Physical and rheological properties of crumb rubber/styrene–butadiene–styrene compound modified asphalts

In order to improve the storage stability and tenacity of crumb rubber modified (CRM) asphalt, CRM compound modified asphalt was prepared by the addition of styrene–butadiene–styrene (SBS) and sulfur. The addition of SBS improved the tenacity of CRM asphalt, due to the formation of a dense polymer network. The storage stability of crumb rubber (CR)/SBS‐modified (CRSM) asphalt was improved by the addition of sulfur. The rheological tests confirmed the effect of SBS and sulfur on the physical properties of CRM asphalt to some extent and showed the susceptibility of CR/SBS/sulfur‐modified (CRSSM) asphalt to dynamic shearing. The morphology observation showed the compatibility of CRSM asphalt was improved greatly by vulcanization. POLYM. COMPOS., 38:1918–1927, 2017. © 2015 Society of Plastics Engineers     

Improved properties of SBS‐modified asphalt with dynamic vulcanization

Storage‐stable styrene‐butadiene‐styrene triblock copolymer (SBS)‐modified asphalt was prepared by dynamic vulcanization. The vulcanization characteristics of the asphalt/SBS/sulfur blend were studied using a strain‐controlled rheometer. The vulcanization of SBS in the asphalt resulted in a marked increase in the torque of the blend. In addition, the vulcanization of a butadiene rubber (BR)/sulfur blend was significantly influenced by the addition of asphalt through a curemeter. The existence of asphalt can accelerate the vulcanization of BR/sulfur blend and reduce its reversion. The preparation process of storage‐stable SBS‐modified asphalt by dynamic vulcanization was identified by a plot of the electric current versus time. The addition of sulfur to the SBS‐modified asphalts resulted in the formation of chemically vulcanized network structures in the modified binders. The physical properties of the SBS‐modified asphalt containing sulfur were compared to those of the modified binders without sulfur. The storage stability of the SBS‐modified asphalt was effectively improved by the addition of sulfur. The rheological properties of the SBS‐modified asphalts before and after adding sulfur were characterized by using dynamic shear rheometry and a rotational viscometer. As indicated by the monitored morphology, the compatibility and high‐temperature storage stability of SBS‐modified asphalts were improved by the addition of sulfur.     

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     

Use of rheological compatibility criteria to study SBS modified asphalts

Polymer‐modified asphalts (PMAs) were prepared using Bachaquero asphalt and styrene–butadiene–styrene (SBS) type copolymers. Their rheological behavior was compared to that of unmodified asphalt and of a compatible commercial PMA. Materials were submitted to frequency sweeps between 10^?1 and 10² rad/s from 0 to 50°C. Storage stability tests were performed for 72 h at 160°C. Ring and ball softening points from the top and the bottom of the blends were compared and were used along with fluorescence microscopy to evaluate stability. Samples prepared with styrene–ethylene–butylene–styrene (SEBS) showed improved compatibility and stability as compared with SBS‐modified asphalts, probably because of a higher stability to thermal degradation from the absence of double bonds. An additional improvement in stability and compatibility was observed for SEBS functionalized with maleic anhydride (SEBS‐g‐MAH)–modified blends. Better compatibility, however, did not improve rheological behavior at low temperatures. The systems studied are so complex from a chemical point of view that the rheological criteria normally used to predict compatibility of polyblends did not give enough information regarding the compatibility of the modified asphalts. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1772–1782, 2003     

Mechanical and piezo‐resistive properties of styrene–butadiene–styrene copolymer covalently modified with graphene/styrene–butadiene–styrene composites

As novel piezoelectric materials, carbon‐reinforced polymer composites exhibit excellent piezoelectric properties and flexibility. In this study, we used a styrene–butadiene–styrene triblock copolymer covalently grafted with graphene (SBS‐g‐RGO) to prepare SBS‐g‐RGO/styrene–butadiene–styrene (SBS) composites to enhance the organic solubility of graphene sheets and its dispersion in composites. Once exfoliated from natural graphite, graphene oxide was chemically modified with 1,6‐hexanediamine to functionalize with amino groups (GO–NH₂), and this was followed by reduction with hydrazine [amine‐functionalized graphene oxide (RGO–NH₂)]. SBS‐g‐RGO was finally obtained by the reaction of RGO–NH₂ and maleic anhydride grafted SBS. After that, X‐ray diffraction, X‐ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and other methods were applied to characterize SBS‐g‐RGO. The results indicate that the SBS molecules were grafted onto the graphene sheets by covalent bonds, and SBS‐g‐RGO was dispersed well. In addition, the mechanical and electrical conductivity properties of the SBS‐g‐RGO/SBS composites showed significant improvements because of the excellent interfacial interactions and homogeneous dispersion of SBS‐g‐RGO in SBS. Moreover, the composites exhibited remarkable piezo resistivity under vertical compression and great repeatability after 10 compression cycles; thus, the composites have the potential to be applied in sensor production. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46568.     

