Polylactide toughening with epoxy‐functionalized grafted acrylonitrile–butadiene–styrene particles

Glycidyl methacrylate functionalized acrylonitrile–butadiene–styrene (ABS‐g‐GMA) particles were prepared and used to toughen polylactide (PLA). The characteristic absorption at 1728 cm^?1 of the Fourier transform infrared spectra indicated that glycidyl methacrylate (GMA) was grafted onto the polybutadiene phase of acrylonitrile–butadiene–styrene (ABS). Chemical reactions analysis indicated that compatibilization and crosslinking reactions took place simultaneously between the epoxy groups of ABS‐g‐GMA and the end carboxyl or hydroxyl groups of PLA and that the increase of GMA content improved the reaction degree. Scanning electron microscopy results showed that 1 wt % GMA was sufficient to satisfy the compatibilization and that ABS‐g‐GMA particles with 1 wt % GMA dispersed in PLA uniformly. A further increase of GMA content induced the agglomeration of ABS‐g‐GMA particles because of crosslinking reactions. Dynamic mechanical analysis testing showed that the miscibility between PLA and ABS improved with the introduction of GMA onto ABS particles because of compatibilization reactions. The storage modulus decreased for the PLA blends with increasing GMA content. The decrease in the storage modulus was due to the chemical reactions in the PLA/ABS‐g‐GMA blends, which improved the viscosity and decreased the crystallization of PLA. A notched impact strength of 540 J/m was achieved for the PLA/ABS‐g‐GMA blend with 1 wt % GMA, which was 27 times than the impact strength of pure PLA, and a further increase in the GMA content in the ABS‐g‐GMA particles was not beneficial to the toughness improvement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of acrylonitrile–butadiene–styrene (ABS) morphology and poly(styrene‐co‐acrylonitrile) (SAN) content on fracture behavior of ABS/SAN blends

This study attempted to correlate morphological changes and physical properties for a high rubber content acrylonitrile–butadiene–styrene (ABS) and its diluted blends with a poly(styrene‐co‐acrylonitrile) (SAN) copolymer. The results showed a close relationship between rubber content and fracture toughness for the blends. The change of morphology in ABS/SAN blends explains in part some deviations in fracture behavior observed in ductile–brittle transition temperature shifts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2606–2611, 2004     

Gloss reduction and morphological properties of polycarbonate and poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) blends with SAN‐co‐GMA as a reactive compatibilizer

The gloss properties of the polycarbonate (PC)/poly(methyl methacrylate‐acrylonitrile‐butadiene‐styrene) (MABS) blend with styrene‐acrylonitrile‐co‐glycidyl methacrylate (SAN‐co‐GMA) as a compatibilizing agent were investigated. For the PC/poly(MABS)/SAN‐co‐GMA (65/15/20, wt %) blend surface, the reduction of gloss level was observed most significantly when the GMA content was 0.1 wt %, compared with the blends with 0.05 wt % GMA or without GMA content. The gloss level of the PC/poly(MABS)/SAN‐co‐GMA (0.1 wt % GMA) blend surface was observed to be 35, which showed 65% lower than the PC/poly(MABS)/SAN‐co‐GMA blend without GMA content. The gloss reduction was most probably caused by the insoluble fractions of the PC/poly(MABS)/SAN‐co‐GMA blend that were formed by the reaction between the carboxylic acid group in poly(MABS) and epoxy group in SAN‐co‐GMA. The results of optical and transmission electron microscope analysis, spectroscopy study, and rheological properties supported the formation of insoluble structure of the PC/poly(MABS)/SAN‐co‐GMA blend when the GMA content was 0.1 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46450.     

Effects of the polybutadiene/poly(styrene‐co‐acrylonitrile) ratio in a polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) impact modifier on the morphology and mechanical behavior of acrylonitrile–butadiene–styrene blends

Polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) (PB‐g‐SAN) impact modifiers with different polybutadiene (PB)/poly(styrene‐co‐acrylonitrile) (SAN) ratios ranging from 20.5/79.5 to 82.7/17.3 were synthesized by seeded emulsion polymerization. Acrylonitrile–butadiene–styrene (ABS) blends with a constant rubber concentration of 15 wt % were prepared by the blending of these PB‐g‐SAN copolymers and SAN resin. The influence of the PB/SAN ratio in the PB‐g‐SAN impact modifier on the mechanical behavior and phase morphology of ABS blends was investigated. The mechanical tests showed that the impact strength and yield strength of the ABS blends had their maximum values as the PB/SAN ratio in the PB‐g‐SAN copolymer increased. A dynamic mechanical analysis of the ABS blends showed that the glass‐transition temperature of the rubbery phase shifted to a lower temperature, the maximum loss peak height of the rubbery phase increased and then decreased, and the storage modulus of the ABS blends increased with an increase in the PB/SAN ratio in the PB‐g‐SAN impact modifier. The morphological results of the ABS blends showed that the dispersion of rubber particle in the matrix and its internal structure were influenced by the PB/SAN ratio in the PB‐g‐SAN impact modifiers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2165–2171, 2005     

Flow properties of ABS (acrylonitrile–butadiene–styrene) terpolymer

ABS (acrylonitrile–butadiene–styrene) terpolymer is a two-phase thermoplastic with SAN (styrene–acrylonitrile) copolymer constituting the continuous phase (matrix). The flow properties of ABS with varying molecular parameters were studied using a capillary viscometer at the shear rate range encountered in its processing. The viscosity-average molecular weights (M_v) of matrix SAN with 26% acrylonitrile content are in the range of 90,000 to 150,000, and M_v of poly-butadiene-are in the range of 150,000 to 170,000. The weight-average molecular weight of the matrix SAN is the main controlling factor for the flow properties of ABS at low shear rate, while the molecular weight distribution of the matrix SAN becomes increasingly important with the increase of shear rate. The presence of SAN grafted polybutadiene increases the melt viscosity of ABS by 40–60% over comparable free SAN copolymer and also decreases the activation energy at constant shear stress to 24–25 kcal/mole from the 33–36 kcal/mole for free SAN. The die swell of ABS and SAN can be correlated with the dynamic shear modulus G′, and the melt fracture of ABS and SAN starts at G′ equal to 3.6 × 10⁶ dynes/cm².     

Structure–properties relationship in toughening of poly(butylene terephthalate) with core–shell modifier

The performance of acrylonitrile–butadiene–styrene (ABS) core–shell modifier with different grafting degree, acrylonitrile (AN) content, and core–shell ratio in toughening of poly(butylene terephthalate) (PBT) matrix was investigated. Results show PBT/ABS blends fracture in ductile mode when the grafting degree is high, and with the decrease of grafting degree PBT/ABS blends fracture in a brittle way. The surface of rubber particles cannot be covered perfectly for ABS with low grafting degree and agglomeration will take place; on the other hand, the entanglement density between SAN and PBT matrix decreases because of the low grafting degree, inducing poor interfacial adhesion. The compatibility between PBT and ABS results from the strong interaction between PBT and SAN copolymer and the interaction is influenced by AN content. Results show ABS cannot disperse in PBT matrix uniformly when AN content is zero and PBT/ABS fractures in a brittle way. With the addition of AN in ABS, PBT/ABS blends fracture in ductile mode. The core–shell ratio of ABS copolymers has important effect on PBT/ABS blends. When the core–shell ratio is higher than 60/40 or lower than 50/50, agglomeration or cocontinuous structure occurs and PBT/ABS blends display lower impact strength. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 5363–5371, 2006     

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.     

Synthesis of high rubber styrene–EPDM–acrylonitrile graft copolymer and its toughening effect on SAN

High rubber styrene–EPDM–acrylonitrile (AES) was prepared by the graft copolymerization of styrene (St) and acrylonitrile (AN) onto ethylene–propylene–diene terpolymer (EPDM) in n‐heptane/toluene cosolvent using benzoyl peroxide as an initiator. The effects of reaction conditions, such as reaction temperature, initiator concentration, EPDM content, the solvent component, and reaction time, on the graft copolymerization are discussed. In addition, according to the research on mechanical properties of the SAN/AES blend, a remarkable toughening effect of AES on SAN resin was found. By means of scanning electron microscopy, the toughening mechanism is proposed to be crazing initiation from rubber particles and shear deformation of SAN matrix. Uniform dispersion of rubber particles, as shown by transmission electron microscopy, is attributed to the good compatibility of SAN and AES. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 416–423, 2004     

Influence of epoxy resin on the properties of maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer toughened polyamide 6 blends

Maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer (ABS‐g‐MA) was used as an impact modifier of polyamide 6 (PA6). Epoxy resin was introduced into PA6/ABS‐g‐MA blends to further improve their properties. Notched Izod impact tests showed that the impact strength of PA6/ABS‐g‐MA could be improved from 253 to 800 J/m with the addition of epoxy resin when the ABS‐g‐MA content was set at 25 wt %. Differential scanning calorimetry results showed that the addition of epoxy resin made the crystallization temperature and melting temperature shift to lower temperatures; this indicated the decrease in the PA6 crystallization ability. Dynamic mechanical analysis testing showed that the addition of epoxy resin induced the glass‐transition temperature of PA6 and the styrene‐co‐acrylonitrile copolymer phase to shift to higher temperatures due to the chemical reactions between PA6, ABS‐g‐MA, and epoxy resin. The scanning electron microscopy results indicated that the ABS‐g‐MA copolymer dispersed into the PA6 matrix uniformly and that the phase morphology of the PA6/ABS‐g‐MA blends did not change with the addition of the epoxy resin. Transmission electron microscopy showed that the epoxy resin did not change the deformation mechanisms of the PA6/ABS‐g‐MA blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Compatibility enhancement of ABS/PVC blends

The compatibilizing effect of poly(styrene-co-acrylonitrile) (SAN) whose acrylonitrile (AN) content is 25 wt % (SAN 25) in poly(acrylonitrile-co-butadiene-co-styrene) (ABS)/poly(vinyl chloride) (PVC) blend was studied when the AN content of the matrix SAN in ABS was 35 wt % (SAN 35). When some amount of matrix SAN 35 was replaced by SAN 25 in a ABS/PVC (50/50 by weight) blend, the mixed phase of SAN and PVC at the interface was thickened, and about a twofold increase of impact strength was observed. The changes in morphology, dynamic mechanical properties, and rheological properties by the compatibilizing effect of SAN 25 were observed. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 705–709, 1998     

Application of styrene‐acrylonitrile random copolymer–polyarylate block copolymer as reactive compatibilizer for polyamide and acrylonitrile‐butadiene‐styrene blends

Styrene‐acrylonitrile random copolymer (SAN) and polyarylate (PAr) block copolymer were applied as a reactive compatibilizer for polyamide‐6 (PA‐6)/acrylonitrile‐butadiene‐styrene (ABS) copolymer blends. The SAN–PAr block copolymer was found to be effective for compatibilization of PA‐6/ABS blends. With the addition of 3.0–5.0 wt % SAN–PAr block copolymer, the ABS‐rich phase could be reduced to a smaller size than 1.0 μm in the 70/30 and 50/50 PA‐6/ABS blends, although it was several microns in the uncompatibilized blends. As a result, for the blends compatibilized with 3–5 wt % block copolymer the impact energy absorption reached the super toughness region in the 70/30 and 50/50 PA‐6/ABS compositions. The compatibilization mechanism of PA‐6/ABS by the SAN–PAr block copolymer was investigated by tetrahydrofuran extraction of the SAN–PAr block copolymer/PA‐6 blends and the model reactions between the block copolymer and low molecular weight compounds. The results of these experiments indicated that the SAN–PAr block copolymer reacted with the PA‐6 during the melt mixing process via an in situ transreaction between the ester units in the PAr chain and the terminal amine in the PA‐6. As a result, SAN–PAr/PA‐6 block copolymers were generated during the melt mixing process. The SAN–PAr block copolymer was supposed to compatibilize the PA‐6 and ABS blend by anchoring the PAr/PA‐6 and SAN chains to the PA‐6 and ABS phases, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2300–2313, 2002     

Preparation and properties of PC/SAN alloy modified with styrene‐ethylene‐butylene‐styrene block copolymer

A polycarbonate (PC)/ poly (styrene‐co‐acrylonitrile) (SAN) alloy modified with styrene‐ethylene‐butylene‐styrene (SEBS) block copolymer was prepared and the influence of SEBS content, PC content, and types of modifier on Izod notched impact strength, tensile strength, flexural strength, and Vicat softening temperature was studied. The results showed that the addition of SEBS could obviously increase the Izod notched impact strength and the elongation at break and decrease the tensile and flexural strength and Vicat softening temperature. PC/SAN alloy modified with SEBS had better mechanical properties than the PC/SAN alloy modified with ABS. DSC analysis and SEM photographs revealed that the SEBS was not only distributed in the SAN phase but also distributed in PC phase in a PC/SAN/SEBS alloy while the ABS was mainly distributed in SAN phase in a PC/SAN/ABS alloy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of compatibilizer in acrylonitrile‐butadiene‐styrene toughened nylon 6 blends: Ductile–brittle transition temperature

