Morphology of pyrolyzed polystyrene–isoprene–styrene and polystyrene–butadiene–styrene block copolymers

The surface morphology of thermooxidative‐degraded polystyrene–isoprene–styrene (SIS) and polystyrene–butadiene–styrene (SBS) thermoplastic block copolymers were studied by scanning electron microscopy. Surface changes caused by heating the samples in a pyrolizer for 15 and 30 min were presented in different micrographs. The morphological changes occurring due to the formation of polar groups and their crossing linking during the thermooxidative degradation are discussed. Morphological study of these thermally degraded polymer samples show very good correlation with the thermodegradation results. The rate of thermodegradation is fast in case of SBS compared with SIS block copolymer. ©2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

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     

Blends of styrene–butadiene–styrene triblock copolymer and isotactic polypropylene: morphology and thermomechanical properties

A set of blends of styrene–butadiene–styrene triblock copolymer (SBS) and isotactic polypropylene (i‐PP) in a composition range 0–100 % polypropylene by weight was prepared in a twin screw extruder. The morphology of the blends has been studied by transmission electron microscopy. The blends present phase separation. Dynamic mechanical measurements show an improvement of the mechanical properties of SBS when i‐PP is the dispersed phase. This reinforcing effect can be observed even at high temperatures when i‐PP is in the rubbery state. The mechanical properties of the blends have been interpreted using Takayanagi's block model. The melting and crystallization behaviour of the i‐PP in the blends has been studied by differential scanning calorimetry. The fractionated crystallization phenomenon has been observed in the blends where i‐PP forms the dispersed phase. The results are consistent with the morphology shown by the blends, in particular, with its phase inversion, which occurs at a composition near to 50% i‐PP. © 2000 Society of Chemical Industry     

Novel method for preparation of quaternary ammonium ionomer from epoxidized styrene–butadiene–styrene triblock copolymer and its use as compatibilizer for blending of styrene–butadiene–styrene and chlorosulfonated polyethylene

A novel method for the preparation of a quaternary ammonium ionomer of styrene–butadiene–styrene triblock copolymer (SBS) was developed by a ring‐opening reaction of epoxidized SBS with triethylamine hydrochloride in the presence of a phase transfer catalyst. The optimum conditions were studied. The ionomer was characterized by quantitative analysis, IR spectroscopy, and ¹H‐NMR spectroscopy. Its water absorbency, oil absorbency, dilute solution viscosity, and use as a compatibilizer for the blending of SBS and chlorosulfonated polyethylene (CSPE) were investigated. The results showed that, under optimum conditions, the epoxy groups can be completely converted to the quaternary ammonium groups. The IR spectrum did not exhibit the absorption peak for quaternary ammonium groups, whereas the ¹H‐NMR spectrum and titration method demonstrated it. With increasing ionic group content, the water absorbency of the ionomer increased whereas its oil absorbency decreased. These indicated the amphiphilic character of the SBS ionomer. The dilute solution viscosity of the ionomer in toluene/methanol (9/1) solvent increased with increasing quaternary ammonium group content. The ionomer was used as a compatibilizer for the blends of SBS and CSPE. The addition of a small amount of the ionomer to the blend enhanced the mechanical properties of the blends: 2 wt % ionomer based on the blend increased the tensile strength and ultimate elongation of the blend nearly 2 times. The blends of equal parts SBS and CSPE behaved as oil‐resistant thermoplastic elastomers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1975–1980, 2006     

Grafting of maleic anhydride onto styrene–butadiene–styrene triblock copolymer using supercritical CO2 as a swelling agent

