Phase structure and viscoelastic properties of compatibilized blends of PET and HDPE recyclates

Immiscible blends of recycled poly(ethylene terephthalate) (R‐PET), containing some amount of polymeric impurities, and high‐density polyethylene (R‐PE), containing admixture of other polyolefins, in weight compositions of 75 : 25 and 25 : 75 were compatibilized with selected compatibilizers: maleated styrene–ethylene/butylene–styrene block copolymer (SEBS‐g‐MA) and ethylene–glycidyl methacrylate copolymer (EGMA). The efficiency of compatibilization was investigated as a function of the compatibilizer content. The rheological properties, phase structure, thermal, and viscoelastic behavior for compatibilized and binary blends were studied. The results are discussed in terms of phase morphology and interfacial adhesion among components. It was shown that the addition of the compatibilizer to R‐PET‐rich blends and R‐PE‐rich blends increases the melt viscosity of these systems above the level characteristic for the respective binary blends. The dispersion of the minor phase improved with increasing compatibilizer content, and the largest effects were observed for blends compatibilized with EGMA. Calorimetric studies indicated that the presence of a compatibilizer had a slight affect on the crystallization behavior of the blends. The dynamic mechanical analysis provided evidence that the occurrence of interactions of the compatibilizer with blend components occurs through temperature shift and intensity change of a β‐relaxation process of the PET component. An analysis of the loss spectra behavior suggests that the optimal concentration of the compatibilizers in the considered blends is close to 5 wt %. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1423–1436, 2001     

In situ compatibilization of HDPE/PET blends

The reactive compatibilization of immiscible polymers such as high‐density polyethylene (HDPE) and poly(ethylene terephthalate) (PET) by interfacial grafting of maleic anhydride (MA) without initiator in the molten state was investigated in this study. Grafting reaction of MA onto HDPE was carried out in a Rheocord HAAKE mixer varying reaction parameters such as the temperature, the shear rate, and the time of reaction. Then, the purified copolymers were characterized by infrared spectrometry and the MA content of HDPE‐g‐MA copolymers was determined by volumetric titration. It has been shown that thermomechanical initiation is sufficient to reach grafting yield of 0.3 to 2.5 wt % of MA. We studied then the compatibilization of HDPE/PET blends by interfacial grafting of MA. The in situ interfacial reaction leads to the formation of HDPE‐g‐MA copolymer which acts as a compatibilizer in the blends. The foremost interest of this work is that it provides a simple way of compatibilization of immiscible blends of polyolefin and polyester in one transformation step without using free‐radical initiators. The mechanical properties of the blends are strongly improved by the addition of small quantities of MA. The SEM observations of the compatibilized blends show a deep modification of the structure (i.e., enhanced regularity in the nodule dispersion and better interfacial adhesion). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 874–880, 2001     

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     

Study of morphology influence on rheological properties of compatibilized TPU/SAN blends

The compatibilizing efficiency of three different compatibilizers on the thermoplastic polyurethane/styrene‐co‐acrylonitrile (TPU/SAN) blends properties was investigated after compatibilizer's incorporation via melt‐mixing. The compatibilizers studied were as follows: poly‐ε‐caprolactone (PCL) of different molecular weight (M_w), a mixture of polystyrene‐block‐polycaprolactone (PS‐b‐PCL) and polystyrene‐block‐poly (methyl methacrylate) (PS‐b‐PMMA), and a mixture of polyisoprene‐block‐polycaprolactone (PI‐b‐PCL) and polybutadiene‐block‐poly (methyl methacrylate) (PB‐b‐PMMA). In our study, the effect of 5 wt % added compatibilizers on TPU/SAN blends morphology was examined. The transmission electron microscopy (TEM) was used to study the morphology at different length scales and to determine the compatibilizer's location. Investigations showed the different improvement of properties, because of the different incorporation of compatibilizers in the polymer blend. The morphology influence on the rheological behavior of compatibilized blends was investigated with a stress‐controlled rheometer (Rheometric Dynamic Stress Rheometer, SR‐500). Different compatibilization activity was found for different system. It was also found that compatibilization activity of added compatibilizer strongly depends on the comaptibilizer's M_w. Blends compatibilized with PCL showed superior properties as compared with the other examined blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2303–2316, 2006     

