Structure and properties of a styrene–butadiene–styrene block copolymer

Electron-microscopic texture and physical properties of a styrene–butadiene–styrene (SBS) block copolymer obtained by casting from toluene, carbon tetrachloride, ethyl acetate, and methyl ethyl ketone are discussed. Two peaks are observed in the mechanical loss (tan delta;) curve at ?70 and 100°C which are attributed to segmental motion of polybutadiene and polystyrene, respectively. The polybutadiene peak heights are in the order of solubility in the solvent used; the polystyrene peak heights are in converse order. In addition to these peaks, a third peak is observed at 10°C for specimens cast from ethyl acetate or methyl ethyl ketone. A transition corresponding to this peak is also noticed in thermal analysis. It is proposed that aggregation of styrene blocks is relatively incomplete in specimens cast from solution in poor solvents.     

Nature of melt rheological transition in a styrene–butadiene–styrene block copolymer

Our laboratory previously reported the observation of a high temperature, melt rheological transition in a styrene–butadiene–styrene (S:7 × 10³ and B:43 × 10³) block copolymer from the highly elastic, nonlinear viscous behavior typical of a multiphase structure to linear viscous behavior with insignificant elasticity typical of a single-phase structure. We have investigated the precise nature of this melt rheological transition in the 7S-43B-7S sample by measuring the dynamic viscoelastic properties at more than 11 temperatures, including several in the transition region. A new procedure was developed for accurately measuring the sample temperature in a Weissenberg rheogoniometer. The transition is found to start at about 140°C and proceed over a narrow transition region from 140 to about 150°C. Data at all temperatures superimpose onto a single master curve only at high reduced frequencies. At low reduced frequencies, two characteristic branches of the master curve are formed. The data at temperatures below the transition region superimpose onto the upper branch where the dynamic viscosity η′(ω) is a strong function of ω, whereas the data at temperatures above the transition region superimpose onto the lower branch where η′(ω) is independent of ω. The data at temperatures within the transition region fall between the upper and lower branches, ordered according to their temperature positions. The apparent flow activation energy is found to be constant at about 22.8 kcal/mole below the transition region, but appears to decrease to about 17.4 kcal/mole above the transition region. The narrowness of the rheological transition far above the glass transition temperature of the polystyrene domains and the limiting linear viscoelastic behavior at low frequencies above the transition suggest an accompanying morphological transition rather than a gradual weakening of the polystyrene domains.     

Viscoelasticity of a butadiene–styrene block copolymer

A commercial elastomeric block copolymer of butadiene (B) with styrene (A) is studied. A single chain of the material has the formula A-B-A. Differential thermal analysis studies show the presence of two transitions. The lower transformation temperature corresponds to the T_g of the butadiene chain segments, and the upper transformation temperature corresponds to the T_g of the styrene chain segments. The upper transition of the material is also studied by following the variation of the torsional modulus with temperature. This transition is found to be quite unusual. Our experiments show that the upper transformation of unstressed block copolymer samples is broad. The transition sharpens for samples which, prior to the modulus–temperature experiments, are stress-relaxed at high elongations. These observations (and those of the literature) suggest that the styrene and butadiene chain segments in the block copolymer aggregate in the solid state and give rise to two distinct transition phenomena. Our studies of the upper transformation suggest that stretching of the bulk material enhances the aggregation of the styrene chain segments. Pure polystyrene (A) blocks of the material are recovered by selective cleavage and fractionation experiments. The T_g of the pure polystyrene blocks is found to be similar to the value of the upper transition temperature of the copolymer. The ABA blocks copolymer is found also to undergo a stress-softening phenomenon analogous to that of reinforced rubber.     

Epoxidation of styrene–butadiene–styrene block copolymer and use for gas permeation

The epoxidation of styrene–butadiene–styrene triblock copolymer (SBS) by an in situ generated peracid method is discussed. The presence of an acid acting as catalyst led to side reaction. The reactivities of internal double bonds (the 1, 4-structure) were higher than those of the vinyl bonds (the 1, 2-structure). In the 1, 4-structure, the reactivities of cis-structure were higher than those of trans-structure. The oxirane weight content and total oxygen weight content were determined by titration and element analysis, respectively. The cohesive energy, solubility parameter, and the glass transition temperature of epoxidized SBS increased with increasing total oxygen weight content. But the molecular weight between crosslinking points decreased resulting in an increase of crosslinking density with increasing total oxygen weight content. The changes of properties of epoxidized SBS reduced the gas permeability of oxygen and nitrogen through epoxidized SBS membrane, but increased the gas selectivity between oxygen and nitrogen. When the operating temperature of gas permeation was increased, the permeability of oxygen and nitrogen increased but the selectivity decreased. For epoxidized SBS containing 7.35 wt % oxygen content, the activation energy was 9 and 12.2 kcal/mol for oxygen and nitrogen, respectively.     

