On the mechanism of compatibilization of polyolefin/liquid crystalline polymer blends with graft copolymers

The compatibilization mechanism of some compatibilizers for blends of polyolefins with a liquid crystalline polymer (LCP) was studied. Polyethylene (PE) and polypropylene (PP) were blended with a semirigid LCP (SBH) in a batch mixer, either with and without compatibilizers. The latter were two commercially available samples of functionalized polyolefins, that is, a PE‐g‐MA (HDM) and a PP‐g‐AA (Polybond 1001) copolymer and some purposely synthesized PE‐g‐LCP and PP‐g‐LCP copolymers. Microtomed films of the binary and the ternary blends were annealed at 240°C on the hot stage of a polarizing microscope and the changes undergone by their morphology were recorded as a function of time. The results indicate that the compatibilizers lower the interfacial tension, thereby providing an improvement of the minor phase dispersion. In addition to this, the rate of the coalescence caused by the high‐temperature treatment is appreciably reduced in the systems compatibilized with the PE–SBH and PP–SBH graft copolymers. Among the commercial compatibilizers, only Polybond 1001 displayed an effect comparable to that of the above copolymers. HDM improved the morphology of the as‐prepared PE blends, but failed to grant sufficient morphological stabilization against annealing‐induced coarsening. The results are discussed with reference to the chemical structure of the different compatibilizers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3027–3034, 2000     

Reactive compatibilization of poly(butylene terephthalate)/low‐density polyethylene and poly(butylene terephthalate)/ethylene propylene diene rubber blends with a bismaleimide

The reactive compatibilization effect of a small molecule, bismaleimide (BMI), on poly(butylene terephthalate) (PBT)/low‐density polyethylene (LDPE) and PBT/ethylene propylene diene (EPDM) rubber blends were investigated. All the blends were prepared by melt blending in the mixing chamber of a Haake Rheocord. The particle size of dispersed phase was reduced by >ten times by adding 1.2 wt % of BMI as observed with scanning electron microscopy. The torque‐time curve recorded during mixing showed that the addition of BMI leads to a significant increase in the viscosity of PBT, LDPE, EPDM, and the blends. This indicates that a chemical reaction has taken place. It was confirmed that free radicals are involved in the reactions because the addition of a stabilizer to the blends has removed all the compatibilizing effect, and the torque‐time curve does not show any increase in viscosity. A possible mechanism of compatibilization is proposed. The shear forces during melt mixing cause the rupture of chemical bond in the polymers, which form macroradicals of PBT, LDPE, or EPDM. These macroradicals react with BMI to form PBT‐BMI‐LDPE or PBT‐BMI‐EPDM copolymers. These in situ‐formed copolymers act as compatibilizers to give a significant refinement of the blend morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2049–2057, 1999     

Reactive processing compatibilization of direct injection molded polyamide‐6/poly(ethylene terephthalate) blends

Finely dispersed blends of polyamide 6 (PA‐6) and poly(ethylene terephthalate) (PET) were obtained by direct injection molding throughout the full composition range. The blends comprised a probably pure PA‐6 phase, and a PET phase that was apparently pure in PET‐rich blends and contained slight reacted PA‐6 amounts in PA‐6‐rich blends. This very complex morphology was characterized by the presence of dispersed particles at three levels and by a very large interface area/dispersed phase volume ratio. The linear ductility behavior was attributed to both the presence of reacted copolymers and the large interface area/dispersed volume ratio, and the synergism in both the Young's modulus and yield stress to the increased orientation of the blends related to that of the pure components. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 564–574, 2005     

Compatibilization of a polyolefin blend through covalent and ionic coupling of grafted polypropylene and polyethylene. I. Rheological,thermal, and mechanical properties

A polypropylene/high‐density polyethylene blend containing 70 wt % polypropylene was prepared and compatibilized via the addition of maleic anhydride grafted polypropylene and polyethylene. The functionalized polymer chains were coupled with two types of coupling agents. Dodecane diamine formed covalent bonds with the maleic anhydride, whereas two metallic salts, zinc acetate and sodium hydrogenocarbonate, formed ionic interactions with the carboxylic functions produced by the hydration of the anhydride cycle. The coupling of the grafted polyolefin chains was successfully realized by a single operation in a twin‐screw extruder. The coupling agents were efficient in improving the elongation at break and impact properties of the studied blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 312–320, 2005     

Reactive compatibilization of an immiscible polyester/polyolefin blend with PP‐g‐MAH and PMPI dual compatibilizers

Blends of a polyester hot melt resin and a poly‐α‐olefin hot melt resin were modified using the reactive compounding technique. The effects of the compatibilizers were evaluated by studying the mechanical properties, the morphology, and the thermal properties of the modified blends. A pronounced compatibilizing effect was obtained with dual compatibilizers composed of maleated polypropylene and poly[methylene (phenylene isocyanate)] (PMPI). The addition of 1 phr of PMPI was sufficient to improve the elongation and tensile strength. From the results, it is anticipated that PMPI can be used as an efficient coupler to enhance the compatibility of immiscible polyester/polyolefin blends. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40232.     

