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     

Synthesis and characterization of maleated ionomers via ring‐opening reaction of epoxidized styrene‐butadiene rubber with potassium hydrogen maleate and study of their behavior as compatibilizer

A novel method for synthesizing maleate ionomer of (styrene‐co‐butadiene) rubber (SBR) from epoxidized SBR was developed. The epoxidized SBR was prepared via epoxidation of SBR with performic acid formed in situ by H₂O₂ and formic acid in cyclohexane. The maleated ionomer was obtained by ring‐opening reaction of the epoxidized SBR solution with an aqueous solution of potassium hydrogen maleate. The optimum conditions were studied. It was found that it is necessary to use phase transfer catalyst and ring‐opening catalyst for enhancing the epoxy group conversion. To obtain 100% conversion addition of dipotassium maleate is important. The product was characterized by FTIR spectrophotometry and transmission electron microcroscopy (TEM). The results showed that the product was really an ionomer with domains of maleate ionic groups. Some properties of the ionomer, such as water absorbency, oil absorbency and dilute solution behavior were studied. With increasing ionic groups, the water absorbency of the ionomer increases, whereas the oil absorbency decreases. The dilute solution viscosity of the ionomer increases abruptly with increasing ionic group content. The ionomer can be used as a compatibilizer for the blends of SBS and chlorosulfonated polyethylene (CSPE). Addition of a small amount of the ionomer to the blend can enhance the mechanical properties of the blends. 3 wt % ionomer based on the blend can increase the tensile strength and ultimate elongation of the blend nearly twice. The compatibility of the blends enhanced by adding the ionomer was shown by scanning electron microscopy. The blend of equal parts of SBS and CSPE compatibilized by the ionomer behaves as an oil resistant thermoplastic elastomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 792–798, 2006     

Structural effects of compatibilizer localization and effectivity in thermoplastic polyurethane–polyolefin blends

A study was performed with blends of thermoplastic polyurethanes and polyolefins to determine the structural requirements for a compatibilizer to be located at the interface. It was demonstrated that during the addition of an incompatible polymeric additive (i.e., incompatible with both blend constituents) to a polyurethane–polyolefin blend, the additive migrated to the interface. This interfacial phenomenon was proven to be virtually independent of compatibilizer viscosity or surface activity. Only when the compatibilizer was quite comparable to one of the phases did small differences in polarity govern whether the compatibilizer remained at the interface or formed micelles. This effect was demonstrated with a series of styrene–(ethylene–butylene)–styrene block copolymer compatibilizers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2901–2905, 2002; DOI 10.1002/app.10285     

Study on the microphase structure and mechanical properties of the blends of acrylonitrile–butadiene–styrene and sodium sulphonated styrene–acrylonitrile ionomer

The tensile properties of the blends containing neat acrylonitrile–butadiene–styrene (ABS), styrene–acrylonitrile (SAN) and the sodium sulphonated SAN ionomer have been investigated as a function of ion content of the ionomer in the blend. The tensile toughness and strength of the blends showed maximum values at a certain ion content of the ionomer in the blend. This is attributed to the enhanced tensile properties of the SAN ionomer by introduction of ionic groups into SAN and the interfacial adhesion between the rubber and matrix phase in the blend. The interfacial adhesion was quantified by NMR solid echo experiments. The amount of interphase for the blend containing the SAN ionomer with low ion content (3·1mol%) was nearly the same as that of ABS, but it decreased with the ion content of the ionomer for the blend with ion content greater than 3·1mol%. Changing the ionomer content in the blends showed a positive deviation from the rule of mixtures in tensile properties of the blends containing the SAN ionomer with low ion content. This seems to result from the enhanced tensile properties of the SAN ionomer, interfacial adhesion between the rubber and matrix, and the stress concentration effect of the secondary particles. © 1998 SCI.     

Influence of calcium carbonate filler and mixing type process on structure and properties of styrene–acrylonitrile/ethylene–propylene–diene polymer blends