Effect of morphology on the mechanical and rheo-optical properties of a styrene–butadiene–styrene block copolymer

The mechanical and rheo-optical properties of a styrene–butadiene–styrene block copolymer of a given chemical composition are dependent upon the morphology of the polymer as affected by the solvent system from which a polymer film is cast. Films cast from methyl ethyl ketone and from toluene are compared. Properties found to differ are the stress–strain curve, the birefringence–strain curve, stress relaxation birefringence relaxation, and the dynamic mechanical spectra.     

Structure of styrene–butadiene–styrene block copolymers by diffusion analysis

In this study, solvent sorption was used to investigate the morphology of a styrene–butadiene–styrene (SBS) triblock copolymer. The sorption process was found to deviate from the normal Fickian character, usually found in conventional elastomer–solvent systems, because of the presence of an interfacial region for both polybutadiene and polystyrene. This interphase absorbed solvent at a temperature below its glass transition and contributed to the resulting non-Fickian time-dependent diffusion process. The equilibrium diffusion coefficient was estimated to be 3.2 × 10^?7 cm²/sec regardless of the casting surface. Nevertheless, according to the sorption measurements, the casting surface did have an effect on the approach to equilibrium. The results indicated a denser packing of the molecules and hence a decreased diffusion coefficient for Teflon and glass cast films, because of internal stresses left within the films during casting.     

Crazing in thin films of styrene–butadiene–styrene block copolymers

The mechanism of craze initiation and growth and its relationship to mechanical properties has been studied in thin films of styrene–butadiene–styrene (SBS) block copolymers. Optical microscopy and transmission electron microscopy were used to examine three copolymers which has a spherical rubber domain morphology but varied in rubber content from 20 to 50%. With increasing rubber content, the crazes became longer and less numerous. Widening of the crazes was at least partially responsible for the higher strains achieved in the copolymers, especially for the composition with the highest rubber content where the crazes widened to form micronecks. Transmission electron microscopy revealed that craze initiation and growth at the craze tip occurred by cavitation in the polystyrene phase. Cavitation of the continuous phase rather than the rubber domains was attributed to the concentration of chain-end flaws in the polystyrene. Crazes in the block copolymers followed a meandering pathway and the boundaries between crazed and uncrazed material were indistinct. Incorporation of fibrillated rubber particles into the craze fibrils strengthened the craze. At higher rubber content, the craze widened in the stress direction by voiding and fibrillation, which produced a cellular morphology.     

New anion conducting membranes based on functionalized styrene–butadiene–styrene triblock copolymer for fuel cells applications

In this work, the functionalization of polystyrene‐b‐poly(butadiene)‐b‐polystyrene triblock copolymer (SBS) with vinylbenzyl chloride and benzoyl peroxide (BPO) or α,α′‐azo‐bis‐isobutyronitrile (AIBN) as free radical initiators was reported. The functionalization degree (FD), calculated by ¹H NMR spectroscopy and confirmed by elemental analysis, was highly tunable (from 4 to 10 mol %) and positively correlated to the starting percentage of radical initiator. More specifically, at the same initiator molar percentage grafting efficiency is higher using BPO rather than AIBN. Quaternization reaction of the grafted benzyl chloride groups with the bifunctional tertiary amine 1,4‐diazabicyclo[2.2.2]octane (Dabco) led to a chemically and thermally stable homogeneous anion‐exchange membrane. Electrochemical parameters were evaluated for Dabco‐quaternized grafted copolymers having different FDs, and compared with a commercial Tokuyama benchmark membrane. Experimental data showed a positive correlation between FD and both water swelling and ionic conductivity. Best trade‐off between ionic conductivity and water swelling was found for membrane having FD 9.1 mol %, which conductivity is comparable with the Tokuyama benchmark one and water uptake is only slightly higher. The results are discussed based on the molecular parameters with particular reference to ionic content and distribution. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Free radicals in electron beam irradiated blends of polyethylene and butadiene–styrene block copolymer

Two-components blends, of compositions in a range from 100% of high density polyethylene (PE) to 100% of butadiene–styrene block copolymer (SBS) were investigated from the point of view of basic radiation chemistry and modifications of technological and chemical properties. Irradiations were performed with 10 MeV electrons to doses of 30, 60 and 120 kGy, by the split dose technique to avoid thermal effects. EPR spectra were measured with the Bruker 300 ESP spectrometer, using a computer program for the deconvolution and analysis of spectra.     

