystyrene/poly(n‐butyl methacrylate) composite particles produced by seeded dispersion polymerization

Nonspherical polystyrene (PS)/poly(n‐butyl methacrylate) (PBMA) composite particles with uneven surfaces were produced by seeded dispersion polymerization of BMA with 1.65‐μm, monodisperse, spherical PS seed particles. The composite particles consisted of a PS core and an incomplete PBMA shell. The formation mechanism of such nonspherical particles was discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2013–2021, 2002     

Effect of the composition of structured rubber particles on the toughness of poly(methylmethacrylate)

Composite natural rubber (NR) and monodisperse poly(n-butylacrylate) (PBuA) based latex particles were tested as possible impact modifiers for a poly(methylmethacrylate) (PMMA) matrix. A continuous extrusion process was used for the incorporation of wet latexes directly into a twin-screw extruder. All latexes had been coated by a PMMA shell. Furthermore, polystyrene (PS) subinclusions were introduced into the NR core. The impact resistance of the prepared PMMA blends can be most effectively improved by NR particles containing a large weight fraction of compatibilising PMMA in the shell. The degree of crosslinking of the shell polymer has to be restricted. PBuA based latex particles of 180 nm in size are ineffective to toughen the PMMA matrix. The degree of grafting of the NR phase in core–shell particles containing PS subinclusions is not crucial. Scanning electron microscopy was used to analyse the failure processes in composite rubber particle toughened PMMA blends at fast (impact conditions) and slow (tensile testing) deformation speeds.     

Surface modification effects of core–shell rubber particles on the toughening of poly(butylene terephthalate)

We toughened poly(butylene terephthalate) (PBT) by loading core–shell rubber (CSR) type impact modifiers, consisting of a rubbery poly(n‐butyl acrylate) core and a rigid poly(methyl methacrylate) shell. To optimize the dispersion of CSR particles into the PBT matrix during melt compounding, the shell surface was modified with different grafting ratios of glycidyl methacrylate (GMA) reactive with PBT chain ends. In PBT blends with a 20 wt % CSR loading, the dispersed rubbery phases showed discernible shapes depending on the grafted GMA content, from predetermined spheres with 0.25 ± 0.05 μm diameters to their aggregates in the 2–3 μm diameter range. As a result, the interparticle spacing (τ) could be controlled from 0.25 to 4.0 μm in the PBT blends containing the fixed rubber loading. The Izod impact strengths of these samples increased significantly below τ = 0.4 μm. Additional thermal and morphological analyses strongly supported the hypothesis that the marked increase in toughness of the blends was related to less ordered lamellar formation of the PBT matrix under the confined geometry. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Toughening of unsaturated polyester resins with core–shell rubbers

The effects of core–shell rubbers (CSRs) as tougheners on the fracture properties of unsaturated polyester (UP) resins during curing at 110°C are investigated. CSRs were synthesized by two‐stage soapless emulsion polymerizations; the soft core was made from rubbery poly(n‐butyl acrylate), whereas the hard shell was made from methyl methacrylate, ethylene glycol dimethacrylate, and various concentrations of glycidyl methacrylate. Depending on the content of glycidyl methacrylate in the CSR shell and the amount of CSR added to the UP, the fracture properties of the CSR‐toughened UP resins varied. The experimental results are explained by an integrated approach of measurements of the static phase characteristics of a styrene/UP/CSR system, the reaction kinetics, the cured sample morphology, the glass‐transition temperatures, and the fracture toughness with differential scanning calorimetry, scanning electron microscopy, transmission electron microscopy, and dynamic mechanical analysis. Finally, the toughening mechanism for the CSR‐toughened UP resins is also explored. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of extensional flow on properties of polyamide‐66/poly(2,6‐dimethyl‐1,4‐phenylene oxide) blends: A study of morphology,mechanical properties,and rheology

In this study, polyamide‐66/poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PA66/PPO) blends with high viscosity ratio were processed by a self‐designed triangle‐arrayed triple‐screw extruder (TTSE, which simulates extensional flow) and a commercial twin‐screw extruder (TSE), respectively. Furthermore, in order to improve the mechanical properties of the immiscible PA66/PPO blends, PPO‐grafted maleic anhydride (PPO‐g‐MA) and styrene–ethylene–butylene–styrene (SEBS) block copolymer were used. The mechanical properties, phase morphology, and rheological properties of both binary PA66/PPO blends and toughened PA66/PPO/PPO‐g‐MA blends were comprehensively investigated to compare the above mentioned two processing method. Samples processed with TTSE exhibited better mechanical properties than the TSE‐processed blends. The morphologies of the blends were examined by scanning electron microscopy, exhibiting smaller particles sizes and narrower particle size distributions, which were attributed to the significant effects of extensional flow in TTSE. The toughening mechanism of compatibilized blends was investigated through morphology analysis, dynamic mechanical, and rhelogical analysis. Thus, TTSE with an extensional effect was proved to be efficient in the blending of high viscosity ratio polymers. POLYM. ENG. SCI., 57:1090–1098, 2017. © 2016 Society of Plastics Engineers     

Effects of core‐shell acrylate particles on impact properties of chlorinated polyethylene/polyvinyl chloride blends

The impact properties of core‐shell acrylate (CS‐ACR)/chlorinated polyethylene (CPE)/poly(vinyl chloride) (PVC) blends under different temperatures were investigated. The fracture surface morphologies of the blends were observed by scanning electron microscopy (SEM). The results show that there exists significant synergistic effect between CS‐ACR particles and CPE in toughening PVC, and the impact properties of the blends generally correlate well with SEM morphologies. Besides, with increasing CS‐ACR content, ductile–brittle transition point of the ternary blends remarkably shifts to a lower temperature. Dynamic mechanical analysis exhibited that intensity and area of low‐temperature tan δ peaks of the CPE/PVC blends increase obviously after the addition of CS‐ACR particles, which to some extent are just in line with the changes in impact strength and ductile–brittle transition point of the blends. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Morphologies and dynamic mechanical properties of core‐shell emulsifier‐free latexes and their copolymers for P(BA/MMA)/P(MMA/BA) and P(BA/MMA)/PSt systems in the presence of AHPS

Different poly(methyl methacrylate/n‐butyl acrylate)/poly(n‐butyl acrylate/methyl methacrylate) [P(BA/MMA)/P(MMA/BA)] and poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(BA/MMA)/PSt] core‐shell structured latexes were prepared by emulsifier‐free emulsion polymerization in the presence of hydrophilic monomer 3‐allyloxy‐2‐hydroxyl‐propanesulfonic salt (AHPS). The particle morphologies of the final latexes and dynamic mechanical properties of the copolymers from final latexes were investigated in detail. With the addition of AHPS, a latex of stable and high‐solid content (60 wt %) was prepared. The diameters of the latex particles are ～0.26 μm for the P(BA/MMA)/P(MMA/BA) system and 0.22–0.24 μm for the P(BA/MMA)/PSt system. All copolymers from the final latexes are two‐phase structure polymers, shown as two glass transition temperatures (T_gs) on dynamic mechanical analysis spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3078–3084, 2002