Thermal properties and morphology of α-methylstyrene-butadiene-α-methylstyrene triblock copolymer

Poly(α-methylstyrene-butadiene-α-methylstyrene) (mSBmS) was synthesized by two stages living anionic polymerization. Sodium naphthalene was used as initiator and HMPT as promoter to accelerate cross-over reactions. The microstructure and composition of mSBmS were identified by infrared and nuclear magnetic resonance spectroscopes. The domain size was roughly calculated from TEM observation. It was observed that the morphology changed with the composition. The mSBmS exhibited two T_g^s, ?4 and 172°C, that associated with polybutadiene and poly-α-methylstyrene, respectively. Comparing stress relaxation behaviors of mSBmS and styrene-butadienestyrene (SBS) at various temperatures, mSBmS showed a better thermal stability and degradation resistance than SBS. From the thermal gravimetric analysis, at 200°C, mSBmS gave a weight loss less than 1%, which provided a further evidence of better thermal stability of this material than of SBS.     

Newtonian behavior of a styrene–butadiene–styrene block copolymer

The melt rheological behavior of an anionically polymerized styrene–butadiene–styrene (SBS) block copolymer sample (S: 7 × 10³ and B: 43 × 10³) was studied using a Weissenberg rheogoniometer. Highly non-Newtonian behavior, high viscosity and high elasticity, which are characteristics of ABA type block copolymers, were observed at 125°C, 140°C, and 150°C. The data at these temperatures superimposed well onto a master curve giving a constant flow activation energy. However, the data at 175°C indicated a marked change in the flow mechanism between 150°C and 175°C. At 175°C, the sample showed Newtonian behavior, negligible elasticity, and deviation from the master curve. These findings may be considered as an indication that the SBS block copolymer sample undergoes a structural change from a multiphase structure at low temperatures into a homogeneous structure at some temperature between 150°C and 175°C.     

Ultrasonic absorption and dielectric loss in heterophase block copolymers

A styrene–butadiene–styrene block copolymer (SBS) and a plasticized SBS were studied as a function of temperature by an ultrasonic wave propagation technique at 9 MHz. Two absorption maxima were found for each of these polymers, one being attributable to the primary glass transition of the polybutadiene blocks and the other to that of the polystyrene blocks. The SBS was cast from two different solvents, namely benzene and tetrahydrofuran–methyl ethyl ketone. Parallel dielectric loss measurements were also made of the SBS in the frequency range of 50–10⁵ Hz. Relaxation temperatures determined from the ultrasonic and dielectric loss maxima over a range of measurement frequencies can be correlated by an Arrhenius-type equation. The polystyrene loss peak in the ultrasonic data was found to be much weaker than the polybutadiene loss peak. However, these two peaks were of comparable magnitude in dielectric data. This observation was interpreted as being due to the onset of structured–unstructured (heterophase to homogeneous) transitions at sufficiently high temperatures. Ultrasonic data were also compared with low-frequency dynamic mechanical data (11 Hz) and stress relaxation data (10²–10⁵ sec) through the use of simple time–temperature superposition principle. Considerable discrepancies were found by using this principle, indicating that the heterophase SBS block copolymer was thermorheologically complex.     

线形苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)的粘弹弛豫与相形态

研究了不同温度下苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)的粘弹弛豫与相形态. DSC分析发现, SBS的相结构特别是其中质量分数较低的PS相畴的大小受热历史影响显著. 用TEM表征了SBS的双相连续形态和两相相畴尺寸. 用动态流变学方法研究了不同温度下SBS嵌段大分子的松弛行为. 结果表明, 在低于PS相玻璃化转变温度时, 嵌段分子中的PB段已可发生运动; 而当高于PS玻璃化转变温度后, 由于PB与PS间的相互作用及PB的链缠结所限制, 体系仍保持较高的弹性模量, 呈现“第二平台”特征流变行为.     

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.     

Effects of radiation crosslinking on structures and properties of SBS triblock copolymer

There is considerable interest in the effect of high energy radiation on triblock copolymer, SBS. Basheer and Dole have done some works about that(Basheer and Dole, 1982). In this paper, we study the effects of radiation crosslinking on the structure and mechanical properties of SBS, about which there have been no reports up to now. The following scientific problems are discussed: The variation of glass transition temperatures with dose; The effects of the ratio of B/S on the gel content; Mechanical properties of the irradiated samples.     