Melt rheological properties of PBT/SEBS and reactively compatibilized PBT/SEBS/SEBS‐g‐MA polymer blends

Melt rheological properties of PBT/SEBS and PBT/SEBS/SEBS‐g‐MA blends at SEBS volume fraction (Φ_d) = 0.00–0.38 were studied at 240°C, 250°C and 260°C using a capillary rheometer. The compatibilizer SEBS‐g‐MA addition resulted in significant reduction in the dynamic interfacial tension which in turn led to increased phase adhesion. The power law exponent n decreased with increasing Φ_d and increasing temperature for both the compatiblized and uncompatiblized blends. The consistency index of PBT/SEBS increased with increasing Φ_d but were smaller than those of PBT/SEBS/SEBS‐g‐MA blends. Melt elasticity such as die swell and first normal stress difference increased with Φ_d. Variations of first normal stress coefficient function (ψ₁), recoverable shear strain (γ_R), relaxation time (λ), and shear compliance (J_c) values versus shear rate were analyzed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41402.     

Melt rheology of compatibilized polystyrene/low density polyethylene blends

Investigations have been made on the melt rheological behaviors of compatibilized blends composed of polystyrene, low density polyethylene and hydrogenated (styrene‐butadiene‐styrene) triblock copolymer used as a compatibilizer. The experiments were carried out on a capillary rheometer. The effects of shear stress, temperature and blending ratio on the activation energy for viscous flow and melt viscosity of the blends are described. The study shows that the viscosity of the blends exhibits a maximum or minimum value at a certain blending ratio. The activation energy for viscous flow decreases with increasing LDPE content. Furthermore, the concept of equal‐viscosity temperature is presented and its role in the processing of the blend is discussed. In addition, the morphology of the extrudate sample of the blends was observed by scanning electron microscopy and the correlation between the morphology and the rheological properties is explored. © 1999 Society of Chemical Industry     

Improved compatibility of PET/HDPE blend by using GMA grafted thermoplastic elastomer

ABSTRACT

Herein, graft-modified ethylene-1-octene copolymer (POE-g-GMA) and styrene-butadiene-styrene triblock copolymer (SBS-g-GMA) were found to be excellent reactive compatibilizers for immiscible poly(ethylene terephthalate) (PET)/high-density polyethylene (HDPE) blends via in-situ reaction compatibilization. With increase in compatibilizer amount, uniform phase morphology was observed in all the blends. Thus, exhibiting enhanced mechanical properties, especially, the notched Izod impact strength. In comparison with SBS-g-GMA, compatibilizer POE-g-GMA demonstrated greater impact on the compatibility. The addition of 15% POE-g-GMA produced blends with best mechanical properties. Besides, both POE-g-GMA and SBS-g-GMA enhanced the melt viscosity of PET/HDPE blends.     

Morphology and rheology of HDPE/LCP blends compatibilized by a novel PE-g-LCP copolymer

A novel graft copolymer (PE-g-LCP) consisting of polyethylene (PE) backbones and liquid crystalline polymer (LCP) branches was synthesized via reactive blending of an acrylic acid-functionalized PE (Escor 5000 by Exxon) with a semiflexible LCP (SBH 1 : 1 : 2 by Eniricerche S.p.A.). The crude reactive blending product (COP) was shown by investigation of the fractions soluble in boiling toluene and xylene and of the residue to contain unreacted Escor and SBH, together with the graft copolymer forming the interphase. The compatibilizing activity of COP for PE/SBH blends, compared to that of pure Escor, was investigated using two PE grades. The COP addition into 80/20 PE/SBH blends caused a much stronger reduction of the SBH droplet dimensions and morphology stabilization than did that of pure Escor. The rheological behavior of the samples showed that COP leads to a slight increase of interfacial adhesion in the melt as well and that the effect is more pronounced when lower molar mass PE grade is used as the blend matrix. Melt-spinning tests demonstrated that deformation of the SBH droplets into highly oriented fibrils can be obtained for the blends of lower molar mass PE, compatibilized with small amounts of the novel PE-g-SBH copolymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2069–2077, 1999     

