Synthesis and characterization of poly (styrene‐b‐[(butadiene)1−x‐(ethylene‐co‐butylene)x] ‐b‐styrene) star‐like molecular polymers produced by partial hydrogenation of SBS

This article reports the synthesis and characterization of four arm star‐shaped poly(styrene‐b‐[(butadiene)_1?x‐(ethylene‐co‐butylene)_x]‐b‐styrene) (SBEBS) copolymers. A series of SBEBS copolymers with different compositions of the elastomeric block were produced by hydrogenating a given poly(styrene‐b‐butadiene‐b‐styrene) (SBS) copolymer using a catalyst prepared from bis(η⁵‐cyclopentadienyl)titanium(IV) dichloride and n‐butyllithium. The characterization was accomplished by proton nuclear magnetic resonance spectroscopy (¹H NMR), infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The results indicate that there is a selective saturation of the polybutadiene block over the polystyrene block; this selectivity was determined by the Ti/Li molar ratio and the concentration of Ti. It was observed that the saturation rate of the 1,2‐vinyl was higher than that of the 1,4‐trans and 1,4‐cis poly(butadiene)‐b isomers. The DSC and DMA results indicate that the degree of hydrogenation had a profound effect on the polymer's relaxation behavior. All samples exhibited a biphasic system behavior with two distinct transitions corresponding to the elastomeric and polystyrene blocks. SBEBS copolymers with higher saturation levels (>33%) exhibited a crystalline character. The TGA results indicated a characteristic weight loss temperature in all samples, with slightly higher thermal degradation stabilities in the materials with higher degrees of saturation. POLYM. ENG. SCI., 54:2332–2344, 2014. © 2013 Society of Plastics Engineers     

Morphology and flame‐retardancy properties of ternary high‐impact polystyrene/elastomer/polystyrene‐encapsulated magnesium hydroxide composites

The effects of elastomer type on the morphology, flammability, and mechanical properties of high‐impact polystyrene (HIPS)/polystyrene (PS)‐encapsulated magnesium hydroxide (MH) were investigated. The ternary composites were characterized by cone calorimetry, mechanical testing, and scanning electron microscopy. Morphology was controlled with poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) triblock copolymer or the corresponding maleinated poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS‐g‐MA). The HIPS/SEBS/PS‐encapsulated MH composites exhibited separation of the filler and elastomer, whereas the HIPS/SEBS‐g‐MA/PS‐encapsulated MH composites exhibited encapsulation of the filler by SEBS‐g‐MA. The flame‐retardant and mechanical properties of the ternary composites were strongly dependent on microstructure. The composites with an encapsulation structure showed higher flame‐retardant properties than those with a separation structure at the optimum use level of SEBS‐g‐MA. Furthermore, the composites with a separation structure showed a higher modulus and impact strength than those with an encapsulation structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Phase structure and morphology of wollastonite‐reinforced polypropylene composites modified with SEBS and SEBS‐g‐MA elastomers

Supermolecular structure of isotactic polypropylene/wollastonite/styrenic rubber block copolymers composites were studied as a function of elastomeric poly‐ (styrene‐b‐ethylene‐co‐butylene‐b‐styrene) triblock copolymer (SEBS) and the SEBS grafted with maleic anhydride (SEBS‐g‐MA) content (from 0 to 20 vol%) by optical, scanning, and transmission electron microscopy, wide‐angle X‐ray diffraction and differential scanning calorimetry. Wollastonite particles disturbed the spherulitization of polypropylene matrix. Both elastomers affected the crystallization of polypropylene matrix mainly by solidification effect. Although SEBS‐g‐MA encapsulated wollastonite particles more expressive than SEBS forming thus core‐shell morphology in higher extent, scanning electron micrographs indicated more constrained wollastonite particles in fractured surfaces of composites with SEBS elastomer. Moreover, SEBS‐g‐MA disorientated wollastonite particles and affected reorientation of the polypropylene crystallites stronger than SEBS elastomer. POLYM. ENG. SCI., 47:2145–2154, 2007. © 2007 Society of Plastics Engineers     