Grafting of maleic anhydride (MA) onto styrene–butadiene–styrene triblock copolymer (SBS) was carried out by free radical polymerization using supercritical carbon dioxide (SC CO₂) as a solvent of MA and swelling agent of SBS. The effect of various factors such as monomer concentration, initiator concentration, SC CO₂ pressure, and reaction time on grafting ratio was studied. SBS and the product (SBS‐g‐MA) were characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). GPC data showed that the molecular weight of SBS‐g‐MA is bigger than that of SBS. DSC testing indicated that the glass transition temperature (T_g) of SBS‐g‐MA is higher than that of SBS. By SEM photo, we can observe that some particles which contain more oxygen atom grew out from the surface of SBS‐g‐MA when grafting ratio reached at 5.6%, and the amount and diameter of particles increased with increasing of grafting ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4425–4429, 2006     

Photooxidative degradation of styrenic polymers: 13C-NMR and morphological changes upon irradiation

Thin films of high impact polystyrene (HIPS 8350) and styrene–butadiene–styrene triblock copolymers (SBS) were exposed to polychromatic light for different time intervals in SEPAP 12/24 at 55°C in atmospheric air. The photooxidized samples were analyzed by ¹³C-NMR spectroscopy in the liquid state. Epoxides and alcohols were photoproducts in the SBS. Epoxides were not observed in the HIPS. The morphological changes of the solution cast HIPS and SBS films caused by irradiation were studied by scanning electron microscopy. The property deterioration was explained in terms of scission reactions in the HIPS and SBS matrix. The micrographs indicate that both materials are of a two phasic system. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 637–645, 1998     

Effects of molecular weight and arm number on properties of star‐shape styrene–butadiene–styrene triblock copolymer

A star‐shape styrene–butadiene–styrene triblock copolymer SBS (802) was synthesized and fractionated into four fractions coded as 802‐F1 (four arms), 802‐F2 (two arms), 802‐F3 (one arm), and 802‐F4 by repeating fractional precipitation. Their weight‐average molecular weight (M_w) was measured by size‐exclusion chromatography combined with laser light scattering to be 16.0 × 10⁴, 8.2 × 10⁴, 4.3 × 10⁴, and 1.19 × 10⁴, respectively. The samples were, respectively, compression‐molded and solution‐cast to obtain the sheets coded as 802C, 802‐F1C, 802‐F2C, and 802S, 802‐F1S, 802‐F2S. The structures and mechanical properties of the sheets were characterized by ¹H‐NMR, scanning electron microscope, wide‐angle X‐ray diffractometer, tensile testing, and dynamic mechanical thermal analysis. The results indicated that the compression‐molded 802‐F1C exhibited the higher tensile strength (σ_b, 28.4 MPa) and elongation at break (ε_b, 1610%), and its optical transmittance is much higher than those of 802C and 802‐F2C. This work revealed that the star‐shape SBS with four arms could be helpful in the enhancement of the properties as a result of good miscibility of the compression‐molded SBS sheets. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 832–840, 2005     

Preparation and properties of styrene–ethylene–butylene–styrene block copolymer/clay nanocomposites: I. Effect of clay content and compatibilizer types

BACKGROUND: Polymer/clay (silicate) systems exhibit great promise for industrial applications due to their ability to display synergistically advanced properties with relatively small amounts of clay loads. The effects of various compatibilizers on styrene–ethylene–butylene–styrene block copolymer (SEBS)/clay nanocomposites with various amounts of clay using a melt mixing process are investigated. RESULTS: SEBS/clay nanocomposites were prepared via melt mixing. Two types of maleated compatibilizers, styrene–ethylene–butylene–styrene block copolymer grafted maleic anhydride (SEBS‐g‐MA) and polypropylene grafted maleic anhydride (PP‐g‐MA), were incorporated to improve the dispersion of various amounts of commercial organoclay (denoted as 20A). Experimental samples were analyzed using X‐ray diffraction and transmission electron microscopy. Thermal stability was enhanced through the addition of clay with or without compatibilizers. The dynamic mechanical properties and rheological properties indicated enhanced interaction for the compatibilized nanocomposites. In particular, the PP‐g‐MA compatibilized system conferred higher tensile strength or Young's modulus than the SEBS‐g‐MA compatibilized system, although SEBS‐g‐MA seemed to further expand the interlayer spacing of the clay compared with PP‐g‐MA. CONCLUSION: These unusual results suggest that the matrix properties and compatibilizer types are crucial factors in attaining the best mechanical property performance at a specific clay content. Copyright © 2007 Society of Chemical Industry     