Mechanical properties and the two-phase structure inside the heterophase domains of blends from HDPE and SBS star block copolymers

Blends from polyethylene (PE) and polystyrene-b-polybutadiene-b-polystyrene star block copolymers (SBS) (thermoplastic elastomers) are studied with polyolefine recycling in view. Each component, dispersed in a heterogeneous blend, exhibits a two-phase morphology. This structure is investigated by small angle X-ray scattering (SAXS) and compared to mechanical properties as a function of SBS grade and content. Increasing the SBS content one observes a vanishing PE-related long period reflection, while an SBS-related peak emerges. Best mechanical properties are obtained at concentrations, where the width of the observed long period reflection is broadest. For a quantitative analysis of the SAXS, the interface distribution function (IDF) analysis is employed. Data are fitted with a function modeling arrangement as well as disorder of domains inside the two different kinds of dispersed grains. The analysis yields that the observed broadening of the long spacing peak is caused only by an increased fluctuation of the thicknesses of amorphous layers in the PE stacks. This fluctuation again decreases for SBS concentrations beyond 15 wt %. The effect is strongest for blends containing the SBS grade with the lowest molecular weight and is discussed in terms of its compatibilization effect. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1423–1432, 1998     

Stability of human insulin in solutions containing sodium bisulfite.

The stabilities of human insulin (HI) in aqueous solutions were investigated in the pH range of 4.0-7.0 in the presence (1.0-3.0 x 10(-3) M) and absence of sodium bisulfite (SBS) both in the dark and under scattered light (1000 lux) using high performance liquid chromatography. Increasing concentrations of SBS tended to degrade HI. In the presence of SBS, with an increase in the pH value, the stability of HI decreased in the pH range of 4.0-7.0. There was a partial difference in the stability of HI in the presence of SBS in the dark and that under scattered light. HI was stabilized by glucose in the presence of SBS in the dark, and the stability of HI was revealed to depend on the concentration of free SBS. The reason for this phenomenon was postulated to be the formation of bisulfite-glucose adduct.     

Fracture energies of styrene-butadiene-styrene block copolymers (I). Effects of rate,temperature, and casting solvent

Specimens of styrene-butadiene-styrene (SBS) block copolymers, Kraton D-1102, were prepared by solution casting using three different solvents: toluene, cyclohexane, and a mixture of tetrahydrofuran and methyl ethyl ketone (THF/MEK). Measurements of fracture energies of SBS specimens were carried out at various temperatures and rates using two methods (i.e., a conventional tear test and a recently developed cutting test). Effect of casting solvent on the fracture energy was investigated as well. It was found that stick-slip tearing dominates at low temperatures (−50 ∼20°C). Tear strength increased with decreasing temperature. Eventually, a value of 180 kJ/m² was reached at −70°C, close to the glass transition temperature of polybutadiene phase. At temperatures higher than 20°C, however, steady tearing was found and the tear strength gradually decreased with increasing temperature. Tear strength was virtually zero at 100°C, above the glass transition temperature of polystyrene phase. Effect of temperature on tear strength is more pronounced than that of tearing rate. In contrast, the intrinsic strength of SBS block copolymers determined from cutting test remains unchanged, about 570 J/m², over a wide range of temperatures and rates. Specimens cast from THF/MEK solution exhibit yielding phenomena when stretched. Moreover, they possess a relatively larger tear strength, compared to those cast from either toluene or cyclohexane solution. A more continuous polystyrene phase is expected to develop in THF/MEK as-cast specimens which is believed to account for the large tear strength. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2003–2015, 1997     

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.     

Microwave assisted fabrication of polymethyl methacrylate-graphene composite nanoparticles applied for the preparation of SBS modified asphalt with enhanced high temperature performance

In order to improve the high temperature rutting resistance ability and stability of styrene-butadiene-styrene (SBS) modified asphalt, microwave heating emulsion polymerization strategy was used to prepare polymethyl methacrylate (PMMA) and graphene nanoparticles (GNPs) composite (PMMA-GNPs) which was used to prepare PMMA-GNPs/SBS modified asphalt. Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy and thermogravimetric analysis characterizations showed that PMMA-GNPs particles were successfully prepared having a weight ratio of GNPs: PMMA of 1:9. Microwave heating reduced the reaction time from 5 h to 30 min compared to conventional oil bath heating. Dynamic shear rheological test and multi-stress creep recovery test confirmed that 0.06% PMMA-GNPs/SBS modified asphalt (0.06% PMMA-GNPs of the mass of base asphalt) exhibited an increase of 14.2% in elastic modulus (G′), while rutting resistance was enhanced and sensitivity to stress changes was reduced as compared to those of 5% SBS modified asphalt. Fluorescence microscopy analysis and phase separation test revealed that an appropriate amount of PMMA-GNPs can be uniformly dispersed in SBS modified asphalt and enhance the mutual interaction of SBS with base asphalt. Based on the results of mechanical tests and characterizations, a suitable modification mechanism of PMMA-GNPs particles in the original SBS modified asphalt was described in detail. This study proposes a simple, cost effective and fast strategy for the preparation of PMMA-GNPs incorporated SBS modified asphalt and hence can be envisioned of great promise in construction and highway industries.     