Correlation between the morphology and dynamic mechanical properties of ethylene vinyl acetate/linear low‐density polyethylene blends: Effects of the blend ratio and compatibilization

The effects of the blend composition and compatibilization on the morphology of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were studied. The blends showed dispersed/matrix and cocontinuous phase morphologies that depended on the composition. The blends had a cocontinuous morphology at an EVA concentration of 40–60%. The addition of the compatibilizer first decreased the domain size of the dispersed phase, which then leveled off. Two types of compatibilizers were added to the polymer/polymer interface: linear low‐density polyethylene‐g‐maleic anhydride and LLDPE‐g phenolic resin. Noolandi's theory was in agreement with the experimental data. The conformation of the compatibilizer at the blend interface could be predicted by the calculation of the area occupied by the compatibilizer molecule at the interface. The effects of the blend ratio and compatibilization on the dynamic mechanical properties of the blends were analyzed from ?60°C to +35°C. The experiments were performed over a series of frequencies. The area under the curve of the loss modulus versus the temperature was higher than the values obtained by group contribution analysis. The loss tangent curve showed a peak corresponding to the glass transition of EVA, indicating the incompatibility of the blend system. The damping characteristics of the blends increased with increasing EVA content because of the decrease in the crystalline volume of the system. Attempts were made to correlate the observed viscoelastic properties of the blends with the morphology. Various composite models were used to model the dynamic mechanical data. Compatibilization increased the storage modulus of the system because of the fine dispersion of EVA domains in the LLDPE matrix, which provided increased interfacial interaction. Better compatibilization was effected at a 0.5–1% loading of the compatibilizer. This was in full agreement with the dynamic mechanical spectroscopy data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4526–4538, 2006     

Melt rheology and morphology of LLDPE/EVA blends: Effect of blend ratio,compatibilization, and dynamic crosslinking

The melt rheological properties of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were investigated with special reference to the effect of blend ratio, temperature, shear rate, compatibilization, and dynamic vulcanization. The melt viscosity of the blends determined with a capillary rheometer is found to decrease with an increase of shear rate, which is an indication of pseudoplastic behavior. The viscosity of the blend was found to be a nonadditive function of the viscosities of the component polymers. A negative deviation was observed because of the interlayer slip between the polar EVA and the nonpolar LLDPE phases. The melt viscosity of these blends decreases with the increased concentration of EVA. The morphology of the extrudate of the blends at different shear rates and blend ratios was studied and the size and distribution of the domains were examined by scanning electron microscopy. The morphology was found to depend on shear rate and blend ratio. Compatibilization of the blends with phenolic‐ and maleic‐modified LLDPE increased the melt viscosity at lower wt % of compatibilizer and then leveled off. Dynamic vulcanization is found to increase the melt viscosity at a lower concentration of DCP. The effect of temperature on melt viscosity of the blends was also studied. Finally, attempts were made to correlate the experimental data on melt viscosity and cocontinuity region with different theoretical models. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3210–3225, 2002     

Novel reactive compatibilization strategy on immiscible polypropylene and polystyrene blend

Polypropylene (PP) and polystyrene (PS) are immiscible and incompatible. Since both PP and PS components possess no reactive functional group, reactive compatibilization of a PP/PS blend is impossible unless certain reactive functional groups are imparted to either PP or PS. In this study we provide a simple approach to reactively compatibilize the nonreactive PP/PS blend system by physically functionalizing PP and PS with the addition of maleic anhydride grafted PP (PP‐g‐MA) and styrene maleic anhydride random copolymer (SMA), respectively. An epoxy monomer, serving as a coupler and possessing four epoxy groups able to react with the maleic anhydride of PP‐g‐MA and SMA, was then added during melt blending. Observations of the finer PS domain sizes and improved mechanical properties support the plausibility of reactive compatibilization of this nonreactive PP/PS blend by combining physically functionalized PP and PS with tetra‐glycidyl ether of diphenyl diamino methane (TGDDM) in a one‐step extrusion process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and characterization of polymethyltrifluoropropylsilicone modified acrylonitrile–butadiene rubber/fluorosilicon rubber blend