Membrane of epoxidized styrene–butadiene–styrene block copolymer complexing with (N,N′-disalicylideneethylenediamine) cobalt (II) and use for oxygen permeation

The complex formation reaction of epoxidized styrene-butadiene-styrene triblock copolymer (ESBS) with (N,N-disalicylideneethylenediamine) cobalt(II) (CoS) in chloroform solution is studied. The coordination number and formation constant are determined by the Miller method. The membranes of ESBS complexing with CoS (ESBS–CoS) are made by solution casting method. The kinetics of oxygen binding to ESBS–CoS membrane is studied and the equilibrium constant, association, and dissociation constant are determined. The membrane of ESBS–CoS has the affinity to absorb oxygen with reversibility and that is confirmed by the studies of DSC. Due to the reversible absorption of oxygen to ESBS–CoS, the permeation of oxygen through ESBS–CoS membrane can be explained by dual mode.     

Steady flow and dynamic viscosity of branched butadiene–styrene block copolymers

Steady flow and dynamic viscosities were determined for symmetrical linear and starbranched block copolymers of butadiene and styrene above their upper (polystyrene) glass transition. Block structures examined were B-S-B, (B-S-)₃, S-B-S, (S-B-)₃ and (S-B-)₄. At constant molecular weight and total styrene content viscosities were greater for polymers terminating in styrene blocks, irrespective of branching. Branching decreased the viscosity of either polybutadiene-terminated or polystyrene-terminated block polymers, compared at equal M _w. However, comparisons at equal block lengths showed that the length of the terminal blocks, not the total molecular weight, governs the viscoelastic behavior of these polymers to a surprisingly good approximation. This unusual result is rationalized in terms of the two-phase domain structure of these polymers, which persists to a significant degree in the melt. Below the glass transition of the polystyrene blocks the effects of branching were masked by differences in the morphology of the domain structure unrelated to branching.     

Wavelength sensitivity of acrylonitrile–butadiene–styrene

The wavelength sensitivity of unpigmented 100 mil thick ABS exposed to sunlight and filtered xenon are radiation was determined by the sharp cut filter technique based on three types of photochemical changes: bleaching, yellowing and loss in impact strength. Bleaching of the yellow-colored species formed in the processed material is caused by wavelengths between 380 and 525 nm with maximum color change by the 475–485 nm region. Photochemical yellowing is due to wavelengths between 300 and 380 nm with all wavelengths being almost equally effective. The spectral sensitivity based on change in impact strength shifts from the UV to the visible region as photochemical yellowing progresses. Addition of two stabilizers, a benzotriazole ultraviolet absorber and a hindered amine stabilizer, shifts the wavelength sensitivity based on yellowing to wavelengths shorter than 330 nm, but has no influence on the spectral effects based on impact strength. It is postulated that the rate of yellowing is reduced mainly by the ultraviolet absorber and stabilization against loss in impact strength is due largely to the hindered amine. Differences in rates and spectral response of the three types of photochemical changes indicate that they are due to different initiating mechanisms and thus require different types of stabilization. The significance to stability testing is discussed.     

Nonlinear viscoelastic behavior of styrene‐[ethylene‐(ethylene‐propylene)]‐styrene block copolymer

Studies on the nonlinear viscoelastic behavior of styrene‐[ethylene‐(ethylene‐propylene)]‐styrene block copolymer (SEEPS) were carried out. The nonlinear viscoelastic region was determined through dynamic strain sweep test, and the critical shear strain (γ_c) of transition from linear viscoelastic region to nonlinear viscoealstic region was obtained. The relaxation time and modulus corresponding to the characteristic relaxation modes were also acquired through simulating the linear relaxation modulus curves using Maxwell model, and the damping functions were evaluated. Meanwhile, it is found that the nonlinear relaxation modulus obtained at relatively low shear strains follows the strain–time separation principle, and the damping function of SEEPS can be fit to Laun double exponential model well. Moreover, the successive start‐up of shear behavior, the steady shear behavior, and the relaxation behavior after steady shear were investigated, respectively. The results showed that Wagner model, derived from the K‐BKZ (Kearsley‐Bernstein, Kearsley, Zapas) constitutive equation, could simulate the experiment data well, and in addition, experiment data under the lower shear rates are almost identical with the fitting data, but there exists some deviation for data under considerable high shear rates. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1309–1319, 2006     

Solution behavior of styrene–ethylene oxide block copolymers

Hydrophobic–hydrophilic water-soluble block copolymers were prepared by “living” anionic polymerization. They consist of a polystyrene block and a polyethylene oxide block. From data on solution viscosity and high-resolution NMR in water, the molecular dimensions of the two-blocks copolymers are found similar to that of polyethylene glycols of the same molecular weight in the same solvent. These block copolymers exhibit microphase separation.     

