Dynamic mechanical behaviour of styrene/butadiene copolymers and their blends

The dynamic mechanical behaviour of high impact polystyrene (PS-HI), styrene/butadiene/styrene block copolymer (SBS) and PS-HI + SBS blends were investigated. Dynamic mechanical analysis (DMA) was performed in the temperature range −100°C to 100°C. The primary viscoelastic functions were determined. The copolymers PS-HI and SBS as well as PS-HI+SBS blends were investigated in creep-fatigue regime and relaxation at temperatures 25, 30, 35, 40 and 45°C. Dynamic mechanical behavior of PS-HI, SBS and PS-HI + SBS blends depends on the copolymer and blends composition, the hard phase content, time and temperature. With the decrement of the hard phase PS concentration, the loss tangent of the soft phase increases while the loss tangent of the hard phase and the storage modulus decrease. All samples have a single T_g of the hard phase and a single T_g of the soft phase. The glass transition temperatures decrease as the content of the PS phase decreases. At the constant load the creep values increase and those of creep modulus decrease over a period of time, for all examined samples. These effects are more pronounced in samples with lower content of hard phase and at higher temperatures. The time-temperature correspondence principle was applied to create master curves for the reference temperature 25°C for the creep modulus of PS-HI, SBS and PS-HI + SBS blends on a time scale far outside of the range measured by DMA experiments. These results enable us to predict the useful life of our copolymers and their blends in a wide range of time and temperature.     

Crystalline structure of polypropylene in blends with thermoplastic elastomers after electron beam irradiation

Isotactic polypropylene (PP) was blended in extruder with 0–50% addition of styrene–ethylene/butylene–styrene (SEBS) and styrene–butadiene–styrene (SBS) block copolymers. Granulated blends were irradiated with electron beam (60 kGy) and 1 week later processed with injection molding machine. Properties of samples molded from irradiated and non-irradiated granulates were investigated using DSC, WAXS, MFR, SEM and mechanical and solubility tests. It was found that the SEBS based systems are more resistant to irradiation in comparison to similar blends with SBS copolymer. Such behavior can be explained by the presence of double bonds in elastic SBS block. Irradiation of PP-SBS blends leads to considerable structure changes of crystalline and amorphous PP phases and elastic SBS phase. It indicates creation of new (inter)phase consisting of products of grafting and cross-linking reactions. Irradiated PP-SBS blends show significant improvement of impact strength at low temperatures.     

Block copolymers as compatibilizers for blends of linear low density polyethylene and polystyrene

Compatibilization of blends of linear low-density polyethylene (LLDPE) and polystyrene (PS) with block copolymers of styrene (S) and butadiene (B) or hydrogenated butadiene (EB) has been studied. The morphology of the LLDPE/PS (50/50) composition typically with 5% copolymer was characterized primarily by scanning electron microscopy (SEM). The SEB and SEBS copolymers were effective in reducing the PS domain size, while the SB and SBS copolymers were less effective. The noncrystalline copolymers lowered the tensile modulus of the blend by as much as 50%. Modulus calculations based on a coreshell model, with the rubbery copolymer coating the PS particle, predicted that 50% of the rubbery SEBS copolymer was located at the interface compared to only 5–15% of the SB and SBS copolymers. The modulus of blends compatibilized with crystalline, nonrubbery SEB and SEBS copolymers approached Hashin's upper modulus bound. An interconnected interface model was proposed in which the blocks selectively penetrated the LLDPE and PS phases to provide good adhesion and improved stress and strain transfer between the phases. © 1995 John Wiley & Sons, Inc.     

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.     

Effect of selected structural parameters of styrene–butadiene block copolymers on their compatibilization efficiency in polystyrene/polybutadiene blends

The effects of the block length and block number of linear styrene–butadiene (S–B) block copolymers on their compatibilization efficiency in blending polystyrene with polybutadiene were studied. For this purpose, two sets of model S–B copolymers and both homopolymers were prepared by anionic polymerization. Diblocks, triblocks, or pentablocks of S–B copolymers were blended with these homopolymers, and the structures and some end‐use properties of the blends were determined. The supramolecular structure (determined by small‐angle X‐ray scattering), morphology (determined by transmission and scanning electron microscopy), and stress‐transfer characteristics (impact and tensile strengths) of the blends were chosen as criteria for the compatibilization efficiency of the copolymers used. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2612–2623, 2002     

Effect of Styrene-Butadiene-Styrene Block Copolymer on Dynamic-Mechanical Properties of High-Impact Polystyrene

Abstract

For the selection of the polymer materials and polymer blends for various fields of applications, dynamic-mechanical properties, the primary viscoelastic functions as well as the stability of materials on different loads are very important. Since polymer materials are viscoelastic, their mechanical properties are dependent on temperature and time. The dynamic-mechanical properties of high-impact polystyrene, (PS-HI) and blends of PS-HI and styrene-butadiene-styrene block copolymer, (SBS) were investigated. Under the conditions of dynamic-mechanical load, the investigated systems will have different behavior due to the various content of the hard phase, polystyrene and soft phase, polybutadiene. The investigations were done by DMA analysis. The primary viscoelastic functions were determined. The influence of the constant stress on the strain and moduls at various temperatures was examined. The effects of the time on moduls changes was obtained by generating the master curves. The viscoelastic functions and the stability on the constant load, the changes of the moduls with time and temperature depend on the amount of polystyrene in the examined copolymers and blends. This investigation presents the possibility of predicting a useful lifetime of materials.     

