The Use of Ethylene/Propylene Copolymers as Compatibilizers for Recycled Polyolefin Blends

Compatibilizing effects of ethylene/propylene (EPR) diblock copolymers on the morphology and mechanical properties of immiscible blends produced from recycled low‐density polyethylene (PE‐LD) and high‐density polyethylene (PE‐HD) with 20 wt.‐% of recycled poly(propylene) (PP) were investigated. Two different EPR block copolymers which differ in ethylene monomer unit content were applied to act as interfacial agents. The morphology of the studied blends was observed by scanning‐ (SEM) and transmission electron microscopy (TEM). It was found that both EPR copolymers were efficient in reducing the size of the dispersed phase and improving adhesion between PE and PP phases. Addition of 10 wt.‐% of EPR caused the formation of the interfacial layer surrounding dispersed PP particles with the occurrence of PE‐LD lamellae interpenetration into the layer. Tensile properties (elongation at yield, yield stress, elongation at break, Young's modulus) and notched impact strength were measured as a function of blend composition and chemical structure of EPR. It was found that the EPR with a higher content of ethylene monomer units was a more efficient compatibilizer, especially for the modification of PE‐LD/PP 80/20 blend. Notched impact strength and ductility were greatly improved due to the morphological changes and increased interfacial adhesion as a result of the EPR localization between the phases. No significant improvements of mechanical properties for recycled PE‐HD/PP 80/20 blend were observed by the addition of selected block copolymers.     

Compatibilization effects of block copolymers in high density polyethylene/syndiotactic polystyrene blends

Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.     

HDPE/sPS共混体系结构与性能的研究

用2种分子量不同的苯乙烯-(乙烯/丁烯)-苯乙烯三嵌段共聚物(SEBS)和一种苯乙烯-b-乙烯/丁烯(SEB)两嵌段共聚物为增容剂,对高密度聚乙烯(HDPE)/间规聚苯乙烯(sPS)共混物进行增容.采用扫描电镜(SEM)及拉伸试验研究了增溶剂的分子量及结构对共混物形态结构及力学性能的影响.结果表明:3种增容剂SEBS(SEB)均可有效地降低sPS分散相的尺寸并增加HDPE/sPS共混物的界面强度,从而提高其力学性能.sPS 的掺入可以显著提高HDPE的耐热性能.     

Rheology,structure, and properties of ethylene–vinyl acetate/metallocene‐catalyzed ethylene–α‐olefin copolymer blends

The rheology, morphology, thermal, mechanical, and adhesive properties of blends containing ethylene–vinyl acetate and metallocene‐catalyzed ethylene–α‐olefin copolymers, containing butene and octene comonomers, were investigated. On the basis of the thermal and rheological properties and scanning electron microscopy observations, we deduced that these blends were immiscible, both in the solid and melt states over the whole range of compositions. Rheological properties were correlated to blend morphology with the Palierne emulsion model. The butene‐based blends had better mechanical properties, which was attributed to their finer morphology, lower interfacial tension, and better adhesive properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 881–889, 2004     

Effects of processing conditions and copolymer molecular weight on the mechanical properties and morphology of compatibilized polymer blends

The mechanical properties and morphology of melt mixed polystyrene (PS)/polyethylene (PE) blends that were modified by the addition of up to 16% of a semicrystalline PS-b-hPB (hydrogenated polybutadiene) diblock copolymer with varying molecular weight are reported. As a result of the blocks of the copolymer penetrating the corresponding homopolymers, these diblock copolymers are capable of reinforcing the PS/PE interface significantly. This increase in interfacial strength between the immiscible blend components does not necessarily result in an improvement in the mechanical properties of the blends as measured by Izod or tensile tests. This may be because the effect of the copolymers on the rheological properties of the blends during processing outweighs their emulsifying/reinforcing effects. If found to be universally true for polymer blends, these results suggest that the relationship between the effects of copolymers on interfacial strength, their emulsifying effects, and the mechanical properties of copolymer modified blends are not as simple as suggested by many statements found in the literature.     