The properties of styrene–acrylonitrile (SAN) and ethylene–propylene–diene (EPDM) blends containing different types of calcium carbonate filler were studied. The influence of mixing type process on the blend properties was also studied. Two different mixing processes were used. The first one includes mixing of all components together. The other process is a two‐step mixing procedure: masterbatch (MB; EPDM/SAN/filler blend) was prepared and then it was mixed with previously prepared polymer blend. Surface energy of samples was determined to predict the strength of interactions between polymer blend components and used fillers. The phase morphology of blends and their thermal and mechanical properties were studied. From the results, it can be concluded that the type of mixing process has a strong influence on the morphological, thermal, and mechanical properties of blends. The two‐step mixing process causes better dispersion of fillers in blends as well as better dispersion of EPDM in SAN matrix, and therefore, the finest morphology and improved properties are observed in blends with MB. It can be concluded that the type of mixing process and carefully chosen compatibilizer are the important factors for obtaining the improved compatibility of SAN/EPDM blends. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Morphology of pyrolysed 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 was studied by scanning electron microscopy. Surface changes caused by heating the samples in a pyrolyzer for 15 and 30 min were presented in different micrographs. The morphological changes occurring due to the formation of polar groups and their crosslinking during the thermooxidative degradation are discussed. Morphological study of these thermally degraded polymer samples shows very good correlation with the thermodegradation results. The rate of thermodegradation is fast in case of SBS when compared with SIS block copolymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2549–2553, 2006     

Amphiphilic styrene–butadiene–styrene triblock copolymer grafted with polyoxyethylene

A styrene–butadiene–styrene triblock copolymer (SBS) was grafted with polyoxyethylene via a ring‐opening reaction of an epoxidized styrene–butadiene– styrene triblock copolymer (ESBS) with monocarboxylic‐group‐terminated methoxypoly(ethylene glycol) (CMPEG). The latter was prepared through the esterification of methoxypoly(ethylene glycol) with maleic anhydride. The optimum conditions for the preparation of the graft copolymer were studied. The graft copolymer was characterized with Fourier transform infrared spectrophotometry. Its water absorbency, oil absorbency, emulsifying property, phase‐transfer catalysis property in the Williamson solid–liquid reaction, and use as a compatibilizer in the blending of SBS with oil‐resistant chlorohydrin rubber (CHR) were also studied. The optimum conditions were a CMPEG/epoxy group molar ratio of 1.5, an N,N‐dimethyl aniline/ESBS concentration of 5 wt %, and an ESBS concentration of 12–14 g/100 mL at 75–80°C for 10 h. The polyoxyethylene content could reach 0.27 mmol/g. The graft copolymer absorbed a certain amount of water, fairly resisted kerosene, and possessed good emulsifying and phase‐transfer catalysis properties, both of which were enhanced with increasing polyoxyethylene graft content. The graft copolymer could be used as a compatibilizer for a blend of SBS and CHR. A 3 wt % concentration of the graft copolymer based on a 50/50 blend could increase both the tensile strength and ultimate elongation of the blend about 1.7 times. The blend behaved like an oil‐resistant thermoplastic elastomer. Scanning electron microscopy demonstrated the improved compatibility of the two components by the graft copolymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

SBS和SBS环氧化与顺酐化研究

SBS是(苯乙烯-丁二烯-苯乙烯)三嵌段共聚物，是含有聚苯乙烯玻璃化微区及聚丁二烯连续相的多相聚合物，具有热塑性橡胶的性质。它具有良好的拉伸性能、耐湿性、透气性、溶解性及抗滑性，而被大量用于橡胶制品、粘舍剂及沥青和树脂的改性剂等。其缺点是耐油性差，与极性物质不相容，不粘接等。用环氧化及顺酐化改性可改进这方面的缺点。SBS的环氧化改性多半使用过甲酸或过乙酸在溶液中进行。产物可作为压敏胶、热熔胶、密封胶等，用于粘接极性材料，也可作为耐油热塑性橡胶。SBS的顺酐化改性可在熔融态进行，也可在溶液中进行。产物可用作极性聚合物与非极性聚合物的共混增容剂、胶粘剂及进一步合成离聚体。     

The nature and location of SEBS–MA compatibilizer in polyethylene–wood flour composites

A maleic-anhydride-grafted styrene–ethylene—butylene–styrene (SEBS–MA) triblock copolymer has been used as a compatibilizer in low-density polyethylene–wood flour (LDPE–WF) composite system. The location of compatibilizer was studied using transmission electron microscopy (TEM). The unsaturated parts of the copolymer were stained with osmium tetraoxide (OsO₄) to enhance contrast between the different phases. TEM micrographs indicated that part of the compatibilizer was located at the interface between the wood particles and PE matrix and that wood was also stained by the OsO₄. The nature of the interface between the wood surface and the SEBS–MA was studied using Fourier transform infrared spectroscopy (FTIR). The results indicated that MA reacts with wood through esterification and hydrogen bonding and also possibly through interaction between the styrene and wood. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 201–209, 1998     