高密度聚乙烯/聚对苯二甲酸乙二醇酯原位成纤增强复合材料的形态与力学性能

用挤出-拉伸-注塑法制得了高密度聚乙烯/聚对苯二甲酸乙二醇酯(HDPE/PET)原位成纤增强复合材料,研究了PET质量分数对PET成纤性和材料拉伸强度及模量的影响及其作用机制。熔体拉伸时分散相液滴的聚结-形变成纤对PET相形态随PET质量分数的变化起关键作用,分散相对基体增强效应和两相界面缺陷效应相互竞争是决定拉伸强度随PET质量分数变化的重要因素,纤维对基体增刚作用受纤维数量和细度的双重控制是决定材料拉伸模量与PET质量分数关系的支配因素。     

PP/PET共混熔体的流变性能研究

以PP-g-AA作增容剂,研究了PP/PET共混熔体的流变行为。讨论了温度、剪切速率以及PET和增容剂含量对熔体表观粘度、非牛顿指数等方面的影响。结果表明,PP/PET共混物熔体表观粘度随剪切速率的增大而降低,随PET及增容剂含量的增加而下降,随温度的升高而下降。PET和增容剂的加入,在共混熔体中起到了增塑剂的作用。     

Rheological behavior of noncompatibilized and compatibilized PP/PET blends with SEBS‐g‐MA

The rheological behaviors of noncompatibilized and compatibilized polypropylene/polyethylene terephthalate blends (80/20) in relation with their morphology were studied at two constant levels using maleic anhydride‐modified styrene‐ethylene‐butylene‐styrene polymer. By scanning electron microscopy of cryofractured surfaces, the morphology of the blends was examined after etching. The frequency sweep and step strain experiments were carried out for the blends. The frequency sweep results indicated that increasing the compatibilizer causes behavioral changes of the rheological properties, which could be related to the aggregation of the dispersed particles with rubbery shell. Also, the frequency sweep and step strain experiments in linear region, after cessation of simple steady shear flow with various preshear rates (higher shear stress values than G′_p), were done on compatibilized blend. The results showed that the morphology characteristics, defined by the aggregation of the dispersed particles based on rheological experimental data, were destroyed and replaced by an alignment in the flow direction for present imposed shear rates. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

LDPE/starch blends compatibilized with PE-g-MA copolymers

In the present study, low-density polyethylene (LDPE) and plasticized starch (PLST) blends, containing different percentages of PLST, were prepared. In these blends, two different polyethylene/maleic anhydride graft (PE-g-MA) copolymers containing 0.4 and 0.8 mol % anhydride groups, respectively, were added as compatibilizers at 10 wt % PLST. The compatibilization reaction was followed by FTIR spectroscopy. The morphology of the blends was studied using scanning electron microscopy (SEM). It was found that as the amount of anhydride groups in the copolymers increases a finer dispersion of PLST in the LDPE matrix is achieved. This is reflected in the mechanical properties of the blends and especially in the tensile strength. The blends compatibilized with the PE-g-MA copolymer containing 0.8 mol % anhydride groups have a higher tensile strength, which in all blends, even in those containing 20 and 30 wt % PLST, is similar to that of pure LDPE. The biodegradation of the blends followed the exposure to activated sludge. It was found that the compatibilized blends have only a slightly lower biodegradation rate compared to the uncompatibilized blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1503–1521, 1998     