Phase behavior in mixtures of a homopolymer and a block copolymer 1. FTIR and DSC studies

Miscibility in blends of three styrene-butadiene-styrene and one styrene-isoprene-styrene triblock copolymers containing 28%, 30%, 48%, and 14% by weight of polystyrene, respectively, with poly(vinyl methyl ether) (PVME) were investigated by FTIR spectroscopy and differential scanning calorimetry (DSC). It was found from the optical clarity and the glass transition temperature behavior that the blends show miscibility for each kind of triblock copolymers below a certain concentration of PVME. The concentration range to show miscibility becomes wider as the polystyrene content and molecular weight of PS segment in the triblock copolymers increase. From the FTIR results, the relative peak intensity of the 1100 cm^-1 region due to COCH₃ band of PVME and peak position of 698 cm^-1 region due to phenyl ring are sensitive to the miscibility of SBS(SIS)/PVME blends. The results show that the miscibility in SBS(SIS)/PVME blends is greatly affected by the composition of the copolymers and the polystyrene content in the triblock copolymers. Molecular weights of polystyrene segments have also affected the miscibility of the blends. ©1995 John Wiley & Sons, Inc.     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Investigation of the micromechanical deformation behavior of styrene–butadiene star block copolymer/polystyrene blends with high‐voltage electron microscopy

The deformation behavior of blends consisting of a styrene–butadiene star block copolymer and a polystyrene homopolymer was studied by high‐voltage electron microscopy with a tensile device. The mechanical properties and micromechanical deformation mechanisms in the star block copolymer/polystyrene blends were directly influenced by their morphology. Although the pure block copolymer deformed in a very unequal manner (because of a thin‐layer‐yielding mechanism) and revealed no local deformation zones, a transition to the formation of crazelike zones was observed in the blends. This transition in the deformation mechanisms was correlated to the abrupt change in the macroscopic strain at break of the injection‐molded specimens. At lower contents of added polystyrene, a craze‐stopping mechanism was observed, whereas the blends with higher polystyrene contents demonstrated crazing like that in pure polystyrene. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1157–1167, 2003     

Morphology and micromechanical behaviour of styrene/butadiene block copolymers and their blends with polystyrene

The correlation between the morphology and the deformation mechanism in styrene/butadiene block copolymers having modified architecture and in blends with homopolymer polystyrene (hPS) was studied. It was demonstrated that the morphology formation in the block copolymers is highly coupled with their molecular architecture. In particular, the micromechanical behaviour of a star block copolymer and its blends with polystyrene was investigated by using electron microscopy and tensile testing. A homogeneous plastic flow of polystyrene lamellae (thin layer yielding) was observed if the lamella thickness was in the range of 20 nm. The deformation micromechanism switched to the formation of craze-like deformation zones when the average PS lamella thickness changed to about 30 nm and more.     

Effect of butadiene/styrene ratio,block structure and carbon nanotube content on the mechanical and electrical properties of thermoplastic elastomers after UV ageing

Thermoplastic elastomers based on a triblock copolymer styrene-butadiene-styrene (SBS) with different butadiene/styrene ratios, block structure and carbon nanotube (CNT) content were submitted to accelerated weathering in a Xenontest, in order to evaluate their stability to UV ageing. It was concluded that ageing mainly depends on butadiene/styrene ratio and block structure, with radial block structures exhibiting faster ageing than linear block structures. Moreover, the presence of carbon nanotubes in the SBS copolymer slows down the ageing of the copolymer. The evaluation of the influence of ageing on the mechanical and electrical properties demonstrates that the mechanical degradation is higher for the C401 sample, which is the SBS sample with the largest butadiene content and a radial block structure. On the other hand, a copolymer derivative from SBS, the styrene-ethylene/butadiene-styrene (SEBS) sample, retains a maximum deformation of ∼1000% after 80 h of accelerated ageing. The hydrophobicity of the samples decreases with increasing ageing time, the effect being larger for the samples with higher butadiene content. It is also verified that cytotoxicity increases with increasing UV ageing, with the exception of SEBS, which remains non-cytotoxic up to 80 h of accelerated ageing time, demonstrating its potential for applications involving exposure to the environment.     