Grafting of N‐carbamyl maleamic acid onto a styrene–butadiene–styrene copolymer

A styrene–butadiene–styrene block copolymer (SBS) was functionalized with N‐carbamyl maleamic acid (NCMA) using two peroxide initiators with the aim of grafting polar groups onto the molecular chains of the polymer. The influence of the concentration of benzoyl peroxide (BPO) and 2,5‐dimethyl, 2,5‐diterbuthylperoxihexane (DBPH) was studied. The concentration of peroxy groups ranged between 0.75 and 6 × 10^?4 mol % while the concentration of NCMA was constant at 1 wt %. The reaction temperature was chosen according to the type of peroxide employed, being 140°C for BPO and 190°C for DBPH. FTIR spectra confirmed that NCMA was grafted onto the SBS macromolecules. It was found that the highest grafting level was achieved at a concentration of peroxy groups of about 3 × 10^?4 mol %. Contact angle measurements were used to characterize the surface of the SBS and modified polymers. The contact angle of water drops decreased with the amount of NCMA grafted from 95°, the one corresponding to the SBS, to about 73°. T‐peel strength of polymer/polyurethane adhesive/polymer joints made with the modified polymers was larger than those prepared with the original SBS. The peel strength of SBS modified with 1.5 and 3 × 10^?4 mol % of peroxy groups from BPO were five times larger than that of the original SBS. The materials modified using BPO showed peel strengths higher than the ones obtained with DBPH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4468–4477, 2006     

Swelling behaviours of styrene–isoprene–styrene triblock copolymers in supercritical methane

Styrene–isoprene–styrene triblock copolymers (SIS) are representative thermoplastic elastomers possessing both elastomeric and thermoplastic feature. SIS have been used in self-healing cement for natural gas wells, but the mechanism behind the application was not unravelled. We hypothesise such self-repairing function should be associated with the swelling of SIS in natural gas whose main component is methane. It was found that all the four SIS copolymers show similar swelling trend irrespective of their structure difference, and the swelling ratio increases as decreasing the polystyrene block content in SIS. These preliminary pioneering findings show the swelling behaviour of the rubbers displayed quite differently before and after supercritical point, and it is helpful for the further research about the swelling behaviour of rubber in natural gas wells.     

Synergistic effect of dual rubber system in toughening styrene maleic anhydride copolymers

Styrene maleic anhydride (SMA) copolymers were toughened by blending with two distinctly different rubber modifiers: styrene‐butadiene‐styrene (SBS) block copolymer and methacrylated butadiene‐styrene emulsion‐made graft copolymer (MBS). The modifiers were used both individually and in combination for the examination of their roles in toughening SMA. SMA was miscible with poly(methylmethacrylate) shell of MBS, whereas it was partially miscible with the polystyrene (PS) phase of SBS. When 40–50% of SBS was used in blends, the PS phase of SBS became immiscible with SMA. SBS did not improve the Izod impact strength of SMA appreciably. A prominent synergistic toughening effect was experimentally observed when SBS and MBS were used in combination in brittle SMA. This effect may be attributed to the fact that the large SBS particles initiate crazes and small MBS particles with good adhesion to SMA matrix improve the ligament thickness, which may play a critical role in craze growth and termination. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2260–2267, 2003     