回收PE/PET共混物的原位微纤化和反应增容研究

通过原位微纤化技术和反应增容,制备了含回收聚对苯二甲酸乙二醇酯(PET)、低密度聚乙烯(LDPE)和线性低密度聚乙烯(LLDPE)以及高密度聚乙烯(HDPE)的原位微纤化共混物(MRB).探讨了原位成纤作用下,相容剂马来酸酐接枝聚乙烯(PE-g-MAH)用量对共混物力学性能的影响,同时利用差示扫描量热仪(DSC)和扫描电镜(SEM)研究了含4份PE-g-MAH共混物的非等温结晶特性和共混物形态.结果表明,成纤和增容双重作用对共混物的拉伸强度、断裂伸长率、弯曲模量和弯曲强度都有提高,而冲击强度有所下降;微纤对基体聚乙烯结晶有促进作用且注塑共混物比拉伸共混物更明显.HDPE与LLDPE发生了共结晶;拉伸共混物中的微纤比注塑共混物中的微纤长.     

Morphology monitoring of PE/PBT blends by reactive processing

Polyethylene (PE)/poly(butylene terephthalate) (PBT) blends were in situ compatibilized during a processing operation by the addition of a partially hydroxylated ethylene vinyl acetate copolymer (EVAh). This copolymer, obtained from ethylene vinyl acetate (EVA), was as compatible with PE as EVA was before modification. In the presence of EVAh, the dispersion of PBT in the PE matrix was finer, and the interfacial adhesion was improved. These results are relevant for the compatibilization of PE/PBT blends. Moreover, such blends present good toluene barrier properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3568–3577, 2001     

An investigation on recycled PET/PP and recycled PET/PP‐EP compatibilized blends: Rheological,morphological, and mechanical properties

The effectiveness of P(E‐co‐MA‐co‐GMA) as a compatibilizer for recycled PET/PP and recycled PET/PP‐EP (polypropylene (ethylene‐propylene) heterophase copolymer) blends was investigated by means of morphological (scanning electron microscopy), rheological (small amplitude oscillatory shear), mechanical (tensile, flexural and impact tests), and thermal (differential scanning calorimetry) properties. Compatibilizer concentration ranged from 1 to 5 wt % with respect to the whole blend. All blends were obtained in a 90/10 composition using a twin screw extruder. Compatibilization effects for PETr/PP‐EP were more pronounced due to ethylene segments present in both PP‐EP and P(E‐co‐EA‐co‐GMA). PETr/PP‐EP has shown greater dispersed phase size reduction, a more solid‐like complex viscosity behavior and larger storage modulus at low frequencies in relation to PETr/PP blend. For both investigated blends, mechanical properties indicated an improvement in both elongation at break and impact strength with increasing compatibilizer content. PETr/PP‐EP blends showed improved performance for the same level of compatibilizer content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41892.     

Study of compatibilization of HDPE–PET blends by adding grafted or statistical copolymers

The reactive compatibilization of blends of HDPE–PET [high‐density polyethylene–poly(ethylene terephthalate)] was investigated in this study. The compatibilizers used were two grafted copolymers prepared by reactive extrusion containing 1.20–2.30 wt % GMA such as HDPE‐g‐GMA and one statistical copolymer containing 1 wt % GMA such as Lotader AX8920. HDPE was successfully functionalized using a melt free‐radical grafting technique. Grafting was initiated in two ways: adding an initiator in the polymer–monomer mixture or activation by ozone of polymer. Ozonization of HDPE by the introduction of a peroxide lead to a better grafting yield and to better grafting efficiency of the samples. The effects of the three compatibilizers were evaluated by studying the morphology and the thermal and mechanical properties of HDPE–PET (70/30 wt %) blends. Significant improvements were observed, especially in morphology, elongation at break, and Charpy impact strength of the compatibilized blends. A more pronounced compatibilizing effect was obtained with the statistical copolymer, for which the elongation at break and the impact strength were increased by 100%, while the uncompatibilized blends showed a 60% decrease in the Young's modulus and the strength at break. We also were able to show that the grafting yield increase of 1.20–2.30 wt % of GMA did not affect the properties of the blends because the grafted copolymers possess very similar chemical structures. However, compatibilization of blends with grafted copolymers is an interesting method, particularly for recycled blends, because the synthesis of these compatibilizers is easy and cheap in comparison to statistical copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2377–2386, 2001     

