Synthesis and evaluation of high‐performance ethylene–propylene–diene terpolymer/organoclay nanoscale composites

The main objective of this study was to synthesize and characterize the properties of ethylene–propylene–diene terpolymer (EPDM)/clay nanocomposites. Pristine clay, sodium montmorillonite (Na⁺–MMT), was intercalated with hexadecyl ammonium ion to form modified organoclay (16Me–MMT) and the effect of intercalation toward the change in interlayer spacing of the silicate layers was studied by X‐ray diffraction, which showed that the increase in interlayer spacing in Na⁺–MMT by 0.61 nm is attributed to the intercalation of hexadecyl ammonium ion within the clay layers. In the case of EPDM/16Me–MMT nanocomposites, the basal reflection peak was shifted toward a higher angle. However, gallery height remained more or less the same for different EPDM nanocomposites with organoclay content up to 8 wt %. The nanostructure of EPDM/clay composites was characterized by transmission electron microscopy, which established the coexistence of intercalated and exfoliated clay layers with an average layer thickness in the nanometer range within the EPDM matrix. The significant improvement in thermal stability and mechanical properties reflects the high‐performance nanocomposite formation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2429–2436, 2004     

Modification of fast-cure ethylene–propylene diene terpolymer rubber by maleic anhydride and effect of electron donor

Grafting of maleic anhydride (MA) onto fast-cure ethylene–propylene diene terpolymer rubber was studied. The effect of the amount of the MA, initiator (dicumyl peroxide), and electron donor (stearamide) on graft content are described. The potentiometric method and Fourier transform infrared spectroscopy are used to obtained the graft content. The stearamide suppresses the side reactions, such as crosslinking and chain scission. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1–5, 1998     

Dynamic mechanical properties of polypropylene‐g‐maleic anhydride and ethylene–propylene–diene terpolymer blends: Effect of blend preparation methods

In this work, we attempted two different ways of processing to improve interfacial adhesion of polypropylene (PP) and ethylene–propylene–diene terpolymer (EPDM) by introducing maleic anhydride (MAH); In one way, the in situ grafting and dynamic vulcanization (ISGV) were performed simultaneously from PP and EPDM with MAH in the presence of dicumyl peroxide (DCP) in an intensive mixer. In another way, PP was first grafted with MAH and then the PP‐g‐MAH was blended with EPDM in the intensive mixer in the presence of DCP by the dynamic vulcanization (DV). It was found that the glass transition temperatures (T_gs) of both PP and EPDM phases were shifted to higher temperature as the EPDM content increased for the blends prepared by both IGSV and DV methods, mainly due to the crosslinking of EPDM. The higher T_gs and larger storage moduli were observed for the blends prepared by the ISGV method than those prepared by the DV method, while the morphology showed that the size reduction of dispersed particles in latter blends was larger than that of the former blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2777–2784, 2000     

A comparison of white rice husk ash and silica as fillers in ethylene–propylene–diene terpolymer vulcanizates

White rice husk ash (WRHA) and silica filled ethylene–propylene–diene terpolymer (EPDM) vulcanizates were prepared using a laboratory size two‐roll mill. Curing characteristics and physical properties of vulcanizates were studied with respect to the filler loading and filler type. Filler loading was varied from 0–50 parts per hundred resin (phr) at 10 phr intervals. Curing was carried out using a semi‐efficient vulcanization system in a Monsanto rheometer. Enhancement of the curing rate was observed with increasing WRHA loading, whereas the opposite trend was observed for silica‐filled vulcanizates. It was also indicated by the maximum torque and Mooney viscosity results that WRHA offers processing advantages over silica. Compared to the silica‐filled vulcanizates, the effect of filler loading on the physical properties of WRHA‐filled vulcanizates was not significant. According to these observations, WRHA could be used as a diluent filler for EPDM rubber, while silica can be used as a reinforcing filler. © 2001 Society of Chemical Industry     

Structure and mechanical properties of nanodispersed fibrous silicate‐reinforced ethylene–propylene–diene monomer nanocomposites