The blending of polymethyltrifluoropropylsilicone‐modified acrylonitrile–butadiene rubber (MNBR) and fluorosilicon rubber (FSR) at 70 : 30 ratio was investigated. The grafting of mercapto‐functionalized polymethyltrifluoropropylsilicone onto acrylonitrile‐butadiene rubber (NBR) by thiol‐ene reaction was carried out with 2,2′‐azobisisobutyronitrile as initiator in a Haake torque rheometer. The rheological properties of NBR grafting obtained at varying dosages of polymethyltrifluoropropylsilicone in a Haake torque rheometer were studied using torque curves. Grafting reaction was confirmed by ¹H nuclear magnetic resonance and energy‐dispersive X‐ray spectroscopy. Results of scanning electron microscopy and dynamic mechanical analysis showed better compatibility of MNBR/FSR blend than NBR/FSR reference blend. Meanwhile, the macro‐mechanical properties of the blend significantly improved. The tensile strength and tear strength of MNBR/FSR blend were improved to 14.34 MPa and 44.94 KN/m, respectively, which were 2.92 MPa and 13.03 KN/m higher than those of NBR/FSR reference blend. The low‐temperature brittleness of the blend was improved to ?57°C, an increase of ?6°C compared with that of NBR. These results indicated that MNBR/FSR blend at 70 : 30 ratio had improved compatibility because of the grafting chains that acted as interfacial agents. The low‐temperature resistance of the blend was also enhanced. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42328.     

Compatibilization of recycled poly(ethylene terephthalate) and polypropylene blends: Effect of compatibilization on blend toughness,dispersion of minor phase,and thermal stability

Blending of recycled polyethylene terephthalate (RPET) from waste bottles with polypropylene (PP) was performed in an attempt to enhance the processability of RPET. The idea of blending RPET with PP sprouted from the intention of recycling PET bottles together with their PP‐based caps. Therefore, preliminary blending of RPET with neat PP (RPET/PP) was performed at various PP and compatibilizer contents. Morphological analyses on the extruded pellets of uncompatibilized blends indicate that the PP particle size and state of dispersion at skin and core regions were vastly different. The particles at the skin were at least 10 times smaller than that at the core although the size distribution was very wide. With the incorporation of just 5 phr of compatibilizer, the particles at the core region became significantly smaller and appeared to emulate that of the skin region. Furthermore, the overall homogeneity of the blends was vastly improved irrespective of PP content in the blend. The reduction in particle size and improved homogeneity inherently reduced stress concentration points and enhanced the mechanical performance of the blends. More importantly, the incorporation of PP into RPET significantly increased the degradation temperature of the blends, provided the dispersion of PP phase in RPET was excellent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reactive compatibilization of the poly(butylene terephthalate)–EVA blend by maleic anhydride. II. Correlations among gel contents,grafting yields,and mechanical properties

Correlations among the degree of crosslinking of ethylene vinyl acetate copolymer (EVA), the grafting yield of maleic anhydride (MAH) onto EVA, and the mechanical properties of the blends of poly(butylene terephtalate) (PBT) with EVA‐g‐MAH were investigated. The EVA was functionalized by melt grafting reaction in the presence of MAH and dicumyl peroxide (DCP) using a plasticorder. The grafting yield of MAH was increased by increasing the concentration of MAH and DCP. The flexural strength of PBT–EVA‐g‐MAH blends depends on both the grafting yield of MAH and the degree of crosslinking of EVA, while the crosslinked parts of EVA‐g‐MAH hindered rather than improved the tensile strength regardless of the increase of the grafting yield of MAH. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1305–1310, 2003     

Assessment of compatibilization efficiency of SEBS in the PP/PS blend

The compatibilization efficiency of styrene–ethylene/butylene–styrene (SEBS) triblock copolymer in immiscible polypropylene (PP)/polystyrene (PS) 20/80 blends was evaluated in terms of not only morphology, but also rheology and fractionated crystallization behavior. Besides varying SEBS loading, four different mixing protocols were used to vary SEBS dispersion state. PP²/PS/SEBS blend, prepared by two‐step method mixing PS and SEBS primarily, presents the largest droplet size (1.278 μm) at the critical compatibilizer concentration (CCC = 1 wt %). However, the CCC of blends prepared by the other protocols is 2 wt %. And at the CCC, PP/PS²/SEBS (two step method mixing PP and SEBS primarily) shows the smallest droplet size (0.908 μm), followed by PP/PS/SEBS (one step method). The rheology and crystallization behavior of PP/PS blends could also be utilized to assess the compatibilization efficiency of SEBS, but only in the case of mixing under the same protocol and the content of SEBS below a CCC. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46244.     