Photodegradation and stabilization of styrene–butadiene–styrene rubber

Photooxidative degradation and stabilization of a polystyrene–block–polybutadiene–block–polystyrene thermoplastic elastomer using a polychromatic UV light in air at 60°C has been studied by monitoring the appearance of the hydroxyl and carbonyl groups in Fourier transform infrared spectroscopy. The extent of photooxidative degradation in different samples has been compared. The rate of photooxidation was also estimated in the presence of different concentrations of 2,6‐di‐tert‐butyl‐4‐methylphenol [BHT], 2‐(2′‐hydroxy‐5′‐methylphenyl)benzotriazole [Tinuvin P] and tris(nonylphenyl) phosphite [Irgafos TNPP], and 1,2,2,6,6‐pentamethyl piperidinyl‐4‐acrylate was grafted onto the surface of the SBS film. The kinetic evolution of the oxidative reaction was determined. The morphological changes upon irradiation in the solution cast SBS films were studied by scanning electron microscopy. Based on the experimental data a suitable photooxidative degradation mechanism also has been proposed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1097–1102, 2000     

Polystyrene nanocomposite materials by in situ polymerization into montmorillonite–vinyl monomer interlayers

A different series of new polystyrene–clay nanocomposites have been prepared by grafting polymerization of styrene with vinyl‐montmorillonite (MMT) clay. The synthesis was achieved through two steps. The first step is the modification of clay with the vinyl monomers, such as N,N‐dimethyl‐n‐octadecyl‐4‐vinylbenzyl‐ammonium chloride, n‐octadecyl‐4‐vinylbenzyl‐ammonium chloride, triphenyl‐4‐vinylbenzyl‐phosphonium chloride, and tri‐n‐butyl‐4‐vinylbenzyl‐phosphonium chloride. The second step is the polymerization of styrene with different ratios of vinyl‐MMT clay. The materials produced were characterized by different physical and chemical methods: (1) IR spectra, confirming the intercalation of the vinyl‐cation within the clay interlayers; (2) thermogravimetric analysis (TGA), showing higher thermal stability for PS–nanocomposites than polystyrene (PS) and higher thermal stability of nanocomposites with of phosphonium moieties than nanocomposites with ammonium moieties; (3) swelling measurements in different organic solvents, showing that the swelling degree in hydrophobic solvents increases as the clay ratio decreases; (4) X‐ray diffraction (XRD), illustrating that the nanocomposites were exfoliated at up to a 25 wt % of organoclay content; and (5) scanning electron microscopy (SEM), showing a complete dispersion of PS into clay galleries. Also, transmission electron microscopy (TEM) showed nanosize spherical particles of ～ 150–400 nm appearing in the images. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3739–3750, 2007     

Synthesis and properties of vinyltrimethoxysilane–EPDM–styrene graft terpolymer

The graft copolymerizations of vinyltrimethoxysilane (VTMO) and styrene (St) onto ethylene–propylene–diene terpolymer (EPDM) were carried out with benzoyl peroxide (BPO) as an initiator in toluene. The effects of EPDM concentration, mole ratio of VTMO to St, reaction time, reaction temperature, and initiator concentration on the graft copolymerizations were examined. The synthesized VTMO–EPDM–St graft terpolymers (VES) were confirmed by infrared and ¹H-NMR spectroscopies. The molecular weight, thermal stability, light resistance, and weatherability of the graft terpolymer were investigated by gel permeation chromatography, thermogravimetric analysis, and Fade-o-Meter. The number-average molecular weight was 109,000. It was found that the heat resistance and light resistance as well as weatherability of VES are considerably better than those of acrylonitrile–butadiene–styrene terpolymer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1345–1352, 1998     

Dynamic mechanical properties of polycarbonate and acrylonitrile–butadiene–styrene copolymer blends

Blends of polycarbonate (PC) and poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) with different compositions are characterized by means of dynamic mechanical measurements. The samples show phase separation. The shift in the temperatures of the main dynamic mechanical relaxation shown by the blend with respect to those of the pure components is attributed to the migration of oligomers present in the ABS toward the PC in the melt blending process. A comparison with other techniques (dielectric and calorimetric analysis) and the application of the Takayanagi three block model confirm this hypothesis. In all the studied blend compositions (ABS weight up to 28.6%) the PC appears as the matrix where a disperse phase of ABS is present. The scanning and transmission electron microscopy micrographs show that the size of the ABS particles increases when the proportion of ABS in the blend increases. The FTIR results indicate that the interaction between both components are nonpolar in nature and can be enhanced by the preparation procedure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1507–1516, 2002     