Syndiotactic polystyrene‐b‐atactic polypropylene block copolymer alloy as a compatibilizer for syndiotactic polystyrene/isotactic polypropylene blends

A polymeric alloy (SP–A) containing syndiotactic polystyrene (sPS), atactic polypropylene (aPP), and about 66 wt % sPS‐b‐aPP diblock copolymer, was prepared by the sequential feed of monomers in the presence of the half‐titanocene Cp*Ti(OBz)₃ (where Cp* is C₅Me₅ and Bz is PhCH₂), modified methylaluminoxane, and external triisobutylaluminum. The effects of the SP–A alloy as a compatibilizer for sPS and isotactic polypropylene (iPP) blends were evaluated. The blending of sPS and iPP, with and without SP–A, was performed in a single‐screw miniextruder with a side channel that allowed the continuous recycling of materials. The influence of SP–A on the mechanical and thermal properties of the immiscible sPS/iPP blends was investigated over a range of composition. The presence of the SP–A alloy resulted in a significant improvement of the impact strength of the blends compared with that of pure sPS and their pure blends. This improvement was particularly obvious in the sPS/iPP (90/10 wt %) blend containing 5 wt % SP–A. Morphological analysis of the impact‐fractured surface of the ternary blends indicated that the sPS‐b‐aPP diblock copolymer contained in the SP–A alloy acted as an efficient compatibilizer by decreasing the dispersed‐phase iPP particle size, improving the interfacial adhesion, and generating a stable microphase‐separated state. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1596–1605, 2003     

Deposition of poly-p-xylylene films by plasma decomposition of cyclodi-p-xylylene

Morphology development was investigated during blending of linear low-density polyethylene (LLDPE) and polystyrene (PS) (the minor phase) in a Haake internal mixer. In addition, the blending was studied using 5 wt % Kraton styrene–ethylene/propylene (SEP) diblock or styrene–ethylene/butylene–styrene (SEBS) triblock copolymers as compatibilizing agents. Scanning electron microscopy (SEM) examinations of blends show a bimodal particle size distribution of the minor phase during the initial stage of morphological development. Morphology observations suggest that the main function of the compatibilizer during blending lies in reducing the interfacial tension between two immiscible polymer phases. The addition of the copolymer reduces the average domain size from a micron to a submicron range. Compatibilization mechanisms of the copolymers with the immiscible blends are proposed. The superiority of SEBS triblock over SEP diblock as a stabilizer of the morphology was shown. © 1995 John Wiley & Sons, Inc.     

Preparation and characterization of syndiotactic polystyrene/ethylene‐propylene copolymer blends

The reactive compatibilization of syndiotactic polystyrene (sPS)/oxazoline‐styrene copolymer (RPS)/maleic anhydride grafted ethylene‐propylene copolymer (EPR‐MA) blends is investigated in this study. First, the miscibility of sPS/RPS blends is examined by thermal analysis. The cold crystallization peak (T_cc) moved toward higher temperature with increased PRS, and, concerning enthalpy relaxation behaviors, only a single enthalpy relation peak was found in all aged samples. These results indicate that the sPS/RPS blend is miscible along the various compositions and RPS can be used in the reactive compatibilization of sPS/RPS/EPR‐MA blends. The reactive compatibilized sPS/RPS/EPR‐MA blends showed finer morphology than sPS/EPR‐MA physical blends and higher storage modulus (G') and complex viscosity (η*) when RPS contents were increased. Moreover, the impact strength of sPS/RPS/EPR‐MA increased significantly compared to sPS/EPR‐MA blend, and SEM micrographs after impact testing show that the sPS/RPS/EPR‐MA blend has better adhesion between the sPS matrix and the dispersed EPR‐MA phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2084–2091, 2002     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Compatibilization effects of styrenic/rubber block copolymers in polypropylene/polystyrene blends

Compatibilizing effects of styrene/rubber block copolymers poly(styrene‐b‐butadiene‐b‐styrene) (SBS), poly(styrene‐b‐ethylene‐co‐propylene) (SEP), and two types of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS), which differ in their molecular weights on morphology and selected mechanical properties of immiscible polypropylene/polystyrene (PP/PS) 70/30 blend were investigated. Three different concentrations of styrene/rubber block copolymers were used (2.5, 5, and 10 wt %). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the phase morphology of blends. The SEM analysis revealed that the size of the dispersed particles decreases as the content of the compatibilizer increases. Reduction of the dispersed particles sizes of blends compatibilized with SEP, SBS, and low‐molecular weight SEBS agrees well with the theoretical predictions based on interaction energy densities determined by the binary interaction model of Paul and Barlow. The SEM analysis confirmed improved interfacial adhesion between matrix and dispersed phase. The TEM micrographs showed that SBS, SEP, and low‐molecular weight SEBS enveloped and joined pure PS particles into complex dispersed aggregates. Bimodal particle size distribution was observed in the case of SEP and low‐molecular weight SEBS addition. Notched impact strength (a_k), elongation at yield (ε_y), and Young's modulus (E) were measured as a function of weight percent of different types of styrene/rubber block copolymers. The a_k and ε_y were improved whereas E gradually decreased with increasing amount of the compatibilizer. The a_k was improved significantly by the addition of SEP. It was found that the compatibilizing efficiency of block copolymer used is strongly dependent on the chemical structure of rubber block, molecular weight of block copolymer molecule, and its concentration. The SEP diblock copolymer proved to be a superior compatibilizer over SBS and SEBS triblock copolymers. Low‐molecular weight SEBS appeared to be a more efficient compatibilizer in PP/PS blend than high‐molecular weight SEBS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 291–307, 1999     

