Synthesis of nylon 6-g-poly(ethylene glycol) copolymer and its compatibilizing effect in nylon 6/poly(ethylene glycol) blends

Summary A graft copolymer of poly(ethylene glycol) onto nylon 6 was prepared by two-step reactions; poly(ethylene glycol) (PEG) was chlorinated with thionyl chloride in carbon tetrachloride and the chlorinated PEG was then grafted onto nylon 6 by reacting each other with triethylamine and tin chloride in o-chlorophenol. Blends were also prepared from the graft copolymer with nylon 6 or PEG. The thermal properties and crystalline structure of the graft copolymer and the blends were studied using differential scanning calorimeter and X-ray diffractometer. It was found that the grafting of PEG onto nylon 6 changed the crystal structure of nylon 6. It was observed that compatibilization of the nylon 6/PEG blend of 50/50 composition by weight was achieved in the presence of the graft copolymer.     

Kinetic studies and process analysis of the reactive compatibilization of nylon 6/polypropylene blends

This article describes a study on the reactive compatibilization of nylon 6 (N6) and polypropylene (PP) blends through a functionalized PP. A graft copolymer was formed in-situ by reacting an acid modified PP with N6 during blend compounding. The compatibilization reactions are studied in detail. Kinetics were estimated by means of experiments in a batch mixer. Three time constants were estimated, corresponding to (a) reactions, (b) melting of polymers, and (c) melt mixing. The effects of temperature and rotor speed on the reaction kinetics were also measured. There was a substantial increase in initial reaction rate, as the rotor speed was increased. Increasing the temperature did not significantly affect the reaction rate. Process parameters important for such a reactive compatibilization process were identified by statistically designed experiments in a co-roatating intermeshing twin-screw extruder. Screw speed, presence of venting, and sequence of feeding were shown to have a noticeable effect on the reactive compatibilization process during continuous compounding.     

Compatibilization of polypropylene/nylon 6 blends with a polypropylene solid‐phase graft

The compatibilization of polypropylene (PP)/nylon 6 (PA6) blends with a new PP solid‐phase graft copolymer (gPP) was systematically studied. gPP improved the compatibility of PP/PA6 blends efficiently. Because of the reaction between the reactive groups of gPP and the NH₂ end groups of PA6, a PP‐g‐PA6 copolymer was formed as a compatibilizer in the vicinity of the interfaces during the melting extrusion of gPP and PA6. The tensile strength and impact strength of the compatibilized PP/PA6 blends obviously increased in comparison with those of the PP/PA6 mechanical blends, and the amount of gPP and the content of the third monomer during the preparation of gPP affected the mechanical properties of the compatibilized blends. Scanning electron microscopy and transmission electron microscopy indicated that the particle sizes of the dispersed phases of the compatibilized PP/PA6 blends became smaller and that the interfaces became more indistinct in comparison with the mechanical blends. The microcrystal size of PA6 and the crystallinity of the two components of the PP/PA6 blends decreased after compatibilization with gPP. The compatibilized PP/PA6 blends possessed higher pseudoplasticity, melt viscosity, and flow activation energy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 420–427, 2004     

Toughening and compatibilization of polyphenylene sulfide/nylon 66 blends with SEBS and maleic anhydride grafted SEBS triblock copolymers

In this study, styrene‐b‐ethylene/butylene‐b‐styrene triblock copolymer (SEBS) and maleic anhydride grafted SEBS (SEBS‐g‐MA) were used as compatibilizers for the blends of polyphenylene sulfide/nylon 66 (PPS/PA66). The mechanical properties, including impact and tensile properties and morphology of the blends, were investigated by mechanical properties measurements and scanning electron microscopy. Impact measurements indicated that the impact strength of the blends increases slowly with elastomer (SEBS and SEBS‐g‐MA) content upto 20 wt %; thereafter, it increases sharply with increasing elastomer content. The impact energy of the elastomer‐compatibilized PPS/PA66 blends exceeded that of pure nylon 66, implying that the nylon 66 can be further toughened by the incorporation of brittle PPS minor phase in the presence of SEBS or SEBS‐g‐MA. The compatibilization efficiency of SEBS‐g‐MA for nylon‐rich PPS/PA66 was found to be higher than SEBS due to the in situ forming SEBS interphase between PPS and nylon 66. The correlation between the impact property and morphology of the SEBS‐g‐MA compatibilized PPS/PA66 blends is discussed. The excellent impact strength of the nylon‐rich blends resulted from shield yielding of the matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of nylon 6 on fracture behavior and morphology of tough blends of poly(2, 6‐dimethyl‐1,4‐phenylene oxide) and maleated styrene‐ethylene‐butadiene‐styrene block copolymer

