In situ compatibilization of PET/PS blends through reactive copolymers

Polymer blends of poly(ethylene terephthalate) (PET) and polystyrene (PS) are immiscible and incompatible, which has been well recognized. Styrene–glycidyl methacrylate (SG) copolymer has been synthesized by suspension polymerization and employed in this study as an in situ compatibilizer for the polyblends of PET and PS. This copolymer contains reactive epoxy functional groups that are able to react with PET end groups ? OH and ? COOH) under melt conditions to from SG-graft-PET copolymer. The presence of a small amount of phosphonium catalyst (200 ppm) accelerated the graft reaction and results in a better compatibilized blend. The compatibilized PET/PS blend has a smaller phase domain and higher viscosity than does the corresponding noncompatibilized blend. Mechanical properties of the compatibilized blends have also been improved significantly over the corresponding noncompatibilized blends. © 1993 John Wiley & Sons, Inc.     

Rheological,thermal, and morphological properties of ABS–PA1010 blends

Noncompatibilized and compatibilized ABS–nylon1010 blends were prepared by melt mixing. Polystyrene and glycidyl methacrylate (SG) copolymer was used as a compatibilizer to enhance the interfacial adhesion and to control the morphology. This SG copolymer contains reactive glycidyl groups that are able to react with PA1010 end groups ( NH₂ or  COOH) under melt conditions to form SG‐g‐Nylon copolymer. Effects of the compatibilizer SG on the rheological, thermal, and morphological properties were investigated by capillary rheometer, DSC, and SEM techniques. The compatibilized ABS–PA1010 blend has higher viscosity, lower crystallinity, and smaller phase domain compared to the corresponding noncompatibilized blend. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 683–688, 1999     

Polymer blends of polyamide-6 and poly(phenylene oxide) compatibilized by styrene-co-glycidyl methacrylate

Incompatible polymer blends between polyamide-6 (PA6) and poly(phenylene oxide) (PPO) have been compatibilized in situ by the styrene-glycidyl methacrylate (SG) reactive copolymers. The epoxy functional groups in SG copolymers can react with the PA6 amine and carboxylic endgroups at interface to form various SG-g-PA6 copolymers. These in situ-formed grafted copolymers tend to anchor along interface to function as compatibilizer of the blends. The styrene and the SG segments of the grafted copolymers are miscible (or near miscible) with PPO; whereas the PA6 segments are structurally identical with PA6 phase. The compatibilized blend, depending on quantity of the compatibilizer addition and the glycidyl methacrylate (GMA) content in the SG copolymer, results in smaller phase domain, higher viscosity, and improved mechanical properties. About 5% GMA is the optimum content in SG copolymer that produces the best compatibilization of the blends. This study demonstrates that SG reactive copolymers can be used effectively in compatibilizing polymer blends of PA6 and PPO. © 1996 John Wiley & Sons, Inc.     

Reactive compatibilization of the poly(ethylene terephthalate)/liquid crystalline polymer blends by solid epoxy resin as a coupling agent

A selected reactive coupling agent can be served as an effective compatibilizer for certain immiscible and incompatible blends should both blend constituents possess the necessary functional groups that can react with the coupling agent at comparable rates. Solid epoxy resin with two epoxide endgroups per molecule was demonstrated to be an efficient reactive compatibilizer for the incompatible blends of poly(ethylene terephthalate) (PET) and copolyester liquid crystalline polymer (LCP) by functioning as a coupling agent. The main chain structure of the epoxy resin is neither identical not miscible with PET and LCP and tends to reside at interface during melt mixing. This preferential residence gives the epoxy compatibilizer greater opportunity to react with both PET and LCP simultaneously to produce the in situ–formed epoxy-b-LCP mixed copolymer. This in situ–formed mixed copolymer is highly effective in compatibilizing the PET/LCP blends. This reactive epoxy compatibilizer enhances the LCP fibril formation and results in substantial improvements on stiffness and toughness of the PET/LCP blends. © 1996 John Wiley & Sons, Inc.     