Fundamental characterization of SBS‐modified asphalt mixed with sulfur

The purpose of this study was to characterize the mechanical behavior of asphalt modified by styrene–butadiene–styrene (SBS) and sulfur. Viscosity, microscopy, and rheological tests were conducted to understand the engineering properties of the polymer‐modified asphalt (PMA). Without the addition of sulfur, the polymer‐modified asphalt was microheterogeneous and was made up of two distinct finely interlocked phases, especially at high SBS concentrations. After the addition of sulfur, the PMA was observed to have smaller asphalt domains and a fairly homogeneous dispersion of the asphalt in the SBS matrix. The compatibility between polymer and asphalt produced an elastic network into the asphalt. The addition of sulfur resulted in an excellent elastic system and substantially increased the rheological properties of the PMA. Because of the colloidal nature of asphalt cements, their engineering properties were greatly improved because of the reinforcement of the SBS polymer and the physical‐chemical interaction between SBS and asphalt. The difference in the softening point between the top and bottom layers decreased significantly, and elastic recovery increased when was sulfur was present. A viscoelastic model was examined and shown to be appropriate for predicting the rheological properties ofthe asphalt–SBS blend mixed with sulfur. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2817–2825, 2007     

SBS的侧链羧基官能化改性及在改性沥青中应用

以3–巯基丙酸(MPA)为改性剂,偶氮二异丁腈(AIBN)为引发剂,利用巯基–烯加成反应对苯乙烯–丁二烯–苯乙烯三嵌段共聚物(SBS)进行侧链羧基官能化改性,得到改性产品SBS-g-COOH。利用傅立叶变换红外光谱(FTIR)和核磁共振(~1H–NMR)对不同接枝度的SBS-g-COOH进行结构表征,考察了反应温度、反应时间、改性剂用量对侧链羧基接枝度的影响。利用荧光显微镜考察了不同接枝度的SBS-g-COOH在沥青中的分散性,结果表明,SBS-g-COOH的接枝度随反应温度、反应时间和改性剂含量的增加而增加。低接枝度的SBS-g-COOH能明显改善其与沥青的相容性及热存储稳定性,接枝度在10%左右最佳。     

Effect of montmorillonite on properties of styrene–butadiene–styrene copolymer modified bitumen

Clay/styrene–butadiene–styrene (SBS) modified bitumen composites were prepared by melt blending with different contents of sodium montmorillonite (Na‐MMT) and organophilic montmorillonite (OMMT). The structures of clay/SBS modified bitumen composites were characterized by XRD. The XRD results showed that Na‐MMT/SBS modified bitumen composites may form an intercalated structure, whereas the OMMT/SBS modified bitumen composites may form an exfoliated structure. Effects of MMT on physical properties, dynamic rheological behaviors, and aging properties of SBS modified bitumen were investigated. The addition of Na‐MMT and OMMT increases both the softening point and viscosity of SBS modified bitumens and the clay/SBS modified bitumens exhibited higher complex modulus, lower phase angle. The high‐temperature storage stability can also be improved by clay with a proper amount added. Furthermore, clay/SBS modified bitumen composites showed better resistance to aging than SBS modified bitumen, which was ascribed to barrier of the intercalated or exfoliated structure to oxygen, reducing efficiently the oxidation of bitumen, and the degradation of SBS. POLYM. ENG. SCI., 47:1289–1295, 2007. © 2007 Society of Plastics Engineers     