Ternary blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO), nylon 6, and styrene‐ethylene‐butadiene‐styrene block copolymer grafted with maleic anhydride (SEBS‐g‐MA) were prepared via a melt extrusion, and the fracture behavior, morphology, mechanical properties, and rheology were studied. The compatibilization of the blended components was confirmed by differential scanning calorimetry (DSC) analysis. Mechanical properties evaluation demonstrated that incorporation of nylon 6 resulted in an improvement of the tensile strength, but reduction of both the notched Izod impact strength and elongation at break. Transmission electron microscopy (TEM) observation revealed that the network structure of SEBS‐g‐MA domain was gradually destroyed by incorporating the nylon 6. A conversion of SEBS‐g‐MA domain from the network to the irregular dispersed phase took place when the nylon 6 content reached 20 wt %, which resulted in a reduction of the impact strength. Fracture morphology implied that increase of the tensile strength was caused by the plastic deformation of matrix. Rheology investigation indicated that the melt viscosities could be reduced significantly with increasing the content of nylon 6; thus, the processability was improved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3336–3343, 2006     

Compatibilization of immiscible nylon 6/poly(vinylidene fluoride) blends using graphene oxides

A new strategy to compatibilize immiscible blends is proposed, using graphene oxide (GO) nanosheets taking advantage of their unique amphiphilic structures. When 0.5 or 1 wt% GOs were incorporated in immiscible nylon 6/poly(vinylidene fluoride) (PVDF) (90/10 wt%) blends, the dimension of PVDF dispersed particles was markedly reduced and became more uniform, revealing a well‐defined compatibilization effect of GOs on the immiscible blends. Correspondingly, the ductility of the compatibilized blends increased several times compared with uncompatibilized immiscible blends. In order to explore the underlying compatibilization mechanism, Fourier transform infrared and Raman spectra were applied to suggest that the edge polar groups of GOs can form hydrogen bonds with nylon 6 while the basal plane of GOs can interact with electron‐withdrawing fluorine on PVDF chains leading to the so‐called charge‐transfer C–F bonding. In this case, GOs exhibit favorable interactions with both nylon 6 and PVDF phase, therefore stabilizing the interface during GO migrations from PVDF/GO masterbatch to nylon 6 phase, which can minimize the interfacial tension and finally lead to compatibilization effects. Obviously, this work may open a broad prospect for GOs to be widely applied as a new compatibilizer in industrial fields. © 2012 Society of Chemical Industry     

Studies on polymer blend of nylon 6 and polypropylene or nylon 6 and polystyrene using the reaction of polymer

In the presence of maleic anhydride-grafted polypropylene, marked dispersibility of the polymer blend of isotactic polypropylene and nylon 6 was obtained. This appeared to be caused by the formation of a certain graft polymer between maleic anhydride in polypropylene and terminal amino groups of nylon 6. The same phenomenon was observed when polystyrene and nylon 6 were blended with styrene–methacrylic acid copolymer as the interpolymer. The existence of such a graft polymer was confirmed by solvent extraction, estimation of the amino group of nylon 6, and identification by differential scanning calorimetry. The physical properties, especially mechanical properties of nylon 6–polypropylene polymer blends, were remarkably improved with increase of maleic anhydride added to the polymer blend. On the other hand, the physical properties those of nylon 6–polystyrene polymer blends were very little improved even in the presence of good dispersibility.     

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.     

Toughening of nylon 6 with core-shell impact modifiers: Effect of matrix molecular weight

Rubber particle size is an important issue in toughening of engineering thermoplastics. Use of core-shell impact modifiers offers the advantage of a predetermined particle size; however, these particles must be appropriately dispersed in the matrix polymer to be effective for toughening. Recent work has shown that core-shell modifiers having a poly(methyl methacrylate) (PMMA) shell can be dispersed in nylon 6 with the aid of certain styrene/maleic anhydride (SMA) copolymers. These materials are miscible with PMMA and can also react with polyamides during melt processing. Enhanced interaction between the rubber and matrix phases as a result of the formation of in situ graft copolymers at the interface was suggested to contribute to the improved dispersion. However, rheological issues also influence the dispersion of core-shell modifier particles in the matrix. This article examines the influence of the matrix melt viscosity on the dispersion of the core-shell particles in the nylon 6 matrix and the resulting mechanical properties of the blends using four nylon 6 materials of different molecular weights. © 1996 John Wiley & Sons, Inc.     