Influence of a compatibilizer on the properties of polyethylene–octene elastomer/starch blends

The effect of a compatibilizer on the properties of corn starch‐reinforced metallocene polyethylene–octene elastomer (POE) blends was studied. The compatibility between POE and starch was improved markedly with an acrylic acid‐grafted POE (POE‐g‐AA) copolymer as a compatibilizer. Fourier transform infrared spectroscopy, X‐ray diffraction spectroscopy, differential scanning calorimetry, and scanning electron microscopy were used to examine the blends produced. The size of the starch phase increased with an increasing content of starch for noncompatibilized and compatibilized blends. The POE/starch blends compatibilized with the POE‐g‐AA copolymer lowered the size of the starch phase and had a fine dispersion and homogeneity of starch in the POE matrix. This better dispersion was due to the formation of branched and crosslinked macromolecules because the POE‐g‐AA copolymer had anhydride groups to react with the hydroxyls. This was reflected in the mechanical properties of the blends, especially the tensile strength at break. In a comparison with pure POE, the decrease in the tensile strength was slight for compatibilized blends containing up to 40 wt % starch. The POE‐g‐AA copolymer was an effective compatibilizer because only a small amount was required to improve the mechanical properties of POE/starch blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1792–1798, 2002     

Synthesis of compatibilizers and characterization of the compatibilized and noncompatibilized blends of PP/Rodrun LC3000

The addition of a liquid crystalline polymer (LCP) to a matrix of a flexible thermoplastic (TP) has been used in the last two decades as an in situ reinforcement of the matrix. Owing to the immiscibility of the two phases and the high degree of orientation typical of LCPs, the dispersed phase is, after processing, essentially constituted by fibrillar structures, which are responsible for the reinforcement of the matrix and the decrease of viscosity with respect to the matrix. The low degree of adhesion typical of LCP/TP blends often requires the use of compatibilizers, which will act reducing the interfacial tension between the two components. In this work, we present the synthesis of three different compatibilizers, as well as the mechanical characterization of the corresponding compatibilized blends. Some scanning electron microphotographs will be also presented to better explain the mechanical results. The mechanical properties of these blends were compared with the noncompatibilized blend, as well as with the ones presented by blends obtained with two commercial compatibilizers, leading to the conclusion that, considering our compatibilizer C, the one that leads to the higher enhancement of the Young's modulus, when compared with the noncompatibilized blend, we obtain a Young's modulus 27% higher than the one presented by the noncompatibilized blend. Comparing this result with those presented by the blends compatibilized with the two commercial compatibilizers, D and E, we conclude that this enhancement is higher than those presented by those blends (increase in Young's modulus of 16% for both compatibilizers). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Compatibilizers for thermotropic liquid crystalline polymer/polyethylene blends prepared by reactive mixing

This paper describes the effects of composition and processing conditions on the efficiency of the compatibilizer prepared from a thermotropic liquid crystalline polymer (TLCP) and the sodium salt of a poly(ethylene‐co‐r‐acrylic acid) ionomer (EAA‐Na) in TLCP/low‐density polyethylene (LDPE) blends and TLCP/high‐density polyethylene (HDPE) blends. The TLCP‐ionomer graft copolymer formed by a melt acidolysis reaction effectively reduced the interfacial tension between TLCP and polyethylene, which improved impact strength and toughness of the compatibilized blends. Higher processing temperatures for the reactive extrusion produced a more efficient compatibilizer, presumably due to increased graft‐copolymer formation, but the reaction temperature had little effect on the impact strength of compatibilized blends for temperatures above 300°C. The addition of the compatibilizer to TLCP/LDPE blends significantly increased the melt viscosity due to increased interfacial adhesion. The TLCP/EAA‐Na ratio used to prepare the compatibilizer had little effect on the performance of the compatibilizer. Although the compatibilizer can be prepared in situ by blending and extruding a ternary blend of TLCP/EAA‐Na/polyethylene, pre‐reacting the compatibilizer resulted in blends with improved toughness and elongation.     