Influences of ethylene–butylacrylate–glycidyl methacrylate on morphology and mechanical properties of poly(butylene terephthalate)/polyolefin elastomer blends

Elastomer ethylene–butylacrylate–glycidyl methacrylate (PTW) containing epoxy groups were chosen as toughening modifier for poly(butylene terephthalate) (PBT)/polyolefin elastomer (POE) blend. The morphology, thermal, and mechanical properties of the PBT/POE/PTW blend were studied. The infrared spectra of the blends proved that small parts of epoxy groups of PTW reacted with carboxylic acid or hydroxyl groups in PBT during melt blending, resulting in a grafted structure which tended to increase the viscosity and interfere with the crystallization process of the blend. The morphology observed by scanning electron microscopy revealed the dispersed POE particles were well distributed and the interaction between POE and PBT increased in the PBT/POE/PTW blends. Mechanical properties showed the addition of PTW could lead to a remarkable increase about 10‐times in impact strength with a small reduction in tensile strength of PBT/POE blends. Differential scanning calorimetry results showed with increasing PTW, the crystallization temperature (T_c) and crystallinity (X_c) decreased while the melting point (T_m) slightly increased. Dynamic mechanical thermal analysis spectra indicated that the presence of PTW could improve the compatibility of PBT/POE blends. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40660.     

Effect of pellet size and compatibilization on thermal decomposition kinetic of recycled polyethylene terephthalate/recycled polypropylene blend

This study considers the effects of pellet geometry and compatibilization on its moisture absorption and thermal degradation behavior of recycled polyethylene terephthalate (RPET) and recycled polypropylene (RPP) blend with the ultimate goal of optimizing the design of pellets to enhance their processability. The isoconversion of Flynn–Wall–Ozawa (FWO) was used for the kinetic study, which was suitable for thermal degradation of RPET/RPP blend in N₂ while the second order polynomial function was fitted for thermal oxidative degradation in air. Finer geometries, such as powders, were found to have higher moisture absorption rates due to their large surface area although they could also be easily dried. Furthermore, large surface area of fine powder as well as good interaction between RPP disperse particles and RPET matrix eased to decompose in the presence of oxygen thus accelerated chain breaking during thermal oxidative degradation especially at low heating rate. Meanwhile, larger pellets exhibited higher degradation activation energies, which suggest that they are more resistant to thermal degradation than smaller grains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal,mechanical, and dielectric behaviors of crosslinked linear low density polyethylene/polyolefin elastomers blends

Crosslinked linear low density polyethylene (XLPE) containing polyolefin elastomers (POE) has been evaluated. The blends with different dicumyl peroxide (DCP) and POE contents have been prepared and processed by compression molding. A series of the samples obtained have been investigated by gel content determination, scanning electron microscopy (SEM), different scanning calorimetry (DSC), mechanical, and dielectric behaviors measurements. The results obtained clearly show the relevant influence of the POE content, as well as of the DCP content, which tends to enhance crosslinking. As expected, the toughness of XLPE is improved by using adequate content of POE, and the blends exhibit a much more similar tensile behavior to that of elastomer. In addition, the results indicate that the blends possess the excellent dielectric behaviors, such as dielectric constant and dissipation factor. The crystallinity of the blends decreases as the DCP and POE contents increase. The melting temperature of the blends also decreases with the increase of DCP content, while POE content has few influences on the melting temperature of the blends. The SEM images strongly reveal that the blends are partially compatible, and the POE can be dispersed well in the matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1920–1927, 2007     

Encapsulated phase structure and morphology evolution during quiescent annealing in ternary polymer blends with PA6 as matrix