Melting,crystallization behaviors,and nonisothermal crystallization kinetics of PET/PTT/PBT ternary blends

The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (T_g) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t_1/2 and the parameters Z_c showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Linear viscoelastic behavior of compatibilized PMMA/PP blends

In this work, the morphology and linear viscoelastic behavior of PMMA/PP blends to which a graft copolymer PP‐g‐PMMA has been added was studied. The copolymer concentration varied from 1 to 10 wt % relative to the dispersed phase concentration. The rheological data were used to infer the interfacial tension between the blended components. It was observed that PP‐g‐PMMA was effective as a compatibilizer for PMMA/PP blends. For PP‐g‐PMMA concentration added below the critical concentration of interface saturation, two rheological behaviors were observed depending on the blend concentration: for 70/30 blend, the storage modulus, at low frequencies, increased as compared to the one of the unmodified blend; for 90/10 blend, it decreased. For 90/10 blend, the relaxation spectrum presented an interfacial relaxation time related to the presence of the compatibilizer (τ_β). For PP‐g‐PMMA concentrations added above the critical concentration of interface saturation, the storage modulus of all blends increased as compared with the one of the unmodified blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of reactively compatibilized polyester and polyamide blends

The functionalization of poly(butylene terephthalate) (PBT) has been accomplished in a twin screw extruder by grafting maleic anhydride (MA) using a free radical polymerization technique. The resulting PBT‐g‐MA was successfully used as a compatibilizer for the binary blends of polyester (PBT) and polyamide (PA66). Enhanced mechanical properties were achieved for the blend containing a small amount (as low as 2.5 %) of PBT‐g‐MA compared to the binary blend of unmodified PBT with PA66. Loss and storage moduli for blends containing compatibilizer were higher than those of uncompatibilized blends or their respective polymers. The grafting and compatibilization reactions were confirmed using FTIR and ¹³C NMR spectroscopy. The properties of these blends were studied in detail by varying the amount of compatibilizer, and the improved mechanical behaviour was correlated with the morphology with the help of scanning electron microscopy. Morphology studies also revealed the interfacial interaction in the blend containing grafted PBT. The improvement in the properties of these blends can be attributed to the effective interaction of grafted maleic anhydride groups with the amino group in PA66. The results indicate that PBT‐g‐MA acts as an effective compatibilizer for the immiscible blends of PBT and PA66. © 2000 Society of Chemical Industry     

Mechanical behaviors of ethylene/styrene interpolymer compatibilized polystyrene/polyethylene blends

In this study, ethylene/styrene interpolymer was used as a compatibilizer for the blends of polystyrene (PS) and high‐density polyethylene (HDPE). The mechanical properties including tensile and impact properties and morphology of the blends were investigated by means of uniaxial tension, instrumented falling‐weight impact measurements, and scanning electron microscopy. Tensile tests showed that the yield strength of the PS/HDPE/ESI blends decreases considerably with increasing HDPE content. However, the elongation at break of the blends tended to increase significantly with increasing HDPE content. The excellent tensile ductility of the HDPE‐rich blends resulted from shield yielding of the matrix. Izod and Charpy impact measurements indicated that the impact strength of the blends increases slowly with HDPE content up to 40 wt %; thereafter, it increases sharply with increasing HDPE content. The impact energy of the HDPE‐rich blends exceeded that of pure HDPE, implying that the HDPE polymer can be further toughened by the incorporation of brittle PS minor phase in the presence of ESI compatibilizer. The correlation between the impact property and morphology of the blends is discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4001–4007, 2007