Novel approach for the preparation of a compatibilized blend of nylon 11 and polypropylene with polyhydroxybutyrate: Mechanical,thermal, and barrier properties

This article comprises of the interaction in the immiscible polymer system of nylon 11 (PA 11), polypropylene (PP), and polyhydroxybutyrate (PHB). Reactive compatibilization extrusion method with maleic anhydride-grafted polypropylene (PP-g-MA) is used to achieve compatibility within the polymer. To further improve the interaction of the blend at interphase, PHB was added as a dispersive phase in a concentration varying from 10 to 40% of the total batch. Addition of PHB motives the excellent dispersion of PP chain in PA 11 and assures the compatibility between the phases of PA 11 and PP-g-MA. The entire system of tertiary and binary phases was blended in a twin-screw extruder at different composition. The macro-optimal tensile strength, Young's modulus, bending strength, and notched impact strength of PA11/PP systems were found to be superior as compared to their noncompatibilized systems. The degradation temperature of the blends of PA11/PP and PA11/PHB/PP with and without compatibilizer was evaluated by thermogravimetric analysis (TGA). It was found that the high temperature of degradation was required for compatibilized ternary blend than that of the compatibilized binary blend. The distortion temperature of the systems was studied with the help of heat deflection temperature (HDT) and found to be advanced for blend having a higher concentration of the dispersed phase. Differential scanning calorimetry (DSC) was used to determine the % crystallinity, melting, and crystallization temperature of this system. Chemical resistance and barrier properties of the different compatibilized and noncompatibilized blends were studied. PHB dispersed phase with a reactive compatibilizer cause enhancement in chemical resistance and barrier properties of the blend. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48152.     

Polymer blends of poly(ethylene‐2,6‐naphthalate) with polystyrene compatibilized by styrene‐glycidyl methacrylate copolymers. I. Rheology,morphology, and mechanical properties

The compatibilization of blends of poly(ethylene‐2,6‐naphthalate) (PEN) with polystyrene (PS), through the styrene‐glycidyl methacrylate copolymers (SG) containing various glycidyl methacrylate (GMA) contents, was investigated in this study. SG copolymers are able to react with PEN terminal groups during melt blending, resulting in the formation of desirable SG‐g‐PEN copolymers in the blend. These in situ formed copolymers tend to reside along the interface preferentially as the result of interfacial reaction and thus function as effective compatibilizers in PEN/PS blends. The compatibilized blends exhibit higher viscosity, finer phase domain, and improved mechanical properties. It is found that the degree of grafting of the in situ formed SG‐g‐PEN copolymer has to be considered as well. In blends compatibilized with the SG copolymer containing higher GMA content, heavily grafted copolymers would be produced. The length of the styrene segment in these heavily grafted copolymers would be too short to penetrate deep enough into the PS phase to form effective entanglements, resulting in the lower compatibilization efficiency in PEN/PS blends. Consequently, the in situ formation of SG‐g‐PEN copolymers with an optimal degree of grafting is the key to achieving the best performance for the eventually produced PEN/PS blends through SG copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 967–975, 2003     

In situ compatibilized polymer blends of phenoxy and ABS

The combination of styrene-acrylonitrile-glycidyl methacrylate (SAG) reactive copolymer and sodium lauryl sulfonate catalyst is able to function as an effective in situ compatibilizer for the otherwise immiscible and incompatible polymer blends of phenoxy and acrylonitrile-butadiene-styrene (ABS). The copolymer formed from the reaction between phenoxy and SAG under melt blending conditions tends to reduce interfacial tension in the melt and results in finer morphological domains of the blends. The presence of this in situ formed compatibilizer also raises the interphase adhesion of the blends and results in significant improvements in mechanical properties. © 1994 John Wiley & Sons, Inc.     