Characterization of morphology in chemically modified styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene by solid‐state nuclear magnetic resonance

Multiphase triblock styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS) copolymers chemically modified with maleic anhydride (MAH) in the presence of a radical initiator by reactive extrusion were studied by solid‐state ¹H‐NMR and ¹³C‐NMR. In the experiments performed, the concentrations of MAH and initiator were kept constant, whereas the temperature profile in the extruder was varied. Samples with known extents of grafting and crosslinking were analyzed with NMR with techniques based on proton spin diffusion to investigate the microphase structure of the modified copolymers. The ¹³C‐NMR results show that the size of the rigid domains was about 15 nm and was not significantly changed by the modification. Alterations in the rubbery phase were illustrated by measured changes in proton spin‐spin (T₂) relaxation times. The fraction of protons having intermediate mobilities increased slightly in modified SEBS with respect to that observed in unmodified copolymers. These results were found to be independent of the extruder temperature profiles used, at least in the range studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical properties of wollastonite‐reinforced polypropylene composites modified with SEBS and SEBS‐g‐MA elastomers

Mechanical properties of isotactic polypropylene/wollastonite/styrene rubber block copolymers (iPP/wollastonite/SRBC) composites were studied as a function of elastomeric poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) triblock copolymer (SEBS) and SEBS grafted with maleic anhydride (SEBS‐g‐MA) content from 0 to 20 vol%. Microphase morphology was stronger influenced by SRBC elastomers than by different wollastonite types. Higher encapsulation ability of SEBS‐g‐MA than SEBS caused more expressive core‐shell morphology and consequently higher notched impact strength as well as yield parameters, but lower Young's modulus. Higher ductility of the composites with SEBS than with SEBS‐g‐MA has been primarily caused by better miscibility of the polypropylene chains with SEBS molecules. Surface properties of components and adhesion parameters also indicated that adhesion at SEBS‐g‐MA/wollastonite interface, which was stronger than the one at the SEBS/wollastonite interface, influenced higher encapsulation of wollastonite particles by SEBS‐g‐MA. POLYM. ENG. SCI., 47:1873–1880, 2007. © 2007 Society of Plastics Engineers     

Compatibilization effects of styrenic/rubber block copolymers in polypropylene/polystyrene blends

Compatibilizing effects of styrene/rubber block copolymers poly(styrene‐b‐butadiene‐b‐styrene) (SBS), poly(styrene‐b‐ethylene‐co‐propylene) (SEP), and two types of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS), which differ in their molecular weights on morphology and selected mechanical properties of immiscible polypropylene/polystyrene (PP/PS) 70/30 blend were investigated. Three different concentrations of styrene/rubber block copolymers were used (2.5, 5, and 10 wt %). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the phase morphology of blends. The SEM analysis revealed that the size of the dispersed particles decreases as the content of the compatibilizer increases. Reduction of the dispersed particles sizes of blends compatibilized with SEP, SBS, and low‐molecular weight SEBS agrees well with the theoretical predictions based on interaction energy densities determined by the binary interaction model of Paul and Barlow. The SEM analysis confirmed improved interfacial adhesion between matrix and dispersed phase. The TEM micrographs showed that SBS, SEP, and low‐molecular weight SEBS enveloped and joined pure PS particles into complex dispersed aggregates. Bimodal particle size distribution was observed in the case of SEP and low‐molecular weight SEBS addition. Notched impact strength (a_k), elongation at yield (ε_y), and Young's modulus (E) were measured as a function of weight percent of different types of styrene/rubber block copolymers. The a_k and ε_y were improved whereas E gradually decreased with increasing amount of the compatibilizer. The a_k was improved significantly by the addition of SEP. It was found that the compatibilizing efficiency of block copolymer used is strongly dependent on the chemical structure of rubber block, molecular weight of block copolymer molecule, and its concentration. The SEP diblock copolymer proved to be a superior compatibilizer over SBS and SEBS triblock copolymers. Low‐molecular weight SEBS appeared to be a more efficient compatibilizer in PP/PS blend than high‐molecular weight SEBS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 291–307, 1999     