This work is aim to study the encapsulated morphology development in ternary blends of polyamide 6/high density polyethylene/maleic anhydride‐grafted‐ethylene propylene diene monomer (PA6/HDPE/EPDM‐g‐MA) and polyamide 6/maleic anhydride‐grafted‐high density polyethylene/ethylene propylene diene monomer (PA6/HDPE‐g‐MA/EPDM) through thermodynamically control described by Harkins spreading theory. The phase morphology was confirmed by using scanning electron microscope (SEM) and selective solvent extraction revealed that PA6/HDPE/EPDM‐g‐MA blend having a composition of 70/15/15 vol % is constituted of polyamide 6 matrix with dispersed composite droplets of HDPE subinclusions encapsulated by EPDM‐g‐MA phase, while for PA6/HDPE‐g‐MA/EPDM blend with the same composition is constituted of polyamide 6 matrix with dispersed composite droplets of HDPE‐g‐MA subinclusions encapsulated by EPDM phase. Quiescent annealing test revealed that for PA6/HDPE/EPDM‐g‐MA blend, a perfect core–shell structure with one HDPE particle encapsulated by EPDM‐g‐MA phase was formed during annealing, and for PA6/HDPE‐g‐MA/EPDM blend, a novel complete inverting HDPE‐g‐MA/EPDM core/shell structure was achieved. Moreover, quantitative analysis about coalescent behaviors of HDPE‐g‐MA and HDPE subinclusions during quiescent annealing were investigated by image analysis and the result suggested that the grafted maleic anhydride group in HDPE‐g‐MA, acted as a role of steric repulsion, could suppress coalescence effects, thus leaded to a lower coalescent rate than that of HDPE subinclusions. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39937.     

Impact modification of poly(ethylene terephthalate)

The tensile and impact resistance of impact‐modified poly(ethylene terephthalate) (PET) is investigated. The impact modifiers are polyolefin‐based elastomers or elastomer blends containing glycidyl methacrylate moieties to improve the adhesion with the polyester. The tensile properties are measured on injection molded specimens at room temperature while the Izod impact strength is measured from ?40 to 20°C. The blend morphology is observed by scanning electron microscopy and the dispersed phase average diameter is determined by image analysis. The relation between the impact resistance and the phase morphology is discussed, and the critical ligament size for PET is determined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2919–2932, 2003     

Effect of various added compatibilizers on the crystalline structure of polypropylene homopolymer/polybutylene terephthalate and polypropylene copolymer/polybutylene terephthalate polymer blends

Blends of semicrystalline isotactic polypropylene homopolymer and polypropylene copolymer with polybutylene terephthalate with different compatibilizers [i.e., styrene acrylonitrile, Surlyn, styrene–ethylene–butadiene styrene (SEBS), block copolymer and SEBS block copolymer grafted with maleic anhydride] were prepared by melt blending. Wide angle‐X‐ray scattering patterns of injection moldings were obtained. The crystallinity index and d‐spacing were calculated with different concentrations of different compatibilizers. X‐ray results in the structural investigation of the compatibilized blends correlated well with the different compatibilizer concentrations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1190–1193, 2003     

Effect of anhydride‐modified ethylene–propylene–diene rubber and ethylene–vinyl acetate copolymers on the compatibilization of nitrile rubber/ethylene–propylene–diene rubber blends

The effects of maleic anhydride modified ethylene–propylene–diene rubber (EPDMMA) and maleic anhydride modified ethylene–vinyl acetate (EVAMA) on the compatibilization of nitrile rubber (NBR)/ethylene–propylene–diene rubber (70:30 w/w) blends vulcanized with a sulfur system were investigated. The presence of EPDMMA and EVAMA resulted in improvements of the tensile properties, whereas no substantial change was detected in the degree of crosslinking. The blend systems were also analyzed with scanning electron microscopy and dynamic mechanical thermal analysis. The presence of EVAMA resulted in a blend with a more homogeneous morphology. The compatibilizing effect of this functional copolymer was also detected with dynamic mechanical analysis. A shift of the glass‐transition temperature of the NBR phase toward lower values was observed. The presence of EPDMMA and EVAMA also increased the thermal stability, as indicated by an improvement in the retention of the mechanical properties after aging in an air‐circulating oven. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2408–2414, 2003     

Blends of nylon with polyethylene: Effect of compatibilization on mechanical and dynamic mechanical properties

Blends of Nylon 6 with very low density polyethylene (VLDPE) have been studied. The blends exhibit two phase morphology wherein VLDPE is dispersed in the form of spherical domains in Nylon 6 matrix. The water absorption of the blends decreased with increasing VLDPE content. The mechanical properties of these blends show loss in tensile and impact strength due to poor adhesion at the interface. Addition of a compatibilizer containing MAH groups was found to result in improved properties. The tensile strength increased significantly whereas impact testing showed no break confirming better stress transfer across the interface. The dynamic mechanical analysis showed presence of microheterogeneity resulting into merging of tan delta peaks as a result of compatibilization. The observed results are ascribed to the possible reaction between reactive groups in Nylon 6 and the compatibilizer leading to compatibilization through copolymer formation. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 161–168, 1998