Recycling of blends of acrylonitrile–butadiene–styrene (ABS) and polyamide

The aim of this work is to evaluate routes to upgrade recycled engineering plastics, especially mixed plastics with acrylonitrile–butadiene–styrene copolymers (ABS) as the major component. A core‐shell impact modifier was successfully used to improve the impact strength of blends of ABS and ABS/polycarbonate (PC) blends recycled from the automotive industry. However, the presence of other immiscible components like polyamide (PA), even in small amounts, can lead to a deterioration in the overall properties of the blends. A styrene–maleic anhydride (SMA) copolymer and other commercial polymer blends were used to promote the compatibilization of ABS and PA. The core‐shell impact modifier was again found to be an efficient additive with regard to the impact strength of the compatibilized ABS/PA blends. The results obtained with fresh material blends were quite promising. However, in blends of recycled ABS and glass‐fiber‐reinforced PA, the impact strength did not exhibit the desired behavior. The presence of poorly bonded glass fibers in the blend matrix was the probable reason for the poor impact strength compared with that of a blend of recycled ABS and mineral‐filled PA. Although functionalized triblock rubbers (SEBS–MA) can substantially enhance the impact strength of PA, they did not improve the impact strength of ABS/PA blends because the miscibility with ABS is poor. The possibilities of using commercial polymer blends to compatibilize otherwise incompatible polymer mixtures were also explored giving promising results. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2535–2543, 2002     

Study on a new kind of polypropylene‐graft‐ polystyrene: Preparation and application

A novel synthetic route for preparing polypropylene‐graft‐polystyrene (PP‐g‐PSt) was set up. With this synthetic route, a series of PP‐g‐PSt copolymers containing different percentages of polystyrene chain were synthesized, based on the different reactivities of two kinds of C? C double bonds on 4‐(3‐butenyl) styrene. Characterization data, including ¹H‐NMR, ¹³C‐NMR, GPC, and DSC, demonstrated that the graft copolymers were all very pure. Furthermore, it was also attempted to use this new kind of propylene–styrene graft copolymer as a compatibilizer. DMA and SEM results illustrated that the PP‐g‐PSt obtained is an efficient compatibilizer for the polypropylene–polystyrene blend. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 314–322, 2004     

Compatibility and thermal properties of poly(acrylonitrile–butadiene–styrene) copolymer blends with poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile)

The mechanical and heat‐resistant properties of acrylonitrile–butadiene–styrene (ABS) binary and ternary blends were investigated. The relationship of compatibility and properties was discussed. The results show that poly(methyl methacrylate) (PMMA) and styrene–maleic anhydride (SMA) can improve the thermal properties of conventional ABS. The Izod impact property of ABS/PMMA blends increases significantly with the addition of PMMA, whereas that of ABS/SMA blends decreases significantly with the addition of SMA. Blends mixed with high‐viscosity PMMA are characterized by higher heat‐distortion temperature (HDT), and their heat resistance is similar to that of blends mixed with SMA. For high‐viscosity PMMA, from 10 to 20%, it is clear that blends appear at the brittle–ductile transition, which is related to the compatibility of the two phases. TEM micrographs show low‐content and high‐viscosity PMMA in large, abnormally shaped forms in the matrix. Compatibility between PMMA and ABS is dependent on both the amount and the viscosity of PMMA. When the amount of high‐viscosity PMMA varied from 10 to 20 wt %, the morphology of the ABS binary blends varied from poor to satisfactory compatibility. As the viscosity of PMMA decreases, the critical amount of PMMA needed for the compatibility of the two phases also decreases. SMA, as a compatibilizer, improved the interfacial adhesiveness of ABS and PMMA, which results in PMMA having good dispersion in the matrix. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2652–2660, 2002     

Effect of a styrene–butadiene copolymer on the phase structure and impact strength of polyethylene/high‐impact polystyrene blends

The effect of a styrene–butadiene block copolymer on the phase structure and impact strength of high‐density and low‐density polyethylene/high‐impact polystyrene blends with various compositions was studied. For both the blends, the type of the phase structure was not affected by addition of a styrene–butadiene compatibilizer. The localization and structure of the compatibilizer in the blends were dependent on their composition. Addition of the compatibilizer improved impact strength of the blends in the whole concentration range. The improvement was the largest for blends with a low amount of the minor phase. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 570–580, 2001     