Dynamic mechanical and dielectric properties of epoxidized SBS triblock copolymer

The morphological and dynamic properties of epoxidized styrene–butadiene–styrene block copolymers were studied and compared with their parent styrene–butadiene–styrene block copolymer (SBS). Two peaks were observed in the mechanical loss (tan δ) curve which can be attributed to segmental motion of epoxidized polybutadiene (EPPB) and polystyrene. Analysis by DSC thermograms also showed the linear increase of glass transition temperature for EPPB domain with the epoxy group content. Phase separated structures of epoxidized SBS as observed by TEM suggests a considerable degree of mixing occurred between phases after 80 mol % of the double bonds in SBS were epoxidized. The interfacial region displays a third peak and causes much steeper drop in modulus at higher temperature than T_g of EPPB. Parallel dielectric relaxation measurements were also made in the frequency range of 30 Hz–1 KHz as a function of temperature. In each dielectric constant (?′) curve, there is a maximum near the T_g of EPPB determined from the dielectric loss tangent curve. The shift in T_g of EPPB versus epoxy group content was consistent with that measured by the thermal and dynamic mechanic analysis. These findings indicated an 8°C shift in glass transition temperature as the epoxy group content in EPPB increased 10%.     

Morphology and mechanical properties of binary triblock copolymer blends

The influence of the morphology on the mechanical properties of binary styrene–butadiene (SB) triblock copolymer blends of a thermoplastic block copolymer and a thermoplastic elastomer (TPE) with different molecular architectures was studied with bulk samples prepared from toluene. Both block copolymers contained SB random copolymer middle blocks, that is, the block sequence S–SB–S. The two miscible triblock copolymers were combined to create a TPE with increased tensile strength without a change in their elasticity. The changes in the equilibrium morphology of the miscible triblock copolymer blends as a function of the TPE content (lamellae, bicontinuous morphology, hexagonal cylinders, and worms) resulted in a novel morphology–property correlation: (1) the strain at break and Young's modulus of blends with about 20 wt % TPE were larger than those of the pure thermoplastic triblock copolymer; (2) at the transition from bicontinuous structures to hexagonal structures (～35 wt % TPE), a change in the mechanical properties from thermoplastic to elastomeric was observed; and (3) in the full range of wormlike and hexagonal morphology (60–100 wt % TPE), elastomeric properties were observed, the strength greatly increasing and high‐strength elastomers resulting. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 429–438, 2005     

Effect of mixing conditions on the morphology and properties of polystyrene/polyethylene blends compatibilized with styrene–butadiene block copolymers

The effect of mixing conditions on the morphology, molten‐state viscoelastic properties, and tensile impact strength of polystyrene/polyethylene (80/20) blends compatibilized with styrene–butadiene block copolymers containing various numbers and lengths of blocks was studied. Under all mixing conditions, an admixture of a styrene–butadiene block copolymer led to a finer phase structure and to an increase in the dynamic viscosity, storage modulus, and tensile impact strength. The effects were stronger for S–B diblock with a short styrene block than for S–B–S–B–S pentablock with long styrene blocks (where S represents styrene and B represents butadiene). For all blends mixed longer than 2 min, the mixing time had only a small effect on their morphology and properties. Surprisingly, the localization of S–B diblock copolymers was strongly dependent on the rate of mixing. The mixing rate had a nonnegligible effect on the viscoelastic properties of the compatibilized blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 609–622, 2003     

Ternary Donor–Insulator–Acceptor Systems for Polymer Solar Cells

A series of block copolymers with fixed length of the semiconductor‐block poly(3‐butylthiophene) (P3BT) and varying length of the insulator‐block polystyrene (PS) are synthesized. These copolymers are blended with phenyl‐C61‐butyric acid methyl ester (PCBM) for the bulk heterojunction photoactive layers. With appropriate insulator‐block length and donor–acceptor ratio, the power conversion efficiency increases by one order of magnitude compared with reference devices with pure P3BT/PCBM. PS blocks improve the miscibility of the active layer blends remarkably. The P3BT‐b‐PS crystallizes as nanorods with the P3BT core covered with the PS‐block, which creates a nanoscale tunneling barrier between donor and acceptor leading to more efficient transportation of charge carriers in the semiconductors.     