Styrene maleic anhydride and styrene glycidyl methacrylate copolymers as in situ reactive compatibilizers of polystyrene/nylon 6,6 blends

The reactive type copolymers styrene maleic, anhydride (SMA) and styrene glycidyl methacrylate (SG) are used as in situ compatibilizers in polyblends of polystyrene (PS) and nylon 6, 6 (N66). Both copolymers can react with N66 to form copolymers as effective compatibilizers to reduce interfacial tension and increase phase adhesion. However, the toughness of the compatibilized blends is significantly lower than of the corresponding noncompatibilized blends. Only a small fraction of SMA is actually reacted in a typical melt blending, and SG copolymer seems to be more reactive than SMA. The unreacted copolymers are expected to be distributed mostly in the PS phase because of their structural similarity. The reacted copolymers are not exclusively distributed along the interface; some may distribute in both matrices. SMA is known as a very brittle polymer, and the way it is distributed can greatly influence the toughness of the resulting blends. PS is also very brittle relative to N66, and moreover a high amount of SMA in the N66 phase is detrimental since N66 is responsible for the toughness of PS/N66 blends. The better compatibilized blends have the tendency to bring more SMA and reacted SMA into the N66 phase. The relative detrimental effect on the inherent toughness of N66 is much more severe than in case of PS, if they contain the same amount of SMA. This study demonstrates that polyblends with good compatibilizers do not guarantee toughness improvement. The way the compatibilizers affect the inherent properties of the matrix needs also to be taken into consideration.     

Evolution of the morphological and rheological properties along the extruder length for compatibilized blends of a commercial liquid‐crystalline polymer and polypropylene

In a previous article, we reported on the evolution of the morphological and rheological properties along the length extruder for blends of a liquid‐crystalline polymer (LCP), Rodrun LC3000, and polypropylene (PP). In this work, we extended this study to compatibilized PP/Rodrun LC3000 blends, containing 10 wt % LCP and different compatibilizers, to determine the influence of the addition of a compatibilizer during the processing and, consequently, on the final properties of such systems. The results revealed that the addition of compatibilizers led to a decrease in the mean diameters of the LCP structures, in comparison with those presented by the noncompatibilized blend containing the same LCP content. This phenomenon occurred more quickly for those blends in which compatibilization was carried out in an efficient way. Linear oscillatory shear was mainly sensitive to the type of morphology present in the blends, whereas nonlinear oscillatory shear was more sensitive to the evolution in the droplet/fibril size and along the extruder length. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 347–359, 2006     

Effects of maleated syndiotactic polystyrene on the morphology,mechanical properties,and crystallization behavior of syndiotactic polystyrene/polyamide 6 blends

The compatibilization of syndiotactic polystyrene (sPS)/polyamide 6 (PA‐6) blends with maleic anhydride grafted syndiotactic polystyrene (sPS‐g‐MA) as a reactive compatibilizer was investigated. The sPS/PA‐6 blends were in situ compatibilized by a reaction between the maleic anhydride (MA) of sPS‐g‐MA and the amine end group of PA‐6. The occurrence of the chemical reaction was substantiated by the disappearance of a characteristic MA peak from the Fourier transform infrared spectrum. Morphology observations showed that the size of the dispersed PA‐6 domains was significantly reduced and that the interfacial adhesion was much improved by the addition of sPS‐g‐MA. As a result of reactive compatibilization, the impact strengths of the sPS/PA‐6 blends increased with an increase in the sPS‐g‐MA content. The crystallization behaviors of the blends were affected by the compatibilization effect of sPS‐g‐MA. A single melting peak of sPS in the noncompatibilized blend was gradually split into two peaks as the amount of the compatibilizer increased. A single crystallization peak of PA‐6 in the noncompatibilized blend became two peaks with the addition of 3 wt % sPS‐g‐MA. The new peak was a result of the fractionation crystallization. As the amount of sPS‐g‐MA increased, the intensity of the new peak increased, and the original peak nearly disappeared. Finally, the crystallization peak of PA‐6 disappeared with 20 wt % sPS‐g‐MA in the blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2502–2506, 2003     