Morphology of compatibilized ternary blends of polypropylene,nylon 66, and polystyrene

The morphologies of a ternary blend of nylon 66 and polystyrene in a polypropylene matrix with and without compatibilization by an ionomer resin (for nylon 66) and a styrene‐block‐ethylene‐co‐butylene‐block‐styrene (SEBS) copolymer (for polystyrene) were investigated by transmission electron microscopy (TEM) of stained thin sections. The morphology found with the two compatibilizers (a five‐component mixture) was essentially that of the binary blends of nylon 66/polypropylene and of polystyrene/polypropylene with their respective compatibilizers, indicating no gross interference between the two compatibilization systems. However, several interactions were discerned: 1) an association of the polystyrene with the nylon in the compatibilized blends (partial wetting), 2) a presence of larger particles when both compatibilizers were added to the binary blends, and 3) a possible synergism, in which less of each compatibilizer was needed when they were both present. Polym. Eng. Sci. 46:385–398, 2006. © 2006 Society of Plastics Engineers.     

Melt rheology and morphology of uncompatibilized and in situ compatibilized nylon‐6/ethylene propylene rubber blends

Melt rheology and morphology of nylon‐6/ethylene propylene rubber (EPR) blends were studied as a function of composition, temperature, and compatibilizer loading. Uncompatibilized blends with higher nylon‐6 content (N90 and N95) and rubber content (N5 and N10) had viscosities approximately intermediate between those of the component polymers. A very clear negative deviation was observed in the viscosity–composition curve over the entire shear rate range studied for blends having composition N30, N50, and N70. This was associated with the interlayer slip resulting from the high‐level incompatibility between the component polymers. The lack of compatibility was confirmed by fracture surface morphology, given that the dispersed domains showed no sign of adhesion to the matrix. The phase morphology studies indicated that EPR was dispersed as spherical inclusions in the nylon matrix up to 30 wt % of its concentration. A cocontinuous morphology was observed between 30 and 50 wt % nylon and a phase inversion beyond 70 wt % nylon. Various models based on viscosity ratios were used to predict the region of phase inversion. Experiments were also carried out on in situ compatibilization using maleic anhydride–modified EPR (EPR‐g‐MA). In this reactive compatibilization strategy, the maleic anhydride groups of modified EPR reacted with the amino end groups of nylon. This reaction produced a graft copolymer at the blend interface, which in fact acted as the compatibilizer. The viscosity of the blend was found to increase when a few percent of modified EPR was added; at higher concentrations the viscosity leveled off, indicating a high level of interaction at the interface. Morphological investigations indicated that the size of the dispersed phase initially decreased when a few percent of the graft copolymer was added followed by a clear leveling off at higher concentration. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 252–264, 2004     

Reactive compatibilization of the polyamide 6/poly(phenylene oxide) blend by means of styrene–maleic anhydride copolymer

The compatibilization of the polymer blend polyamide 6/poly(phenylene oxide) (PA-6/PPO) system has been studied using the reactive random copolymer styrene–maleic anhydride (SMA) as a compatibilizer precursor. SMA is miscible with PPO when the MA content of SMA is not higher than 8 wt %. The anhydride groups of SMA react with the amino end groups of PA-6 during melt blending to form a graft copolymer at the interface with a compatibilizing effect as a result. Two different blending procedures were compared to each other and the compatibilizing effect of the added SMA was evaluated for a matrix/dispersed particle type of morphology. The effect of the different material parameters such as the functionality of SMA (wt % MA in SMA) and the molecular weight of PA-6, and blending parameters such as the extrusion time was analyzed with respect to the blend phase morphology. Finally, the amount of reacted MA groups in the blends PA-6/(PPO/SMA) was determined with FTIR after the use of an extraction method to remove the PA-6 matrix phase. The comparison between the morphological data (particle size reduction of the dispersed PPO/SMA phase) and the FTIR data (amount of reacted MA groups) of the blends considered, turned out to be very logical. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 889–898, 1999     