Poly(methacrylate)‐derived diblock dispersant for TiO2 in aqueous suspensions

In this paper, we propose a newly designed dispersant, ammonium poly(methacrylate)‐block‐poly(2‐phenoxyethyl acrylate) (PMA‐b‐PBEA), and our rheological and zeta potential test results verify its superior dispersion efficiency for aqueous suspensions in comparison to the commercial dispersant ammonium polyacrylate (PAA‐NH₄). The extremely high dispersion efficiency of PMA‐b‐PBEA correlates closely to its diblock structure, which simultaneously exhibits a less polar anchoring head group and a water‐dissociable stabilizing moiety. The unique structure of PMA‐b‐PBEA accounts for its high powder adsorption effectiveness, which is demonstrated in its adsorption capability being double that of PAA‐NH₄.     

Synthesis and characterization of poly(L‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(L‐lactic acid) copolyesters

Random copolyester namely, poly(ethylene terephthalate‐co‐sebacate) (PETS), with relatively lower molecular weight was first synthesized, and then it was used as a macromonomer to initiate ring‐opening polymerization of l ‐lactide. ¹H NMR quantified composition and structure of triblock copolyesters [poly(l ‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(l ‐lactic acid)] (PLLA‐PETS‐PLLA). Molecular weights of copolyesters were also estimated from NMR spectra, and confirmed by GPC. Copolyesters exhibited different solubilities according to the actual content of PLLA units in the main chain. Copolymerization effected melting behaviors significantly because of the incorporation of PETS and PLLA blocks. Crystalline morphology showed a special pattern for specimen with certain composition. It was obvious that copolyesters with more content of aromatic units of PET exhibited increased values in both of stress and modulus in tensile test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Excellent biocompatible polymeric membranes prepared via layer‐by‐layer self‐assembly

Excellent biocompatible polymeric membranes were prepared by combining the antifouling property of poly(ethylene glycol) methyl ether (mPEG) and the anticoagulant property of poly(sodium p‐styrene sulfonate) (PSS). Block copolymers of poly(ethylene glycol) methyl ether‐b‐poly(sodium p‐styrene sulfonate) (mPEG‐b‐PSS) with different chain lengths were synthesized by ATRP using mPEG macroinitiator. The copolymers were then used to modify polyethersulfone (PES) membrane via layer‐by‐layer (LBL) self‐assembly technology. The chemical compositions, surface morphologies and hydrophilicity of the modified membranes were characterized, indicating that the mPEG‐b‐PSS copolymers were successfully deposited on the membranes surfaces. Then, the blood compatibility and cytocompatibility of the modified membranes were systematically investigated. The results indicated that the mPEG‐b‐PSS copolymers could improve the hydrophilicity and the resistance to protein adsorption, and had great effect on suppressing platelet adhesion, prolonging clotting times, and improving cytocompatibility. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41245.     

Recycling of high density polyethylene/poly(vinyl chloride)/polystyrene ternary mixture with the aid of high energy radiation and compatibilizers

Ternary mixtures of waste plastics of high density polyethylene (HDPE), poly(vinyl chloride) (PVC), and polystyrene (PS) was recycled using a single‐screw extruder. Poly(ethylene‐co‐vinyl acetate) and poly(styrene‐b‐ethylene/butylenes‐b‐styrene) were introduced as compatibilizers for HDPE/PVC and HDPE/PS, respectively. After the polymer blends was prepared via extrusion, they were subjected to high energy irradiation. The morphology and the mechanical properties of the hybrid blends were examined. Scanning electron micrographs and transmission electron micrographs showed that both compatibilizers and irradiation improved the uniformity and dispersion of the system. The heterogeneous crosslinking generated by irradiation resulted in an optimum impact strength. High elongation at break was achieved by using compatibilizers. The improvement of tensile strength was moderate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2756–2762, 2003     