In this study, ethylene–propylene–diene monomer (EPDM)/fibrillar silicate (FS) nanocomposites were successfully prepared by mechanically blending EPDM with FS, which was modified by silane coupling agent KH570 containing methacryloxy group. The effects of silane content and modified FS on the dispersion of FS and mechanical properties of the composites were investigated. The impact of water in FS on mechanical properties of the composites was also evaluated. The results showed that modified FS could be dissociated into nanofibers dispersing evenly in the EPDM matrix by increasing substantially the loading of silane through the mechanical blending. The optimum loading level of silane coupling agent was up to 24 phr/100 phr FS. Silane KH570 could improve the dispersion of FS and strengthen nanofibers–rubber interfacial adhesion even at the loading of as high as 50 phr FS, making FS to exhibit excellent reinforcement to EPDM. Too much FS could not be completely dissociated into nanofibers, slowing down further improvement. The EPDM/FS composites exhibited the similar stress–strain behavior and obvious mechanical anisotropy with short microfiber‐reinforced rubber composites. With the increase in silane coupling agent and modified FS, the number of nanofibers increased because of the exfoliation of FS microparticles; thus, the mechanical behaviors would become more obvious. It was suggested that the free water in FS should be removed before mechanically blending EPDM with FS because it obviously affected the tensile properties of the composites. Regardless of whether FS was dried or modified, the EPDM/FS composites changed little in tensile strength after soaked in hot water. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Thermooxidative aging and kinetics of the thermooxidative degradation of ethylene–propylene–diene terpolymer‐graft‐maleic anhydride/calcium carbonate composites

We report the preparation of five different ethylene–propylene–diene terpolymer‐graft‐maleic anhydride/calcium carbonate samples with different calcium carbonate contents by precipitation and their mechanical properties and structural characterization. 1 In this study, we tried to analyze the thermooxidative aging and the kinetics of thermooxidative degradation with retained tensile testing for various thermal‐aging times at 150°C and with hot‐loading‐recovery measurements. The results of the hot‐loading‐recovery measurements and retained tensile testing showed that the sample with the best crosslinked structure had the best thermooxidative‐aging resistance of all the samples. The experimental results for the thermooxidative degradation kinetics showed that the sample with the best crosslinked structure had the highest activation energy of thermal decomposition. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2395–2401, 2007     

The combination of expandable graphite,organic montmorillonite,and magnesium hydrate as fire‐retardant additives for ethylene–propylene–diene monomer/chloroprene rubber foams

The fire retardancy and flame‐retardant mechanism of expandable graphite (EG), organic montmorillonite (OMMT), and magnesium hydrate (MH) in ethylene‐propylene‐diene monomer/chloroprene rubber (EPDM/CR) foams were investigated. The results indicated that the combination of EG and OMMT remarkably improved the fire‐retardant property compared to the control samples, and better fireproof performance was achieved when MH was used as the third coretardant unit. The structure of the obtained EPDM/CR/OMMT composites was characterized by X‐ray diffraction, and the results showed that the composites had an intercalated nanostructure. The limiting oxygen index, vertical burning test, and cone calorimeter test results showed that the LOI values and UL‐94 rating increased while the second peak of the heat release rates (HRR) decreased within the EG/OMMT system. In particular, the second pHRR disappeared when the EG/OMMT/MH system was used as a flame retardant. Moreover, the results of thermogravimetric analysis showed that the combination of EG and OMMT reduced the thermal‐degradation rates and mass‐loss percentages. Furthermore, observation by scanning electron microscopy revealed that EG and OMMT left over after combustion formed a complete, compact, and rigid charred layer with a mosaic structure of expanded graphite embedded in cortical‐honeycomb layers of OMMT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44929.     

Relaxation of stress in polypropylene and ethylene–propylene–diene elastomer blend vulcanizates at moderate and high extensions

Measurements were made of the relaxation of the stress of stretched polypropylene (PP) and ethylene–propylene–diene elastomer blend vulcanizates at various strain levels. It was found that PP-blended vulcanizates showed greater relaxation than that of the gum vulcanizate at all extensions. There was a continual increase in the relaxation rate with the 10% PP-blended vulcanizate but an initial sharp decrease and then a flattening tendency with the above 10% PP-blended vulcanizate at an increasing stain level. An interesting observation of the study was that the rate of stress relaxation decreased linearly in two steps in the case of blend vulcanizates above 10% PP at 100% and above strain levels. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2155–2162, 1998     

Preparation and characterization of nano‐CaCO3 encapsulated by copolymerization of styrene and maleic anhydride