Modification and compatibilization of nylon 6 with functionalized styrenic block copolymers

Much work in recent years had focused on the improvements of the impact properties of engineering thermoplastics by the addition of a low modulus modifier that contains polar moieties as a result of polymerization or that has been modified to contain polar moieties as a result of various grafting techniques. Styrenic block copolymers (styrene-ethylene/butylene-styrene) functionalized with maleic anhydride have proved useful as impact modifiers and compatibilizers in blends with engineering thermoplastics. This paper focuses on the use of these functionalized elastomers to modify nylon 6. In such compositions, a nylon material with unique mechanical performance may be achieved using the functionalized elastomer either alone or in combination with an unfunctionalized styrenic block copolymer. The optimization of performance in these rubber toughened polyamide blends using various types of styrenic block copolymers is discussed. The morphology as it pertains to performance is also reviewed. The information contained herein may prove useful in obtaining a better understanding of the mechanisms of compatibilization and modification of nylon 6 systems.     

Blends of polyamide 6, polycarbonate,and poly(propylene oxide). I. Reactive compatibilization–morphology relationships

The relationship between reactive compatibilization and morphology of the polyamide 6–polycarbonate (PA6–PC) and polyamide 6–polycarbonate–poly(pro-pylene oxide) (PA6–PC–PPO) blends were investigated by means of torque values, scanning electron microscopy, and Fourier transform infrared spectroscopy. The micrographs show that the blends processed for a long period of time presented a PC domain of smaller size and better adherence between the phases than the blends processed for a short period of time. This fact can be related with the presence of the block copolymer of PA6–PC synthesized in situ by the reaction of PA6 and PC and depend on temperature and mixing time. The presence of PPO does not impede the formation of copolymer but interferes on the size of the domain. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 857–864, 1998     

Preparation of conductive nylon 6 film

Electrically conducting nylon 6 films was prepared by introducing amide group or cyan group into the nylon 6 film and then introducing Cu_xS, which is known as the p-type semiconductor, into the grafted nylon films. The graft copolymerization of acrylamide (AM) and acrylonitrile (AN) onto nylon 6 film was investigated using ceric salt as the initiator. The graft yield was influenced by the concentration of ceric salt, sulfuric acid and monomer, and the reaction time. The optimum conditions for the introducing of Cu_xS were studied. Electrical conductivity of Cu_xS-treated nylon film was found to be higher by order of 10⁹ than that of the original nylon 6 film, and then properties of the resulting modified films were investigated.     

Fracture toughening behavior and mechanical properties of polyphenylene oxide/high-impact polystyrene blends

Blends of a poly(phenylene oxide) (PPO) with high-impact polystyrene (HIPS) were injection molded. The static mechanical properties and fracture toughness of the blends were determined by means of the uniaxial tension, Brinell hardness and three-point-bending measurements. From the static mechanical test results, it was shown that the yield strength, Young's modulus and hardness values of the PPO/HIPS blends were considerably higher than those of their PPO and HIPS component polymers. Dynamic mechanical measurements indicated that the PPO/HIPS blends appear to be miscible as shown by the existence of a single glass transition temperature. Furthermore, the J integral method based on ASTM E813-89 procedure was used to characterize the fracture toughness of PPO/HIPS blends. The J integral analysis indicated that the PPO specimen exhibited the lowest fracture toughness (J_c). The PPO containing 50 wt% HIPS blend had the highest J_c. SEM observations revealed that the crack growth zone of the pure PPO is relatively smooth. However, cavitation of the elastomeric particles and shear band formation were observed in the deformed zones ahead of the crack tip of the PPO with 50 wt% HIPS blend. The cavitation and shear band formation would dissipate bulk strain energy and their formation was responsible for the highest J_c value observed in this blend.     