Selective swelling blends of block copolymers for nanoporous membranes with enhanced permeability and robustness

Block copolymers (BCPs) are important precursors to produce membranes with well‐defined porosities. However, it remains challenging to prepare robust and affordable BCP‐based membranes. In this work, cheap commodity styrene‐butadiene‐styrene (SBS) elastic triblock copolymers are mixed with polystyrene‐block‐poly (2‐vinylpyridine) (SV) block copolymers in solutions, leading to macroscopically stable blend films upon casting because of the compatibilizer effect of PS existing in both copolymers. By soaking the blend films in ethanol, the microdomains of poly(2‐vinylpyridine) are selectively swollen and cavitated upon drying, resulting in a hierarchical structure with perforated SV phases interwoven with the SBS phases. The blend membranes with 30% SBS exhibit improved water permeability and mechanical robustness due to the presence of elastic SBS compared to neat SV membranes; meanwhile, the rejections of the blend membranes remain largely unchanged. Moreover, the blend membranes exhibit a pH‐responsive function, and homoporous SV regions are obtained by pre‐aligning the SV phases. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1617–1625     

苯乙烯-丁二烯-苯乙烯/聚乙烯基甲基醚共混体系相容性的FT-IR及DSC研究

嵌段高聚物、均聚物共混体系相容性是近年来研究的热点。本工作以光学显微镜、DSC、FT-IR为手段,研究了三嵌段高聚物苯乙烯-丁二烯-苯乙烯(SBS);SBS-48、SBS-30,SBS-28与聚乙烯基甲基醚共混体系的相容性。DSC结果表明,随SBS中PS含量的升高,体系相容性变好,PS段分子量增大,也有助于体系相容。FT-IR结果表明PVME中COCH_3在1100cm~(-1)附近呈现的双峰的相对强度对体系的相容性十分敏感,而由于苯环C—H振动产生的698cm~(-1)峰位却不象PS/PVME体系那样随相容性的改变而有显著的改变。总而言之,嵌段高聚物SBS/均聚物PVME共混体系中,体系的相容性依赖于嵌段高聚物在体系中的组份含量及嵌段高聚物中PS的重量百分含量,PS段分子量的大小对体系相容性也有影响。     

The compatibilization effect of ethylene/styrene interpolymer on polystyrene/polyethylene blends

In this study, ethylene/styrene interpolymer (ESI) was used as compatibilizer for the blends of polystyrene (PS) and low‐density polyethylene (LDPE). The mechanical properties including impact, tensile properties, and morphology of the blends were investigated by means of uniaxial tension, instrumented falling‐weight impact measurements, and scanning electron microscopy. Impact measurements indicated that the impact strength of the blends increases slowly with LDPE content up to 40 wt %; thereafter, it increases sharply with increasing LDPE content. The impact energy of the LDPE‐rich blends exceeded that of pure LDPE, implying that the LDPE polymer can be further toughened by the incorporation of brittle PS minor phase in the presence of ESI. Tensile tests showed that the yield strength of the PS/LDPE/ESI blends decreases considerably with increasing LDPE content. However, the elongation at break of the blends tended to increase significantly with increasing LDPE content. The compatibilization efficiency of ESI and polystyrene‐hydrogenated butadiene‐polystyrene triblock copolymers (SEBS) for PS/LDPE 50/50 was further compared. Mechanical properties show that ESI is more effective to achieve a combination of LDPE toughness and PS rigidity than SEBS. The correlation between the impact property and morphology of the ESI‐compatibilized PS/LDPE blends is discussed. The excellent tensile ductility of the LDPE‐rich blends resulted from shield yielding of the matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2136–2146, 2007     

Effect of preparation method on nanoscopic structure of conductive SBS/PANI blends: Study using small‐angle X‐ray scattering

Small‐angle X‐ray scattering (SAXS) studies of electrically conductive blends based on polyaniline–dodecylbenzenesulfonic acid (PANI–DBSA)/styrene–butadiene–styrene (SBS) triblock copolymer were performed to investigate the influence of the blend preparation procedure on the nanoscopic structure of the blends. The blends were prepared by mechanical mixing (MM) procedure and by in situ polymerization (ISP) of aniline in the presence of SBS. The results indicate that pure PANI–DBSA presents an extended phase consisting of crystalline islands of nanometric size, with a good spatial correlation between them, embedded into an amorphous PANI phase. This feature was not observed in SBS/PANI–DBSA blends prepared by MM or ISP. In MM blends, the PANI phase is constituted by smaller domains, containing poorly spatially correlated crystalline islands, whereas in ISP blends with low or medium amount of PANI, there is no SAXS peak which could be related to a spatial correlation between PANI crystalline islands. The conductivity of the ISP blends is higher when compared to MM blends because of the higher homogeneity at nanometric scale. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3069–3077, 2007     

Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method

The content of styrene units in nonhydrogenated and hydrogenated styrene‐butadiene‐styrene and styrene‐isoprene‐styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene‐butadiene‐styrene and styrene‐isoprene‐styrene triblock copolymers (r  = 0.974 for styrene contents of 19.3–46.3% for nonhydrogenated ones and r  = 0.970 for the styrene contents of 23–58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene‐isoprene‐styrene or hydrogenated styrene‐butadiene‐styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene‐butadiene‐styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene‐containing polymers in blends such as poly(acrylonitrile‐butadiene styrene).