Investigation on the morphological and mechanical properties of (polyamide 6)/(poly[styrene‐co‐acrylonitrile])/(poly[styrene‐b‐{ethylene‐co‐butylene}‐b‐styrene]) ternary blends

In this work, ternary polymer blends based on (polyamide 6)/(poly[styrene‐co‐acrylonitrile])/(poly[styrene‐b‐{ethylene‐co‐butylene}‐b‐styrene]) (SEBS) triblock copolymer and a varying concentration of the reactive (maleic anhydride)‐grafted SEBS were prepared by using a melt‐blending process. The effects of the material parameters (composition of ternary blends and SEBS/[{maleic anhydride}‐grafted SEBS] concentration ratio) and blending sequence on the morphological and mechanical properties of ternary blends were studied. Taguchi experimental design methodology was employed to design the experiments and select the material and processing parameters for the optimized mechanical properties. Tensile properties (Young's modulus and yield stress) and impact strength were considered as the response variables. It was demonstrated that there is a meaningful relationship between the composition of blends, processing parameters, observed phase structure, and obtained mechanical properties. The mechanical tests showed that the highest impact strength was achieved as the dispersion of the rubbery phase achieved an optimum size of about 1 μm. J. VINYL ADDIT. TECHNOL., 23:329–337, 2017. © 2015 Society of Plastics Engineers     

Synthesis of block copolymers via redox polymerization

Polymerization and copolymerization of vinyl monomers such as acrylamide, acrylonitrile, vinyl acetate, and acrylic acid with a redox system of Ce(IV) and organic reducing agents containing hydroxy groups were studied. The reducing compounds were poly(ethylene glycol)s, halogen‐containing polyols, and depolymerization products of poly(ethylene terephthalate). Copolymers of poly(ethylene glycol)s‐b‐polyacrylonitrile, poly(ethylene glycol)s‐b‐poly(acrylonitrile‐co‐vinyl acetate), poly(ethylene glycol)s‐b‐polyacrylamide, poly(ethylene glycol)s‐b‐poly(acrylamide‐co‐vinyl acetate), poly(1‐chloromethyl ethylene glycol)‐bpoly(acrylonitrile‐co‐vinyl acetate), and bis[poly(ethylene glycol terephthalate)]‐b‐poly(acrylonitrile‐co‐vinyl acetate) were produced. The yield of acrylamide polymerization and the molecular weight of the copolymer increased considerably if about 4% vinyl acetate was added into the acrylamide monomer. However, the molecular weight of the copolymer was decreased when 4% vinyl acetate was added into the acrylonitrile monomer. Physical properties such as solubility, water absorption, resistance to UV light, and viscosities of the copolymers were studied and their possible uses are discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1385–1395, 1999     

Morphology and mechanical properties of high‐impact polystyrene/elastomer/magnesium hydroxide composites

Ternary composites of high‐impact polystyrene (HIPS), elastomer, and magnesium hydroxide filler encapsulated by polystyrene were prepared to study the relationships between their structure and mechanical properties. Two kinds of morphology were formed. Separation of elastomer and filler was found when a nonpolar poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] triblock copolymer (SEBS) was incorporated. Encapsulation of filler by elastomer was achieved by using the corresponding maleinated SEBS (SEBS‐g‐MA). The mechanical properties of ternary composites were strongly dependent on microstructure. In this study, the composites with separate dispersion structure showed higher elongation, modulus and impact strength than those of encapsulation structure. Impact‐fracture surface observation showed that the toughening mechanism was mainly due to the massive cavitation and extensive matrix yielding. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5184–5190, 2006     

The effect of poly[styrene‐b‐(ethylene‐co‐butylene)‐ b‐styrene] on dielectric,thermal, and morphological characteristics of polypropylene/silica nanocomposites