Effects of processing conditions on the mechanical performance of maleic anhydride compatibilized in-situ composites of polypropylene with liquid crystalline polymer

Maleic anhydride compatibilized blends of isotactic polypropylene (PP) and thermotropic liquid crystaline polymer (LCP) were prepared either by the direct injection molding (one-step process), or by twin-screw extrusion blending, after which specimens were injection molded (two-step process). The morphology and mechanical properties of these injection molded in situ LCP composites were studied by means of scanning electron microscopy (SEM), Izod impact testing, static tensile, and dynamic mechanical measurements. SEM observations showed that fine and elongated LCP fibrils are formed in the maleic anhydride compatibilized in situ composites fabricated by means of the one-step process. The tensile strength and modulus of these composites were considerably close to those predicted from the rule of mixtures. Furthermore, the impact behavior of LCP fibril reinforced composites was similar to that of the glass fiber reinforced polymer composites. On the other hand, the maleic anhydride compatibilized blends prepared from the two-step process showed lower mechanical performance, which was attributed to the poorer processing behavior leading to the degradation of PP. The effects of the processing steps, temperatures, and compatibilizer addition on the mechanical properties of the PP/LCP blends are discussed.     

Polyamide 6/ethylene‐butylene elastomer blends generated via anionic polymerization of ε‐caprolactam: Phase morphology and dynamic mechanical behavior

This paper reports about the polymerization of ε‐caprolactam monomer in the presence of low molecular weight hydroxyl or isocyanate end‐capped ethylene‐butylene elastomer (EB) elastomers as a new concept for the development of a submicron phase morphology in polyamide 6 (PA6)/EB blends. The phase morphology, viscoelastic behavior, and impact strength of the polymerization‐designed blends are compared to those of similar blends prepared via melt‐extrusion of PA6 homopolymer and EB elastomer. Polyamide 6 and EB elastomer were compatibilized using a premade triblock copolymer PA6‐b‐EB‐b‐PA6 or a pure EB‐b‐PA6 diblock reactively generated during melt‐blending (extrusion‐prepared blends) or built‐up via anionic polymerization of ε‐caprolactam on initiating ? NCO groups attached to EB chain ends (polymerization‐prepared blends). Two compatibilization approaches were considered for the polymerization‐prepared blends: (i) the addition of a premade PA6‐b‐EB‐b‐PA6 triblock copolymer to the ε‐caprolactam monomer containing nonreactive EB? OH elastomer and (ii) generation in situ of a PA6‐b‐EB diblock using EB? NCO precursor on which polyamide 6 blocks are built‐up via anionic polymerization of ε‐caprolactam. The noncompatibilized blends exhibit a coarse phase morphology, either in the extruded or the polymerization prepared blends. Addition of premade triblock copolymer (PA6‐b‐EB‐b‐PA6) to a EB? OH /ε‐caprolactam dispersion led to a fine EB phase (0.14 μm) in the PA6 matrix after ε‐caprolactam polymerization. The average particle size of the in situ reactively compatibilized polymerization‐prepared blend is about 1 μm. The notched Izod impact strength of the blend compatibilized with premade triblock copolymer was much higher than that of the neat PA6, the noncompatibilized, and the in situ reactively compatibilized polymerization blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2538–2544, 2004     