Chemical initiation of graft copolymerization of methyl methacrylate onto styrene–butadiene block copolymer

When a solution containing both styrene–butadiene block copolymer (SBS) and methyl methacrylate is treated with an initiator both homopolymerization of the methyl methacrylate and graft copolymerization of the methyl methacrylate onto the SBS occur. The amount of graft copolymerization depends upon the time and temperature of the reaction, the concentrations of all species, and the identity of the solvent and initiator. The combination of benzoyl peroxide in chloroform gives the highest graft yield and the reaction occurs by removal of an allylic hydrogen from the SBS by the initiator radical and subsequent addition of monomer units to that site; there is a significant solvent effect. Both AIBN and BPO function by the removal of an allylic hydrogen atom from SBS; BPO is able to effect this reaction relatively easily while AIBN can remove the hydrogen atom only with great difficulty and to a limited extent. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 965–974, 1997     

Stability of urokinase in solutions containing sodium bisulfite

The stabilities of urokinase (UK) in aqueous solution were investigated at pH 5.0-8.0 in the presence (1.0-3.0 x 10(-3) M) and absence of sodium bisulfite (SBS) both under scattered light (1000 lux) and in the dark using the fluorogenic substrate method. Increasing concentrations of SBS tended to increase the inactivation of UK. In the presence of SBS, with the increase in the pH value, UK gained in stability in the pH range of 5.0-8.0. The stability of UK in the presence of SBS in the dark was larger than that under scattered light, especially at pH 5.0. Therefore, it was suggested that the difference in the residual activities of UK between under light and in the dark was due to free radicals formed during the autooxidation of bisulfite under scattered light. UK was stabilized by glucose in the presence of SBS both under scattered light and in the dark. One reason for this phenomenon was postulated to be the formation of inactive bisulfite-glucose addition compound. The degradation products of UK during storage in a solution containing SBS were investigated by sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis. UK was revealed to be split into M.W. 36000 form and M.W. 20000 form by SBS.     

STUDIES ON MICELLE BEHAVIORS OF STYRENE-BUTADIENE-STYRENE (SBS) TRIBLOCK COPOLYMERS IN METHYL ETHYL KETONE (MEK) BY POSITRON ANNIHILATION TECHNIQUE

Positron annihilation technique was used to study the micelle behaviors of two SBS triblock copolymers in MEK solvent at different temperatures. Annihilation lifetime τ_3 of ortho-positronium (o-Ps) exhibited an obvious transition from shorter lifetime to longer lifetime with temperature. It was attributed to the change of micelle behavior of SBS copolymer molecules in the solution. Experimental results of sedimentation velocity of ultracentrifuge were also reported.     

Dynamic mechanical properties of suspensions of micellar casein particles

Small micellar casein particles, so-called submicelles, were obtained by removing colloidal calcium phosphate from native casein by adding sodium polyphosphate. Aqueous submicelle suspensions were characterized using light scattering and rheology as a function of concentration and temperature. The casein submicelles behave like soft spheres that jam at a critical concentration (C(c)) of about 100 g L(-1). The viscosity does not diverge at C(c), but increases sharply, similarly to that of multiarm star polymers. C(c) increases weakly with increasing temperature, which leads to a strong decrease of the viscosity close to and above C(c). Concentrated submicelle suspensions show strong shear-thinning above a critical shear rate and the shear stress becomes independent of the shear rate. The critical shear rates at different temperatures and concentrations are inversely proportional to the zero-shear viscosity. At much higher shear rates, the shear stress fluctuates strongly in time indicating inhomogeneous flow. The frequency dependence of casein submicelle suspensions is characterized by elastic behavior at high frequencies (concentrations) and viscous behavior at low frequencies (concentrations).     