Behavior of ionomers of sulfonated styrene–butadiene–styrene triblock copolymer in polymer blends with crystalline polyolefins and as compatibilizer

The blends of ionomers of sulfonated (styrene–butadiene–styrene) triblock copolymer with two polyolefins as well as the blends of polystyrene (PSt) with two polar, oil‐resistant elastomers, i.e., chlorohydrin rubber (CHR) and chlorosulfonated polyethylene (CSPE), using the ionomer as compatibilizer were studied. The blends of the ionomer with polypropylene or high density polyethylene showed synergistic effects with respect to tensile strength. With increasing PSt content, the blends change their behavior from thermoplastic elastomer to toughened plastics. The synergism is probably because of the thermoplastic interpenetrating polymer networks formed in the blend. The blends exhibited high resistance against diesel oil or toluene. When PSt was blended with CHR or CSPE using the ionomer as compatibilizer, only 2 or 3% ionomer was needed to enhance the mechanical properties of the blends. The effect is due to the ion–polar interaction of the ionomer with the polar polymer. The enhanced compatibility of the blends by the ionomer was demonstrated by DSC and Scanning electron micrograph. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1887–1894, 2006     

Styrene–substituted‐styrene copolymerization using diphenylzinc–metallocene–methylaluminoxane systems

Homopolymerization of disubstituted styrenes (2,4‐ and 2,5‐dimethylstyrene) and trisubstituted styrene (2,4,6‐trimethylstyrene) and their copolymerization with styrene were carried out using diphenylzinc–metallocene–methylaluminoxane initiator systems for metallocene (n‐BuCp)₂TiCl₂ and for half‐metallocene CpTiCl₃. The studied comonomers were found to be less reactive than p‐tertbutylstyrene, p‐methylstyrene and styrene. The results indicate that, even though the methyl group has I+ inductive effect, di‐ and tri‐methylstyrenes are reluctant to undergo either homopolymerization or copolymerization. This behavior suggests that the reactivity is regulated not only by the inductive effect of the alkyl group but also by the steric impediment caused by the crowding of the substituents on the benzene ring. Copyright © 2006 Society of Chemical Industry     

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

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

Recycling of acrylonitrile–butadiene–styrene and high‐impact polystyrene from waste computer equipment

Acrylonitrile–butadiene–styrene (ABS) and high‐impact polystyrene (HIPS) are two of the plastics most frequently used as outer casings for computer equipment such as monitors, keyboards, and other similar components. We assessed the effects of the recycling and blending of ABS and HIPS on mechanical properties. We found that the effects of recycling on ABS and HIPS were similar, in that changes in glass‐transition temperatures, tensile strengths, and tensile moduli were negligible, but strains to failure and impact strengths were reduced considerably. Blending proportions of ABS and HIPS caused no more deterioration in properties than occurred as a result of the recycling process, and the presence of small proportions of one material in the other actually restored significant amounts of ductility, as seen by increases in the strains to failure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 572–578, 2002     

Studies on dynamically vulcanized polypropylene (PP)/butadiene styrene block copolymer (SBS) blends: Crystallization and thermal behavior

Crystallization of polypropylene (PP) in unvulcanized blends of PP with the butadiene–styrene block copolymer (SBS) was studied through differential scanning calorimetry (DSC) and X‐ray diffraction measurements in the composition range of 0–40 wt % SBS content. Analysis of the crystallization exotherms revealed variation in the crystallization behavior, crystallinity, and crystalline morphology of the PP component in the blends at various levels of SBS concentration. The crystallinity determined by X‐ray diffraction and DSC showed identical variations with the blend composition. The tensile and thermal properties of the blends were studied in the entire composition range. Correlations of the tensile properties with the crystallization parameters of the PP component in the blends are also presented. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 151–161, 1999