The ductile–brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile‐butadiene‐styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate‐co‐maleic anhydride (MMA‐MAH) and MMA‐co‐glycidyl methacrylate (MMA‐GMA). The ductile–brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA‐MAH compatibilizer were supertough and showed a ductile–brittle transition temperature at ?10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA‐GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2643–2647, 2003     

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     

Dynamic mechanical properties of polycarbonate and acrylonitrile–butadiene–styrene copolymer blends

Blends of polycarbonate (PC) and poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) with different compositions are characterized by means of dynamic mechanical measurements. The samples show phase separation. The shift in the temperatures of the main dynamic mechanical relaxation shown by the blend with respect to those of the pure components is attributed to the migration of oligomers present in the ABS toward the PC in the melt blending process. A comparison with other techniques (dielectric and calorimetric analysis) and the application of the Takayanagi three block model confirm this hypothesis. In all the studied blend compositions (ABS weight up to 28.6%) the PC appears as the matrix where a disperse phase of ABS is present. The scanning and transmission electron microscopy micrographs show that the size of the ABS particles increases when the proportion of ABS in the blend increases. The FTIR results indicate that the interaction between both components are nonpolar in nature and can be enhanced by the preparation procedure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1507–1516, 2002     

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     

Polycarbonate/acrylonitrile–styrene–acrylic elastomer terpolymer blends with enhanced interfacial adhesion and surface gloss

A blend of bisphenol A polycarbonate (PC) and an acrylonitrile–styrene–acrylic elastomer (ASA) terpolymer with high surface gloss and excellent interfacial properties was developed for automobile applications. Because PC and the styrene‐co‐acrylonitrile (SAN) copolymer that formed the matrix in the PC/ASA blend were not miscible, two different types of compatibilizers were examined to improve the compatibility of the blend. A diblock copolymer composed of tetramethyl polycarbonate and poly(methyl methacrylate) (PMMA) was more effective than PMMA in increasing interfacial adhesion between PC and SAN. The surface gloss of the PC/ASA blend was always lower than that of the pure ASA included in the blend because of PC existing at the surface of the injection‐molding specimen. The PC/ASA blend with optimum surface gloss and enhanced interfacial adhesion was developed through the control of the molecular weight of PC and the compatibilizer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2097–2104, 2005     

Effects of styrene–acrylonitrile contents on the properties of ABS/SAN blends for fused deposition modeling

This paper was to assess the effects of styrene–acrylonitrile (SAN) contents on the glass transition temperature (T_g), melt flow index (MFI), and mechanical properties of acrylonitrile–butadiene–styrene (ABS)/SAN blends for fused deposition modeling (FDM) process. The addition of SAN had little effects on T_g but could decrease the MFI and elongation at break while improving the tensile strength and modulus of ABS/SAN blends. For both longitudinal direction and transverse direction FDM printed specimens, the incorporation of SAN improved mechanical properties without sacrificing dimensional stability. This result was mainly attributed to the increasing content of continuous phase (SAN phase) and improvement in adhesion quality. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44477.     

Effect of matrix SAN in ABS/PMMA blends

The effect of the molecular weight and acrylonitrile (AN) content of the styrene–acrylonitrile copolymer (SAN) on the morphology, mechanical properties, and rheological properties of acrylonitrile–butadiene–styrene terpolymer/poly(methyl methacrylate) (ABS)/PMMA (60/40 by weight) blends were studied. When the AN content of matrix SAN (32%) was close to that of graft SAN (30%) AN, rubber particles existed separately. However, with matrix SAN having 35% AN, rubber particles showed tendency to agglomerate each other. With increasing molecular weight of matrix SAN, impact strength, ultimate elongation, and abrasion resistance of the blend generally increased. Yield strength increased with molecular weight at a constant AN content of matrix SAN, and it decreased with the decrease of AN content in spite of the increasing molecular weight of SAN. Melt properties, rather than the morphological and mechanical properties, were more sensitive to the AN content, rather than the molecular weight of matrix SAN. © 1994 John Wiley & Sons, Inc.