Compatibilization of polymer blends with high‐molecular‐weight peroxides

A novel approach for the compatibilization of heterogeneous polymer blends with interface‐active high‐molecular‐weight peroxides is presented. This three‐step approach includes the synthesis of an anchor peroxide copolymer, the preparation of an interface‐active, peroxide‐containing graft copolymer (precompatibilizer) on its basis, and the localization of the precompatibilizer at the interfaces of the polymer blends during reactive blending with the in situ formation of compatibilizer macromolecules. We found that the precompatibilizer incorporating polypropylene fragments compatibilized blends of polypropylene with polystyrene, polyethylene, and unsaturated polyester resin. This verified a certain universality of the approach proposed for the compatibilization of polymer blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 232–242, 2005     

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     

Polymer blends of PBT and PP compatibilized by ethylene-co-glycidyl methacrylate copolymers

The ethylene-co-glycidyl methacrylate (EG) copolymer is an efficient reactive compatibilizer for polymer blends of poly(butylene terephthalate) (PBT) and polypropylene (PP). During melt processing, the epoxy functional group of the EG copolymer can react with the PBT carboxylic acid and/or hydroxyl terminal groups at the interface to form various EG-g-PBT copolymers. These in situ formed grafted copolymers tend to concentrate along the interface to reduce the interfacial tension at the melt and result in finer phase domains. Higher glycidyl methacrylate (GMA) content in the EG copolymer or a higher quantity of the EG compatibilizer in the blend results in a better compatibilized blend in terms of finer phase domains, higher viscosity, and better mechanical properties. The presence of only 50 ppm catalyst (ethyltriphenyl phosphonium bromide) in the EG compatibilized blend further improves the blend compatibility substantially. © 1996 John Wiley & Sons, Inc.     

Rubber‐toughened polypropylene/acrylonitrile‐co‐butadiene‐co‐styrene blends: Morphology and mechanical properties

The RTPP/ABS (rubber toughened polypropylene/poly (acrylonitrile‐co‐butadiene‐co‐styrene) blends, both noncompatibilized and compatibilized with polypropylene‐g‐polystyrene, were prepared by melt mixing in a Brabender Plasti‐Corder. As the torque ratio of RTPP and ABS was about 2, phase cocontinuity in the blends was achieved at ABS volume fractions around 0.16, which was evidenced by both microscopic analysis and mechanical testing. A new microscopic and image analysis technique was introduced, whose combination provides two semiquantitative parameters: structure roughness and structure cocontinuity. The latter parameter is closely associated with the predictive scheme based on the equivalent box model and percolation theory, which was used in this study. The predicted mechanical properties were confronted with the experimental data for tensile modulus, yield strength, and tensile impact strength. While the modulus of noncompatibilized blends is reasonably fitted by the model, the compatibilizer accounts for a positive deviation attributed to a strong interaction between the compatibilizer and the matrix. The yield strength of noncompatibilized blends indicates poor interfacial adhesion, which is so enhanced by the compatibilizer that no phase debonding occurs before yielding. Tensile impact strength, in contrast to modulus and yield strength, passes through a deep minimum for both types of blends; two tentative explanations of this detrimental behavior were suggested. POLYM. ENG. SCI., 47:582–592, 2007. © 2007 Society of Plastics Engineers.     

Compatibilization of poly(ethylene terephthalat)/liquid crystal polymer blends by means of bisphenol a polycarboate

A compatibilization method that consists of the addition of minor amounts of a commercial thermoplastic, which interacts or reacts with both the matrix and the dispersed liquid crystalline polymer (LCP) of thermoplastic/LCP blends, has been tested in the case of poly(ethylene terephthalate)/Vectra A950 (PET/VA) blends by means of the addition of bisphenol A polycarbonate (PC). The smaller particle size, rougher surface of the fibers and higher ductility of the PET/VA blends of a 30% of the PET substituted by PC clearly showed the suitability of PC as a compatibilizer. The moduli of elasticity of the compatibilized and uncompatibilized blends were similar. This was due to the less‐developed fibrillation of the compatibilized blends, a consequences of their smaller particle size and decreased matrix viscosity. These changes counteracted the effects of improved interfacial adhesion. The improved adhesion led to higher ductility and tensile and impact strengths in most of the compatibilized blends.