Encapsulated nanometer calcium carbonate (nano‐CaCO₃) was prepared using styrene and maleic anhydride (MAH) copolymer in 2‐propanol or methanol–water mixture in the presence of different initiator systems. The particle morphology and physical properties of the encapsulated nano‐CaCO₃ particles, such as the interaction between the encapsulating polymer and the nano‐CaCO₃, and the thermal stability of encapsulated nano‐CaCO₃ were studied by Fourier‐transform infrared spectroscopy (FTIR), Soxhlet extraction experiments, thermogravimetric analysis banded with FTIR (TGA‐FTIR) and transmission electron microscopy (TEM). The encapsulating ratio and the stable encapsulating ratio of encapsulated nano‐CaCO₃ were characterized. The results showed that a strong interfacial interaction was obtained due to the formation of a chemical bond or ion‐dipole between the C?O group of MAH and Ca²⁺ ion of nano‐CaCO₃. The encapsulating ratio and stable encapsulating ratio of nano‐CaCO₃ initiated by AIBN was higher than that initiated by BPO. Addition of maleic anhydride increased the encapsulating ratio and the stable encapsulating ratio of encapsulated nano‐CaCO₃. For the encapsulated nano‐CaCO₃ prepared in methanol–water, the diameter of the encapsulated nano‐CaCO₃ particle increased from 60–70 nm to about 100 nm and the morphology changed from a cube with a sharp edge to spherical with a rough surface. Copyright © 2006 Society of Chemical Industry     

Radiation‐processed polychloroprene‐co‐ethylene–propene diene terpolymer blends: Evaluation of blend morphology,miscibility, and physical properties

The miscibility of polychloroprene rubber (CR) and ethylene–propylene–diene terpolymer rubber (EPDM) was studied over the entire composition range. Different blend compositions of CR and EPDM were prepared by initially mixing on a two‐roll mill and subsequently irradiating to different gamma radiation doses. The blends were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, density measurement, hardness measurement, and solvent permeability analysis. The compatibility of the blends was studied by measuring the glass transition temperature and heat capacity change of the blends. The immiscibility of blends was reflected by the presence of two glass transition temperatures; however, partial miscible domains were observed due to inter diffusion of phases. Permeation data fitted best with the Maxwell's model and indicated that in CR‐EPDM blends, EPDM exists as continuous phase with CR as dispersed phase for lower CR weight fractions and phase inversion occurred in 40–60% CR region. It was observed that CR improved oil resistance of EPDM; however, the effect was prominent for blends of >20% CR content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002     

Changes in morphology and properties by grafting reaction in PP/EOR/CaCO3 ternary composites

The phase morphology and mechanical properties of polypropylene (PP) composites containing ethylene–octene elastomer (EOR) and calcium carbonate (CaCO₃) filler were investigated by comparing the toughening effect of unmodified EOR with EOR grafted with maleic anhydride (EOR–MA). EORs of various MA contents were prepared by free‐radical grafting of MA onto the EOR backbone using a reactive extrusion process. The composite morphology was directly explored by scanning electron microscopy technique and indirectly explored by differential scanning calorimetry and dynamic mechanical analysis. Separate dispersion of the elastomer and filler particles was achieved by using unmodified EOR. Modification of EOR by maleic anhydride grafting resulted in encapsulation of the filler particles. The mechanical properties of the composites were found to depend mainly on composite morphology and composition and, to a lesser degree, on maleic anhydride concentration. The results of this study showed that when composites contained an equal or higher amount of elastomer relative to filler, a composite with a separate dispersion structure was preferred. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3557–3562, 2003     

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     

Synthesis of polypropylene‐graft‐maleic anhydride compatibilizer and evaluation of nylon 6/polypropylene blend properties

Polymer blends based on polyolefins are of a great interest owing to their broad spectrum of properties and practical applications. However, because of poor compatibilities of components, most of these systems generally exhibit high interfacial tension, a low degree of dispersion and poor mechanical properties. It is generally accepted that polypropylene (PP) and nylon 6 (N6) are not compatible and that their blending results in poor materials. The compatibility can be improved by the addition of a compatibilizer, and in this study PP was functionalized by maleic anhydride (MAH) in the presence of an optimized amount of dicumyl peroxide (DCP). The reaction was carried out in the molten state using an internal mixer. Then, once the compatibilizer polypropylene‐graft‐maleic anhydride (PP‐g‐MAH) was prepared, it was added at various concentrations (2.5–10 wt%) to 30/70 glass fibre reinforced N6 (GFRN6) PP, and the mechanical properties were evaluated. It was found that the incorporation of the compatibilizer enhanced the tensile properties (tensile strength and modulus) as well as the Izod impact properties of the notched samples. This was attributed to better interfacial adhesion as evidenced by scanning electron microscopy (SEM). The optimum in these properties was achieved at a critical PP‐g‐MAH concentration. Copyright © 2005 Society of Chemical Industry     