The effect of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) copolymer on the thermal and dielectric properties of polypropylene (PP)—nanosilica (NS) composites in relation with morphological aspects revealed by atomic force microscopy (AFM) was investigated in this article. SEBS hindered the crystallization process of PP in PP/NS composites, leading to a smaller degree of crystallinity and lower perfection of crystalline structure. Broader lamellar thickness distribution was obtained in nanocomposites containing SEBS. Almost two times higher dielectric loss as compared to PP reference and two relaxation processes were detected in ε_r ^′′(f) curves of nanocomposites. The first peak, in the same frequency domain as for the references, was assigned to α‐relaxation of polymer components together with interfacial polarization. The relaxation time follows the Arrhenius law with an activation energy of 80–90 kJ/mol. For the second process, the temperature dependence of the relaxation times obeyed the VFT equation. The dielectric changes following the incorporation of SEBS support its tendency to hinder the motional processes in PP, in accordance with DSC results. A smooth transition from a phase rich in SEBS to one containing mainly PP was detected in the AFM image of the composite with the larger amount of SEBS, emphasizing the good compatibility at the PP/SEBS interface. POLYM. ENG. SCI., 53:2081–2092, 2013. © 2013 Society of Plastics Engineers     

Synthesis of a chiral stationary phase with poly[styrene‐b‐cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate)] by surface‐initiated atom transfer radical polymerization and its chiral resolution efficiency

A chiral stationary phase (CSP) with poly[styrene‐b‐cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate)] was synthesized by the surface‐initiated atom transfer radical polymerization (SI‐ATRP) of cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate)‐6‐acrylate after the SI‐ATRP of styrene on the surface of silicon dioxide supports in pyridine. The successful preparation of the CSP with poly[styrene‐b‐cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate)] was confirmed via Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X‐ray photoelectron spectroscopy, elemental analysis, and thermal analysis. The applicability for the chiral resolution of the CSP with poly[styrene‐b‐cellulose 2,3‐bis(3,5‐diphenylcarbamate)] was evaluated with high‐performance liquid chromatography with 10 racemates under various mobile phases of hexane/alcohol, hexane/tetrahydrofuran (THF), and hexane/chloroform. The results show that the CSP with poly[styrene‐b‐cellulose 2,3‐bis(3,5‐diphenylcarbamate)] could be used in THF and chloroform as eluents. The chiral resolutions of the commercial Chiracel OD, the CSP with cellulose 2,3‐bis(3,5‐dimethylphenylcarabmate), and the CSP with poly[styrene‐b‐cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate)] prepared by SI‐ATRP were examined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigations on the adhesion and interfacial properties of polyurethane foam/thermoplastic materials

The adhesion and interfacial properties of polyurethane (PU) foams with thermoplastic (TP) materials were investigated using different techniques. The adhesion performance of PU foam with TP materials was evaluated using the peel test method, and the adhesion durability was checked after different climate treatments. X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact angle measurements were used to study the surface and interface morphology of PU foam and TP material system. Three types of PU foam samples which differ in their composition and also five commercially available TP blends systems, based on poly(carbonate), poly(styrene‐co‐maleic anhydride), poly(acrylonitrile‐butadiene‐styrene), and silicone acrylate rubber have been used. The slow reacting foam shows the best adhesion properties with all the TP materials. The climate treatments strongly effected the PU foam adhesion durability with poly(carbonate) containing TP materials (70–80% loss in adhesion), but nearly no effect with poly(styrene‐co‐maleic anhydride). The samples with lowered adhesion could be separated by peeling without visible foam residues on the TP surface. AFM, XPS, and surface tension studies have shown that the surface properties of the TP material are still governed by the PU foam. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 479–488, 2007     

Dynamic–mechanical properties of modified poly(ethylene‐co‐vinyl acetate)