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     

Plasticization of nano‐CaCO3 in polystyrene/nano‐CaCO3 composites

The shear rheological properties of polystyrene (PS)/nano‐CaCO₃ composites were studied to determine the plasticization of nano‐CaCO₃ to PS. The composites were prepared by melt extrusion. A poly(styrene–butadiene–styrene) triblock copolymer (SBS), a poly(styrene–isoprene–styrene) triblock copolymer (SIS), SBS‐grafted maleic anhydride (SBS–MAH), and SIS‐grafted maleic anhydride were used as modifiers or compatibilizers. Because of the weak interaction between CaCO₃ and the PS matrix, the composites with 1 and 3 phr CaCO₃ loadings exhibited apparently higher melt shear rates under the same shear stress with respect to the matrix polymer. The storage moduli for the composites increased with low CaCO₃ concentrations. The results showed that CaCO₃ had some effects on the compatibility of PS/SBS (or SBS–MAH)/CaCO₃ composites, in which SBS could effectively retard the movement of PS chain segments. The improvement of compatibility, due to the chemical interaction between CaCO₃ and the grafted maleic anhydride, had obvious effects on the rheological behavior of the composites, the melt shear rate of the composites decreased greatly, and the results showed that nano‐CaCO₃ could plasticize the PS matrix to some extent. Rheological methods provided an indirect but useful characterization of the composite structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Preparation and properties of high viscosity modified asphalt

High viscosity modified (HVM) asphalt was prepared by the addition of styrene–butadiene–styrene (SBS), plasticizer, crosslinker. The effect and proportion of each modifier in the preparation of HVM asphalt were studied. SBS was the major modifier and determined the basic properties of HVM asphalt. Plasticizer (furfural exact oil) and crosslinker (sulfur) as additional modifiers were necessary in improving the workability, stability, and aging resistance of modifier. The effect of aging and additional modifiers on the structure and rheological behavior of SBS modified (SM) asphalt was displayed by adopting various rheological tests. Plasticizer declined the rutting resistance of SM asphalt and increased the viscous behavior of SM asphalt after aging. The use of crosslinker led to the formation of polymer network and improved the aging resistance of SM asphalt. The morphology observation shows crosslinker led to the formation of polymer network and improved the compatibility between SBS and asphalt. Plasticizer prompted the swelling and dispersion of SBS in asphalt and improved the effect of crosslinker further. Aging destroyed the polymer phase seriously and there was still residual polymer phase in asphalt. POLYM. COMPOS., 38:936–946, 2017. © 2015 Society of Plastics Engineers     

Reactive compatibilization of polystyrene/poly(ethylene–co–vinyl acetate) (EVA) blends

A reactive compatibilizer, mercapto‐functionalized EVA (EVASH), in combination with styrene‐butadiene block copolymer (SBS), was used to compatibilize the blends of polystyrene (PS) and ethylene–vinyl acetate copolymer (EVA). The reactive compatibilization was confirmed by the presence of insoluble material and from dynamic‐mechanical analysis. In addition to a more uniform morphology with small phase size, the compatibilization also provided excellent stabilization of the morphology, with an almost complete suppression of coarsening during annealing. As a consequence, a substantial increase on the elongation at break without significant influence on ultimate tensile strength was achieved for compatibilized blends with different compositions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 14–22, 2006     

Compatibility effect of radiation‐grafting‐functionalized styrene–butadiene–styrene on polyamide 6/styrene–butadiene–styrene blends

Styrene–butadiene–styrene (SBS) was grafted with dibutyl maleate (DBM), methacrylic acid (MAA), or maleic anhydride (MAH) by ⁶⁰Co γ‐rays. The grafted SBS was blended with polyamide 6 (PA6). The compatibility of the PA6/SBS blends was studied with scanning electron microscopy and rheological measurements. The results showed significant improvement in the compatibility of PA6 blended with MAH‐ or MAA‐grafted SBS, with the former being more effective, whereas grafting DBM was ineffective in this respect. Mechanisms of the compatibility enhancement and ineffectiveness are discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

SBS改性沥青的研究进展

介绍了目前SBS改性沥青的研究进展,从SBS改性沥青的相容性、相形态结构、流变性及高温贮存稳定性四个方面进行阐述,提出了SBS改性沥青技术的发展趋势。     

SBS改性沥青的结构与性能

通过动态黏弹性能、结构分析和沥青基本性能测试研究了SBS和沥青之间的相容性,以及SBS用量对改性沥青的结构与性能的影响。结果表明,SBS与沥青有一定的相容性,沥青中的某些组分可进入SBS的聚丁二烯(PB)链段区域。使PB的玻璃化转变温度升高,在高剪切力作用下也可进入聚苯乙烯(PS)链段,降低了PS的玻璃化转变温度,但不会使PS物理交联点发生严重解体。当SBS质量分数为5％时,SBS在沥青中呈彼此分离的球状颗粒;当SBS质量分数达到7％或以上时,则形成连续相。随着SBS质量分数的增加。改性沥青的软化点和低温延度升高,针入度和高温贮存稳定性下降。     