Rheological,mechanical and thermal properties of propylene‐ethylene block copolymer/polyalphaolefins blends

The rheological, thermal, and mechanical properties of propylene–ethylene block copolymer (PPB) blends with predominantly atactic molecular structure of low molecular weight polypropylene and propylene copolymers with either ethylene or 1‐butene (APAO) have been studied. It has been found that blend properties depend on comonomer type, content, and molecular weight of APAO as well as blend composition. APAO having ethylene comonomer showed better miscibility with PPB than the other ones, and high comonomer content of APAOs gave dramatic increase in impact strength over 30 wt%. It has been concluded that APAO can be used as an effective modifier of PPB. POLYM. ENG. SCI., 47:1905–1911, 2007. © 2007 Society of Plastics Engineers     

Synthesis and characterization of TPO-PLA copolymer and its behavior as compatibilizer for PLA/TPO blends

A thermoplastic polyolefin elastomer-graft-polylactide (TPO-PLA) was prepared by grafting polylactide onto maleic anhydride-functionalized TPO (TPO-MAH) in the presence of 4-dimethylaminopyridine (DMAP). The characterization of the TPO-PLA copolymers was conducted by FT-IR and ¹H NMR. The effects of reaction temperature and concentration of DMAP on the reactivity of graft polymerization were investigated by FT-IR, which revealed that a high reaction temperature and a high DMAP concentration are associated with dramatic depolymerization of PLA and reduction of steric hindrance effect in the graft reaction. A Molau test, SEM observations of cyro-fractured surface morphology and particle size analysis of PLA/TPO blend system demonstrate that this new copolymer, acting as a premade compatibilizer, significantly improved the compatibility of the PLA/TPO blends. As the concentration of TPO-PLA copolymer increased, elongation at break and tensile toughness increased with compatibilizer concentration up to 2.5 wt%, beyond which it declined, but TPO-PLA copolymer did not affect the tensile strength or modulus. The effect of the chemical composition of the TPO-PLA copolymer on the compatibilization efficiency and mechanical properties of the PLA/TPO blends was examined by altering the number of grafting sites and concentration of DMAP, suggesting that DMAP concentration dominated the properties of the ternary blend system. Two compatibilizers, TPO-MAH and TPO-PLA, were used to compatibilize the PLA/TPO blend; the results suggested that TPO-PLA was more efficient in reducing the interfacial tension between the two immiscible polymers and in improving the mechanical properties of PLA/TPO blending specimens.     

Effect of the viscosity ratio on the morphology and properties of PET/HDPE blends with and without compatibilization

The influence of the molecular weight of polyethylene on the morphology and mechanical properties of blends of high‐density polyethylene (HDPE) dispersed as droplets in a poly(ethylene terephthalate) (PET) matrix at various compositions was investigated. The difference of morphologies can be easily explained by the influence of the molecular weight on the viscosity ratio and therefore, on the critical capillary number. The compatibilizing efficiency of copolymers containing glycidyl methacrylate groups was also addressed in relation to their nature, the protocol for their drying and the molecular weight of the HDPE phase. The increase of adhesion between PET and HDPE was found to have a larger influence on tensile properties than the reduction of interfacial tension. The amount of compatibilizer needed for adhesion improvement depends on the interfacial area that is defined by both the interfacial tension and viscosity ratio of the components. A qualitative relation between the optimum amount of compatibilizer and the critical capillary number can be written. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology and mechanical properties of poly(propylene)/polystyrene blends compatibilized with polystyrene-block-poly(ethylene-co-propylene)