To study the relationship among relaxation peaks observed in dynamic mechanical experiments and the structure of poly(ethylene‐co‐vinyl acetate) (EVA), EVA copolymers with different substitution in the carbonyl group were synthesized. EVA was hydrolyzed to obtain poly (ethylene‐co‐vinyl alcohol) and was subsequently reacted with formic, hexanoic, and octanoic acids. The copolymers synthesized were characterized by infrared spectroscopy. Analysis of the DMA spectra of the copolymers showed that their relaxation behavior depends on the vinyl acetate concentration. The α‐ and β‐transitions were observed in EVA copolymers with 8 and 18 wt % of functional groups, and the relationship among relaxation process with the structure of polymer was investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1371–1376, 2005     

Meticulous analysis and consequences of microstructure changes on melt rheology and dynamic viscoelasticity of thermoplastic vulcanizates upon reprocessing

Thermoplastic vulcanizates (TPVs), which are a special class of elastomer alloy, prepared by dynamic vulcanization possess unique morphology of finely dispersed micron‐size cross‐linked elastomeric particles in a continuous thermoplastic matrix. The present study investigates the microstructure formation of elastomeric phase and its associated morphological changes during reprocessing of TPVs based on poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] triblock co‐polymer (S‐EB‐S) and solution polymerized styrene butadiene elastomer (S‐SBR) by scanning electron microscopy and atomic force microscopy. Semi‐efficient and efficient sulfur‐based curing systems have been adopted to cure the elastomeric phase and a comparative study has been made to demonstrate and explain the effect of reprocessing on the melt rheology and dynamic viscoelasticity of the TPVs. The present work also provides a better insight and guidance to control the microstructure of the cross‐linked elastomeric phase to prepare selectively co‐continuous or dispersed phase morphology. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41182.     

Investigation of modified SEBS‐based thermoplastic elastomers by temperature scanning stress relaxation measurements

Thermoplastic elastomers (TPEs) based on poly(styrene‐b‐ethylene/butylene‐b‐styrene) (SEBS), modified with poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE), were investigated by a new testing method. The development and characterization of TPEs with improved temperature and oil resistance is a current area of research to extend the applications of TPEs, especially in the automotive industry. Thermal scanning stress relaxation (TSSR) was used to investigate the relaxation behavior of compounds containing SEBS, blended with extender oil, various amounts of PPE and in some cases with a thermoplastic polymer. Polyamide 12 (PA12) or polypropylene (PP) were used as the thermoplastic component. TSSR measurements were applied to detect relaxation changes in the glass transition region of the polystyrene blocks mixed with PPE. It was shown that the glass transition temperature increased with addition of PPE to the compound up to a limit of approximately 150°C, which corresponded to a weight fraction of PPE in the polystyrene (PS)‐block of 0.5. The increased glass transition temperature lead to SEBS‐based thermoplastic elastomer compounds with improved upper service temperatures. Phase images obtained by atomic force microscopy showed that the addition of PPE results in an increase of hard phase dimension. The addition of a thermoplastic polymer improved the mechanical properties and temperature resistance, but naturally decreased the elasticity of the compounds. Compounds containing PA12 exhibited an improved oil resistance. POLYM. ENG. SCI., 45:1498–1507, 2005. © 2005 Society of Plastics Engineers     

Comparison of the performance of vulcanized rubbers and elastomer/TPE/iron composites for less lethal ammunition applications

One of the exciting novel potential applications of thermoplastic elastomers (TPEs) is less‐lethal ammunition (LLA). The importance of LLA in crowd control and law enforcement has been acknowledged, and became evident for air marshals after the September 11, 2001 crisis. This article will compare the dynamic mechanical behavior of various elastomer/TPE/iron composites and commercially available LLA based on conventional cured rubbers (ethylene‐propylene‐diene rubber [EPDM], styrene‐butadiene rubber [SBR], and natural rubber [NR]). Optimum combination of properties for LLA application was shown by the poly(styrene‐b‐isobutylene‐b‐styrene) (SIBS)/butyl elastomer (IIR)/iron 50/50/233 composite. POLYM. ENG. SCI., 45:966–975, 2005. © 2005 Society of Plastics Engineers