Studies on thermal degradation of acrylonitrile–butadiene–styrene copolymer (ABS-Br) containing brominated flame retardant

The thermal degradation of acrylonitrile-butadiene-styrene copolymer (ABS-Br; 10 g) containing brominated flame retardant (Br: 9.59 wt.%) was carried out at 450 °C using a semi batch operation using two different temperature programs. The heating rate was found to affect the quality of the degradation oil and yield of products (liquid, gas and residue). Data on the effect of the temperature program on the accumulation of liquid products was presented. It was found that the majority of the bromine was concentrated in the carbon residue and while majority of the nitrogen accumulates in the liquid products irrespective of degradation mode. The use of a one step constant heating rate process (I) produced a higher liquid yield (39%), than a two step process (29%). Differences were also noted in the Br and N contained in the liquids produced by the two processes.     

Morphology and mechanical properties of styrene–butadiene–styrene/poly(methyl methacrylate–co-n-butyl acrylate) interpenetrating polymer networks

A series of interpenetrating polymer networks (IPNs) based on styrenic triblock copolymer, polystyrene-b-polybutadiene-b-polystyrene (SBS), and random copolymer of methyl methacrylate (MMA) and n-butyl acrylate (nBA) were prepared. Corresponding semi-IPNs of the same composition without a crosslinking agent were also synthesized for comparison, and toluene was used as a common solvent to investigate the influence of the presence of the common solvent during the IPN synthesis. Throughout the compositions of IPNs tested, SBS appears to form a continuous phase and the domain size decreases gradually with the increase in SBS concentration. IPNs are found to have finer domain sizes than semi-IPNs because of the higher intermixing between polymers. The microstructure of SBS could be observed using highly magnified transmission electron microscopy (TEM). The dynamic mechanical behavior of the IPNs shows the inward shifting of two glass transition peaks, corresponding to polybutadiene phase of SBS and p(MMA–co-nBA) phase respectively, which indicates enhanced intermixing. The increase in loss tangent of styrene blocks of SBS by the addition of common solvent indicates the structural change of the microstructure in SBS, and this structural change can also be confirmed through the observation of the morphology of SBS-rich phase with higher magnification. © 1997 John Wiley & Sons, Ltd.     

Electric,dielectric, and dynamic mechanical behavior of carbon black/styrene‐butadiene‐styrene composites

The conductivity of styrene‐butadiene‐styrene block copolymers containing different amounts of extraconductive carbon black (CB) was investigated as a function of the mold temperature. The composites exhibited reduced percolation thresholds (between 1.0 and 2.0 vol % CB). The dynamic mechanical analysis characterization revealed that the glass‐rubber‐transition temperatures of both segments were not affected by the CB addition, although the damping of the polybutadiene phase displayed a progressive drop with an increase in the CB concentration. The normalized curves of tan δ/tan δ_max (where tan δ represents the value of the loss tangent at any measurement temperature and tan δ_max represents the loss tangent peak value at the corresponding temperature T_max) versus T/T_max (where T is the temperature and T_max is the maximum temperature), corresponding to both polystyrene and polybutadiene phases as well as the activation energy related to the glass‐rubber‐transition process, did not present any significant change with the addition of CB. The dielectric analysis revealed the presence of two relaxation peaks in the composite containing 1.5 vol % CB, the magnitude of which was strongly influenced by the frequency, being attributed to interfacial Maxwell‐Wagner‐Sillars relaxations caused by the presence of different interfaces in the composite. The mechanical properties were not affected by the presence of CB at concentrations of up to 2.5 vol %. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2983–2997, 2003     

Interphase control in poly(styrene‐block‐butadiene‐block‐styrene) copolymer/magnesium hydroxide composites

The role of isostearic acid (ISA) and maleinised polybutadiene (MPBD) in the interphase control of SBS/magnesium hydroxide composites was investigated. Infrared studies showed that both ISA and MPBD interact chemically with the magnesium hydroxide. Flow microcalorimetry studies showed that model polymers that resemble the two phases of SBS (polybutadiene and polystyrene), were absorbed irreversibly on the surface of magnesium hydroxide. Differences in mechanical responses showed that filler surface modification with MPBD led to increased filler‐matrix adhesion compared to the composite based on untreated. ISA treatment of the filler led to reduced melt viscosities and filler‐matrix interaction, but resulted in higher levels of strain induced crystallization, relative to the composites based on untreated and MPBD treated magnesium hydroxide.