Compatibilizing effects of diblock copolymer polystyrene-block-poly(ethylene-co-propylene) (SEP) on the morphology and mechanical properties of immiscible blends of poly(propylene) (PP) and polystyrene (PS) were investigated. Notched impact strength, yield stress, elongation at yield and Young's modulus were determined as a function of different weight ratios of PP and PS and different amounts of added SEP as well. Scanning electron microscopy revealed a two-phase morphology of PP/PS blends, which exhibit poor mechanical properties. Even 2,5 wt.-% of SEP added to PP/PS blends can improve the notched impact strength and elongation at yield compared to non-compatibilized PP/PS blends. 10 wt.-% of SEP compatibilizer converted the brittle PP/PS blend to quite impactresistant polymeric material. Mechanical properties were improved because of the morphological changes and increased interfacial adhesion as a result of SEP localization between PP and PS phases. An analysis of yield stress data in terms of theoretical models showed that yield stress values of binary PP/PS blends can be predicted with Nielsen's model.     

Compatibilizing effect of poly(styrene)‐block‐poly(isoprene) copolymers in heterogeneous poly(styrene)/natural rubber blends

Compatibility of poly(styrene) (PS)/natural rubber (NR) blend is improved by the addition of diblock copolymer of poly(styrene) and cis‐poly(isoprene) (PS‐b‐PI). The compatibilizing effect has been investigated as a function of block copolymer molecular weight, composition and concentration. The effect of homopolymer molecular weight, processing conditions and mode of addition on the morphology of the dispersed phase have also been investigated by means of optical microscopy and scanning electron microscopy. A sharp decrease in phase dimensions is observed with the addition of a few percent of block copolymers. The effect levels off at higher concentrations. The leveling off could be an indication of interfacial saturation. For concentrations below the critical value, the particle size reduction is linear with copolymer volume fraction and agrees well with the prediction of Noolandi and Hong. The addition of the block copolymer improves the mechanical properties of the blend. An attempt is made to correlate the mechanical properties with the morphology of the blends. © 2001 Society of Chemical Industry     

Synthesis of silane‐grafted ethylene vinyl acetate copolymer and its application to compatibilize the blend of ethylene‐propylene‐diene copolymer and silicone rubber

Vinyltrimethoxysilane‐grafted ethylene vinyl acetate copolymer (EVA‐g‐VTMS) was synthesized and applied to compatibilize ethylene‐propylene‐diene copolymer (EPDM)/methyl vinyl silicone rubber (MVQ) blends. The silane‐grafting was successfully proved by differential scanning calorimetry, FTIR spectroscopy and XPS spectroscopy. The additive amount of the compatibilizer (EVA‐g‐VTMS) was optimized to be 10 phr (parts per hundred of rubber in weight) based on analysis of scanning electron microscopy, mechanical properties, aging properties, dynamic mechanical properties, rheological properties and thermal properties. Compared with the blend without EVA‐g‐VTMS, results show that the blend with 10 phr of EVA‐g‐VTMS exhibits the finest morphology. Tensile strength, elongation at break, modulus at 100% elongation, tear strength and TE index increase by 82.5%, 16.9%, 60.0%, 40.9%, and 41.9%, respectively. Dynamic mechanical analysis reveals storage modulus increase and glass transition temperatures of EPDM and MVQ move closer to each other. Rheological analysis shows a decrease in complex modulus and complex viscosity, and the processibility of the blend was improved. Furthermore, thermogravimetric analysis shows enhancement of thermal stability. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Influence of triblock copolymer interfacial modifiers on fracture behavior of polystyrene/ethylene-propylene rubber blends