从离子交联的磺化乙丙橡胶制备热塑性互穿网络聚合物

研究了离子交联的磺化乙丙胶(简称离聚体)与聚丙烯、高密度聚乙烯或离子交联的磺化丁基胶共混物的熔融行为、力学性能与组成的关系以及其形态结构。结果表明,具有离子微区的上述弹性体与含有结晶微区的聚丙烯或聚乙烯生成热塑性互穿网络聚合物,在抗张强度上表现出明显的协同效应。参与共混的结晶聚合物的熔点随离聚体含量增加而下降,而在形态结构上则呈现交叉连续相,共混物呈现热塑性弹性体行为或增韧塑料行为。     

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     

Effect of the addition of acrylonitrile/ethylene–propylene–diene monomer (EPDM)/styrene graft copolymer on the morphology–properties relationships in poly(styrene‐co‐acrylonitrile)/EPDM rubber blends

Blends of poly(styrene‐co‐acylonitrile) (SAN) with ethylene–propylene–diene monomer (EPDM) rubber were investigated. An improved toughness–stiffness balance of the SAN/EPDM blend was obtained when an appropriate amount of acrylonitrile–EPDM–styrene (AES) graft copolymer was added, prepared by grafting EPDM with styrene–acrylonitrile copolymer, and mixed thoroughly with both of the two components of the blend. Morphological observations indicated a finer dispersion of the EPDM particles in the SAN/EPDM/AES blends, and particle size distribution became narrower with increasing amounts of AES. Meanwhile, it was found that the SAN/EPDM blend having a ratio of 82.5/17.5 by weight was more effective in increasing the impact strength than that of the 90/10 blend. From dynamic mechanic analysis of the blends, the glass‐transition temperature of the EPDM‐rich phase increased from ?53.9 to ?46.2°C, even ?32.0°C, for the ratio of 82.5/17.5 blend of SAN/EPDM, whereas that of the SAN‐rich phase decreased from 109.2 to 108.6 and 107.5°C with the additions of 6 and 10% AES copolymer contents, respectively. It was confirmed that AES graft copolymer is an efficient compatibilizer for SAN/EPDM blend. The compatibilizer plays an important role in connecting two phases and improving the stress transfer in the blends. Certain morphological features such as thin filament connecting and even networking of the dispersed rubber phase may contribute to the overall ductility of the high impact strength of the studied blends. Moreover, its potential to induce a brittle–ductile transition of the glassy SAN matrix is considered to explain the toughening mechanism. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1685–1697, 2004     

Use of maleic anhydride–grafted polyethylene as compatibilizer for HDPE–tapioca starch blends: Effects on mechanical properties

Tapioca starch in both glycerol‐plasticized and in unplasticized states was blended with high‐density polyethylene (HDPE) using HDPE‐g‐maleic anhydride as the compatibilizer. The impact and tensile properties of the blends were measured according to ASTM methods. The results reveal that blends containing plasticized starch have better mechanical properties than those containing unplasticized starch. High values of elongation at break at par with those of virgin HDPE could be obtained for blends, even with high loading of plasticized starch. Morphological studies by SEM microscopy of impact‐fractured specimens of such blends revealed a ductile fracture, unlike blends with unplasticized starch at such high loadings, which showed brittle fracture, even with the addition of compatibilizer. In general, blends of HDPE and plasticized starch with added compatibilizer show better mechanical properties than similar blends containing unplasticized starch. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 863–872, 2001     

Accelerated and environmental weathering studies on polyethylene–starch blend films

Biodegradable polymers are desirable for a variety of applications, such as in packaging, agriculture, and medicine. Polyethylene (PE) blended with starch is already found to be a potential candidate to replace nondegradable thermoplastics in the areas of packaging. Films of polyethylene (PE)–starch blends with and without vegetable oil as a compatibilizer were prepared. The degradation of the films under thermooxidative treatment, ultraviolet light exposure, high temperature, high humidity, and natural ambience (soil burial) were monitored. It is seen that vegetable oil as an additive has a dual role: as a plasticizer, it improves the film quality; as a prooxidant, it accelerates degradation of the film. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2251–2257, 1998     

Preparation and properties of styrene–ethylene/butylene–styrene (SEBS)–clay hybrids

Styrene–ethylene/butylene–styrene triblock copolymer (SEBS)–clay hybrids were prepared by melt blending SEBS and organoclay using an internal mixer. Maleic anhydride modified SEBS (SEBS–MA) was used as a compatibilizer. X‐ray diffraction and transmission electron microscopy revealed that silicate layers of the clay were partially exfoliated and dispersed at a nanometer scale in the polymer matrix. Enhanced mechanical properties of these hybrids were observed from tensile and dynamic mechanical tests. Thermal degradation temperature of the hybrids was increased compared with pristine SEBS. Copyright © 2004 Society of Chemical Industry