Determination of monomer sequence distribution in EPDM by 13C‐NMR: Third monomer effects

The methods for sequencing ethylene–propylene copolymers (EPMs) by ¹³C‐NMR were extended to account for third monomer effects. The equations for calculating the ethylene content and monomer sequence distribution in EPMs were corrected for the presence of the third monomers 1,4 hexadiene, 2‐ethylidene‐5‐norbornene, and 5,8‐dicyclopentadiene that display resonances that overlap with the main chain EPM carbons. These corrections dramatically reduce the standard deviation among equivalent calculation methods. We also examined the effects of experimental conditions on the sequencing data including the choice of solvent, Cr³⁺ doping, and the presence of the nuclear Overhauser effect. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 523–530, 1999     

马来酸酐改性多孔微球的制备及表征

为了提高多孔树脂微球的亲水性,扩大其应用范围,文章通过马来酸酐(MAH)与多孔苯乙烯-二乙烯基苯共聚微球悬挂双键的接枝聚合,制备了改性的多孔树脂微球。用扫描电镜、红外光谱法、酸碱滴定法等对产物进行了表征。考察了微球的交联度、引发剂、反应时间等因素对马来酸酐接枝率和改性微球形貌的影响。在以交联度55%的多孔微球为基球,基球与MAH质量比为5∶3,质量分数为3%的偶氮二异丁腈为引发剂,80℃、反应6 h时,制得了较好多孔形貌的改性微球。结果表明,马来酸酐为改性剂有利于保持多孔微球的多孔形貌。     

Wood-fiber reinforcement of styrene–maleic anhydride copolymers

Styrene–maleic anhydride (SMA) copolymers containing either 7 or 14% maleic anhydride were filled with either pine flour or dry-process aspen fiber from a medium density fiberboard (MDF) plant. Material properties of the filled and unfilled SMA plastics were compared with those of aspen-fiber-filled and unfilled polystyrene (PS). The fiber-filled SMA composites were equivalent or superior to unfilled SMA in strength, stiffness, and notched Izod impact strength. Filled PS composites outperformed or matched the performance of filled SMA composites in the parameters tested. Unnotched Izod impact strength of filled polymers was generally inferior to that of the unfilled polymers. Water absorption from a 90% relative humidity exposure, a 24-h soak, and a 2-h boil showed mixed results when compared to the unfilled polymers. Dynamic mechanical analysis showed no change in glass transition temperature (T_g) after the addition of filler for either SMA or PS composites. The presence of the anhydride functionality on the polymer backbone did not appear to improve the strength of the composite. No evidence was found for chemical bond formation between the SMA and wood fiber. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1567–1573, 1998     

Compatibilizing effect of styrene–maleic anhydride copolymer on the properties of polyamide‐6/liquid crystalline copolyester composites

Liquid crystalline polymer–polyamide‐6 (LCP/PA6) composites containing 20 wt % LCP content were compatibilized by a random styrene–maleic anhydride copolymer (RSMA). The blending was performed via extrusion followed by injection molding. The LCP employed was a commercial copolyester, Vectra A950. The dynamic mechanical (DMA), rheological, thermal, and mechanical properties as well as the morphology of the composites were studied. The DMA and rheological results showed that RSMA is an effective compatibilizer for LCP/PA6 blends. The mechanical measurements showed that the stiffness, tensile strength, and toughness of the in situ composites are generally improved with increasing RSMA content. However, these mechanical properties deteriorated considerably when RSMA content was above 10 wt %. The drop‐weight dart impact test was also applied to analyze the toughening behavior of these composites. The results show that the maximum impact force (F_max) and crack‐initiation energy (E_init) tend to increase with increasing RSMA content. From these results, it appeared that RSMA prolongs the crack‐initiation time and increases the energies for crack initiation and impact fracture, thereby leading to toughening of LCP/PA6 in situ composites. Finally, the correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1964–1974, 2000