纳米碳酸钙/苯乙烯-丁二烯-苯乙烯嵌段共聚物复合改性沥青的制备及性能

采用纳米CaCO3和苯乙烯-丁二烯-苯乙烯嵌段共聚物（SBS）作为外加剂制备纳米CaCO3/SBS复合改性沥青。通过测试基本物理性能确定了外加剂的最佳掺量,通过流变性能测试、离析试验、荧光显微镜观察及热重分析等考察了沥青的性能及微观形貌。结果表明,两种外加剂复配的最佳比例为5%（质量分数,下同）的纳米CaCO3和4%的SBS;在纳米CaCO3改性沥青中掺加SBS后,复合改性沥青在不同温度下的黏度增大,高温抗车辙能力增强,低温性能得到明显改善,储存稳定性良好;纳米CaCO3分子、SBS分子和基质沥青分子三者具有良好的相容性,经复合改性后沥青的热稳定性增强。     

Properties of acrylonitrile–butadiene–styrene/polycarbonate blends with styrene–butadiene–styrene block copolymer

The importance of alloys and blends has increased gradually in the polymer industry so that the plastics industry has moved toward complex systems. The main reasons for making polymer blends are the strengthening and the economic aspects of the resultant product. In this study, I attempted to improve compatibility in a polymer blend composed of two normally incompatible constituents, namely, acrylonitrile–butadiene–styrene (ABS) and polycarbonate (PC), through the addition of a compatibilizer. The compatibilizing agent, styrene–butadiene–styrene block copolymer (SBS), was added to the polymer blend in ratios of 1, 5, and 10% with a twin‐screw extruder. The morphology and the compatibility of the mixtures were examined by scanning electron microscopy and differential scanning calorimetry. Further, all three blends of ABS/PC/SBS were subjected to examination to obtain their yield and tensile strengths, elasticity modulus, percentage elongation, Izod impact strength, hardness, heat deflection temperature, Vicat softening point, and melt flow index. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2521–2527, 2004     

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     

Blends of SBS triblock copolymer with poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polystyrene mixture

Blends of styrene–butadiene–styrene (SBS) or styrene–ethylene/1‐butene–styrene (SEBS) triblock copolymers with a commercial mixture of polystyrene (PS) and poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) were prepared in the melt at different temperatures according to the chemical kind of the copolymer. Although solution‐cast SBS/PPO and SBS/PS blends were already known in the literature, a general and systematic study of the miscibility of the PS/PPO blend with a styrene‐based triblock copolymer in the melt was still missing. The thermal and mechanical behavior of SBS/(PPO/PS) blends was investigated by means of DSC and dynamic thermomechanical analysis (DMTA). The results were then compared to analogous SEBS/(PPO/PS) blends, for which the presence of a saturated olefinic block allowed processing at higher temperatures (220°C instead of 180°C). All the blends were further characterized by SEM and TGA to tentatively relate the observed properties with the blends' morphology and degradation temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2698–2705, 2003     

Formation of SBS thermoplastic block copolymer using hexamethyleneimine alkenyl lithium (N‐Li) initiator

Styrene and butadiene block copolymers (SBS) end functionalized with amino group at the initiating chain ends were synthesized using hexamethyleneimine alkenyl lithium (N‐Li) as initiator, tetrahydrofuran (THF) as polar modifier, and cyclohexane as solvent. By attaching a few number of butadiene molecules to N‐lithium hexamethyleneimine, a new N‐Li initiator that can effectively initiate the polymerization of SBS was obtained. ¹H NMR spectrums of the N‐Li initiator terminated by ethanol, end functionalized polystyrene, and SBS block copolymer proved the structure of N‐Li and its ability to initiate the polymerization of styrene and SBS block copolymer. Kinetics studies suggested that the polymerization rate of styrene in the first block reached the maximum when the ratio of THF/Li was increased to 5, while further increase of the ratio of THF/Li could not improve the polymerization rate. The molecular weight distribution (MWD) of SBS initiated by N‐Li varied with the ratio of THF/Li. The vinyl content of polybutadiene block increased by improving the ratio of THF/Li, while the content of cis‐1,4 and trans‐1,4 structures decreased. The vinyl content of end functionalized SBS was somewhat higher than that of SBS initiated by classical n‐butyllithium when other condition was the same. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 81–88, 2006