Facile preparation of nylon 6 nanocomposites based on clay reinforcement and core‐shell latex toughening: Morphology,properties, and impact fracture behavior

This work is focused on a facile route to prepare a new type of nylon 6‐based nanocomposites with both high fracture toughness and high strength. A series of nylon 6‐matrix blends were prepared via melting extrusion by compounding with poly (methyl methacrylate‐co‐butadiene‐co‐styrene) (MBS) or poly(methyl methacrylate‐co‐methylphenyl siloxane‐co‐styrene) (MSIS) latices as impact modifier and diglycidyl ether of bisphenol‐A (DGEBA) as compatibilizer. Layered organic clay was also incorporated into above nylon 6 blends for the reinforcement of materials. Morphology study suggests that the MBS or MSIS latex particles could achieve a mono‐dispersion in nylon 6 matrix with the aid of DGEBA, which improves the compatibilization and an interfacial adhesion between the matrix and the shell of MBS or MSIS. High impact toughness was also obtained but with a corresponding reduction in tensile strength and stiffness. A moderate amount of organic clay as reinforcing agent could gain a desirable balance between the strength, stiffness and toughness of the materials, and tensile strength and stiffness could achieve an improvement. This suggests that the combination of organic clay and core‐shell latex particles is a useful strategy to optimize and enhance the properties of nylon 6. Morphology observation indicates that the layered organic clay was completely exfoliated within nylon 6 matrix. It is found that the core‐shell latex particles and the clay platelets were dispersed individually in nylon 6 matrix, and no clay platelets were present in MBS or MSIS latex particles. So the presence of the clay in nylon 6 matrix does not disturb the latex particles to promote high fracture toughness via particle cavitation and subsequent matrix shear yielding, and therefore, provides maximum reinforcement to the polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and properties of polyimide‐g‐nylon 6 and nylon 6‐b‐polyimide‐b‐nylon 6 copolymers

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ε‐caprolactam. Nylon 6‐b‐polyimide‐b‐nylon 6 copolymers were prepared by the use of phenyl 4‐aminobenzoate as an end‐capping agent in the preparation of a series of imide oligomers. The oligomers were then used to activate the anionic polymerization of ε‐caprolactam. In both the graft and copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. All the block copolymers had higher moduli and tensile strengths than those of nylon 6. However, their elongations at break were much lower. The graft copolymers based on 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane displayed elongations comparable to that of nylon 6 and the highest moduli and tensile strengths of all the copolymers. The thermal stability, moisture resistance, and impact strength were dramatically increased by the incorporation of only 5 wt % polyimide into both the graft and block copolymers. The graft and block copolymers also exhibited improved melt processability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 300–308, 2006     

Effects of mixing porcedures on properties of compatibilized polypropylene/nylon 6 blends

The paper consides the effects of compatibilization with maleic anhydride grafted polypropylene (PP-g-MAH) on the propertie of immiscible blends of polypropylene (PP) and nylon 6 (N6). We prepared the blends by three different mixing processes; single-step blending, two-step blending with reactive premixing, and two-step blending with nonreactive premixing, to determine the effective mixiing process for fine morphological structure thermal stability, and mechanical properties. Dynamic melt reheological properties were measured to examine the modification of elastic properties by the compatibilizer. In addtion, thermal analysis was also carried out to detect the change in crystallization and thereby to probe the degree of compatibilizaton. The results show that compatibilized blends prepared by teh single-step process exhibit improved phase morphology, thermal stability, and mechanical properties for dried conditions, compared with other blend types. Finally, the water absorption test indicates that the added compatibilizer yields enhanced water resistance in spite of the strong intrinsic hydrophilicity of N6. In particular, two-step blending with reactive premixing is most effective in improving water resistance and reducing degradation of mechanical properties after moisture absorption.     

Blends of nylon 6 with an ethylene-based multifunctional polymer. II. Property–morphology relationships

The tensile properties and impact strength were measured of the three blend systems, nylon 6/CXA 3101, nylon 6/Plexar 3, and nylon 6/EVA, which had been prepared using a twinscrew compounding machine. Scanning electron micrographs (SEM) of the fracture surfaces show that the domain size of the dispersed phase is much smaller in the nylon 6/CXA 3101 blends or nylon 6/Plexar 3 blends than in the nylon 6/EVA blends. This is attributed to the presence of a graft copolymer, formed by chemical reactions between carboxyl or anhydride groups present in the CXA 3101 (or Plexar 3) and the amino end groups of the nylon 6, at the boundaries of the dispersed and continuous phases. The SEM analysis of the fracture surfaces shows that no discrete particles are exposed on the fracture surface of either the nylon 6/CXA 3101 blends or nylon 6/Plexar 3 blends, supporting the theory that a graft copolymer, formed during melt blending, helped the discrete particles adhere to the continuous matrix.