A Facile Approach Toward Scalable Fabrication of Reversible Shape‐Memory Polymers with Bonded Elastomer Microphases as Internal Stress Provider

The present communication reports a novel strategy to fabricate reversible shape‐memory polymer that operates without the aid of external force on the basis of a two‐phase structure design. The proof‐of‐concept material, crosslinked styrene‐butadiene‐styrene block copolymer (SBS, dispersed phase)/polycaprolactone‐based polyurethane (PU, continuous phase) blend, possesses a closely connected microphase separation structure. That is, SBS phases are chemically bonded to crosslinked PU by means of a single crosslinking agent and two‐step crosslinking process for increasing integrity of the system. Miscibility between components in the blend is no longer critical by taking advantage of the reactive blending technique. It is found that a suitable programming leads to compressed SBS, which serves as internal expansion stress provider as a result. The desired two‐way shape‐memory effect is realized by the joint action of the temperature‐induced reversible opposite directional deformabilities of the crystalline phase of PU and compressed SBS, accompanying melting and orientated recrystallization of the former. Owing to the broadness of material selection and manufacturing convenience, the proposed approach opens an avenue toward mass production and application of the smart polymer.     

共聚物组成对线形苯乙烯-丁二烯-苯乙烯嵌段共聚物粘弹弛豫与相形态的影响

研究了不同组成的苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)的相形态与粘弹弛豫.用透射电子显微镜(TEM)表征了SBS的形态,结果显示,几种SBS均呈层状结构,随着苯乙烯含量的降低,聚苯乙烯(PS)相的尺寸稍有减小,而聚丁二烯(PB)相尺寸明显增大.用动态流变学方法考察了不同温度下SBS嵌段大分子的弛豫行为,结果表明,苯乙烯含量减少,PS相玻璃化转变和有序-无序转变温度均降低;苯乙烯含量少的,在有序-无序转变过程中呈现出高且宽的损耗峰,表明有序-无序转变过程中能量的耗散主要由两相溶合时分子链间的内摩擦所决定,分子链越长,内摩擦越大,能量耗散越大.     

Interaction between dispersed photochromic compound and polymer matrix

Thin films containing photochromatic spiropyran (SP) was prepared from polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), poly(n-butyl methacrylate) (PnBMA), and styrene-butadiene-styrene copolymer (SBS). The thin films were illuminated with the ultraviolet light (365 nm) under various temperatures. The photochromic response was monitored with a multichannel photodetector. The results show that the photocoloring rate of SP was faster in PMMA, while the thermal decoloring rate was faster in SBS. In addition, the decoloring rate was higher in a polymer matrix with lower T_g.     

苯亚磺酸钠在聚乙烯醇为粘合剂的光敏热成像材料中的化学增感

以水溶性聚乙烯醇(PVA)为粘合剂,以异位法制备的颗粒尺寸为100nm的AgBr乳剂作光敏元,考察了苯亚磺酸钠(SBS)的用量、增感时间和增感温度对光敏热成像(PTG)材料照相性能的影响.实验结果表明:分别增感硬脂酸银(AgSt)、AgBr或者两者混合物,PTG材料均可取得明显的增感效果;灰雾随着苯亚磺酸钠用量增加而增加;增感温度以及增感时间不同,PTG材料的感光度不同.     

The Determination of Salbutamol Sulfat Based on a Flow‐Injection Coupling Irreversible Biamperometry at Poly(aminosulfonic acid)‐Modified Glassy Carbon Electrode

Abstract

The present work describes the development of a simple and efficient method for electrochemical analysis determination of SBS using polymer film coated modified electrode. A glassy carbon electrode (GCE) is successfully modified with electropolymerized film of aminosulfonic acid (ASA) in pH 6.8 phosphate buffer solution (PBS). Cyclic voltammetry (CV) were used to study the electrochemical properties of the polymer film and the appropriate condition for electropolymerization process. The voltammetric behavior of SBS at the PASA GC CMEs has been investigated, the results suggest that the PASA GC CMEs have good effect of electrocatalytic oxidation action to SBS, also propose the mechanism toward SBS. The flow‐injection irreversible biamperometry analysis method was studied under the applied potential difference of 0 V to determinate SBS. In 0.1 mol l^?1 (pH 6.80) phosphate buffer solution, a sensitive and irreversible oxidation peak was obtained at the PASA GC CMEs. Under the optimum conditions, SBS can be determined from the range 2.0×10^?6 to 1.0×10^?3 mol · 1^?1 with the sampling frequency of 100 samples per hour. The detection limit for SBS is 6.5×10^?7 mol l^?1 and the RSD for 20 replicate determinations of 4.0×10^?5 mol l^?1 SBS is 1.85%. The method is simple, with high selective rapid and sensitive. The method is applied to the determination of SBS in the drug with satisfactory results. Moreover, the physiologically common interferents (i.e., sucrose, lactose, citric acid, and citrate) negligibly affected the response of SBS. The PASA GC CMEs film‐coated electrode exhibited a stable and sensitive response to salbutamol sulfat in the presence of electrocatalysis oxidation.