In a previous study, two triblock copolymers of styrene/ethylene-butylene/styrene (SEBS), of different molecular weights, were used to compatibilize a blend of 80 vol% polystyrene (PS) and 20% ethylene-propylene rubber (EPR). The emulsification curve, which relates the average minor phase particle diameter to the concentration of interfacial agent added, was used to quantify the effect of the interfacial agents on the blend morphology. Links between morphology, interface, and properties were established by combining the emulsification curve with a fracture mechanics approach. The aim of this work is to foster the understanding of the effects of these two triblock copolymers on the fracture behavior of the blend over various loading rates and temperatures. The focus is on the brittle-ductile transition in fracture behavior, which is a critical condition for the application of these materials. It has been found that adding an interfacial agent lowers the temperature at brittle-ductile transition. However, this effect is much more pronounced for the copolymer with a lower molecular weight. The time-temperature dependence of fracture performance of the blend is also affected by the interface and morphology. When loading rate increases, the shift of the temperature at brittle-ductile transition is less significant for the blend with an interfacial agent having a lower molecular weight. The effect of loading rate and temperature on the brittle-ductile transition in fracture performance of the blends is controlled by an energy activation process. Adding the interfacial agents results in a plasticizing effect of the polystyrene matrix and a reduction in the energy barrier controlling the fracture process. With the addition of interfacial agent, the yield stress slightly increases at low concentration, attains a maximum value, and then decreases. The increase in yield stress confirms the coupling role of the copolymer and is in agreement with the observed emulsification curves. The reduction of yield stress and increase in ultimate strain with the copolymer concentration demonstrate the plasticizing effect of the interfacial agent. The result of stress relaxation tests also confirms the above effects of the interfacial agent.     

Effect of composition and comonomer type on the rheology, morphology and properties of ethylene-α-olefin copolymer/polypropylene blends

The rheology, morphology, thermal and mechanical properties of blends containing low molecular weight polypropylene (PP) and metallocene-based ethylene-α-olefin copolymers (ECs) have been investigated. Evaluation of the thermo-rheological properties of the blends showed that they are immiscible, both in the solid and melt state, over the whole range of compositions. Rheological properties were correlated to blend morphology, by using the Palierne emulsion model. The resulting low values of interfacial tension confirmed excellent compatibility between the phases.Addition of ECs in PP resulted in significant ductility improvement. The transition from plastic to elastomeric properties coincided with phase inversion. The butene-based EC was found to be the most beneficial in terms of impact properties.Fine morphologies, with sub-micron sizes of the dispersed phase, were obtained upon post-extrusion shearing of the blends.     

Effect of mixing protocol on compatibilized polymer blend morphology

We investigated the effect of mixing protocol on the morphology of compatibilized polymer blends made with premade compatibilizer and reactively formed in‐situ compatibilizer in a custom‐built miniature mixer Alberta Polymer Asymmetric Minimixer (APAM). The compatibilized blends show a finer morphology than uncompatibilized blends if the polymers are mixed together in the dry state and then fed into the mixer. It is found that premelting one polymer, and premixing polymers and compatibilizer, both greatly affect the compatibilized blends' morphology. The effects are complex since the dispersed phase particle size and distribution of the compatibilized blends may be smaller or larger when compared with the uncompatibilized system, depending on the material's physical and chemical properties; for example, diblock molecular weight or the preference of copolymer to migrate to a particular phase can change the final morphology. Good mobility of the copolymer to reach the interface is crucial to obtain a finer morphology. Micelles are observed when a high molecular weight diblock copolymer P(S‐b‐MMA) is used for a PS/PMMA blend. Because of its enhanced mobility, no micelles are found for a low molecular weight diblock copolymer P(S‐b‐MMA) in a PS/PMMA blend. For PS/PE/P(S‐b‐E) blends, finer morphology is obtained when P(S‐b‐E) is first precompounded with PS. Because the block copolymer prefers the PE phase, if the P(S‐b‐E) block copolymer is compounded with PE first, some remains inside the PE phase and does not compatibilize the interface. In the case of reactive blend PSOX/PEMA, premelting and holding the polymers at high temperature for 5 min decreases final dispersed phase particle size; however, premelting and holding for 10 min coarsens the morphology. POLYM. ENG. SCI. 46:691–702, 2006. © 2006 Society of Plastics Engineers.     

Crosslinking of polyvinyl chloride by electron beam irradiation in the presence of ethylene–vinyl acetate copolymer

Electron beam (EB) irradiation of polyvinyl chloride (PVC) was carried out in the presence of three different ethylene–vinyl acetate copolymers (EVA). The mechanical properties of the original and irradiated blends were tested. The gel content measurement, chlorine loss upon electron irradiation, and gel permeation chromatograph (GPC) were used to characterize the effect of EVA on the irradiation behavior of PVC/EVA blends. The content and the chemical structure of EVA in the blends had considerable effects on the mechanical properties and gel content of the blends. The incorporation of EVA into PVC blend can increase the gel content and reduce chlorine loss of the blends. The GPC analysis of the soluble part in the irradiated PVC samples showed that the addition of EVA into the PVC blend lowered the polydispersity of molecular weight of PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1571–1575, 2004