Blends of nylon 6 with an ethylene-based multifunctional polymer. I. Rheology–structure relationships

An experimental study was conducted to investigate the rheological behavior of a heterogeneous polymer blend system consisting of nylon 6 and an ethylene-based multifunctional polymer (CXA 3101, DuPont Co.). For comparison purposes, we also investigated the rheological behavior of two additional blend systems, namely blends of nylon 6 with a chemically modified polyolefin (Plexar 3, Chemplex Co.) and blends of nylon 6 with ethylene–vinyl acetate copolymer (EVA). We have investigated the thermal and thermomechanical behavior of the blend systems, using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Also, we have attempted to identify the chemical structure of the functional groups present in the CXA 3101 and Plexar 3 resins, using infrared (IR) spectroscopy. This information has enabled us to interpret the observed rheological behavior. Furthermore, we have used both optical and scanning electron microscopies to investigate the state of dispersion of the constituent components in each of the blend systems. We have concluded that, during melt blending, chemical reactions have taken place between carboxyl or anhydride groups present in the CXA 3101 resin and the amino end groups of the nylon 6, forming a graft copolymer which then acted as an “interfacial agent.”     

Morphology of nylon 1212 toughened with a maleated EPDM rubber

BACKGROUND: Polyamides, or nylons, are an attractive class of engineering polymers due to their excellent strength and stiffness, low friction and chemical and wear resistance. However, they are highly notch‐sensitive, i.e. they are often ductile in the un‐notched state, but fail in a brittle manner when notched. A super‐tough nylon 1212 was prepared by blending nylon 1212 with ethylene propylene diene monomer (EPDM) grafted with maleic anhydride (MA). The morphologies of Izod impact fracture surfaces as well as xylene‐etched surfaces of the nylon were thoroughly investigated using scanning electron microscopy (SEM). RESULTS: The fracture morphology and the impact strength of the nylon 1212 blends are very well correlated. The impact fracture surface of the blends exhibits certain characteristic features, such as the observation of fiber‐like sticks when etched with boiling xylene, formed during the impact fracture process. SEM images of xylene‐etched surfaces as well as the results of X‐ray energy dispersive spectroscopy suggest that the successful toughening of nylon 1212 with EPDM‐graft‐MA is due to the reaction between the anhydride of EPDM‐graft‐MA and the amine end‐groups of nylon 1212, leading to the formation of a homogenous graft copolymer system. CONCLUSION: The copolymer system, acting as a surfactant, reduces the interfacial tension between nylon 1212 and EPDM‐graft‐MA and produces a highly compatible super‐tough nylon 1212. Copyright © 2008 Society of Chemical Industry     

Ionomer compatibilised PA6/EVA blends: mechanical properties and morphological characterisation

The compatibilisation of PA6/EVA blends with the addition of an ionomer on the mechanical properties and morphology were studied as a function of ionomer concentration with the primary aim of enhancing the impact strength of PA6 by EVA. The level of EVA was kept at 20%, which formed the dispersed phase, and the ionomer content was varied from 0 to 1.6 wt%. It was found that notched Izod impact strength of PA6/EVA/ionomer blends increased with the incorporation of ionomer to about three times of the value for uncompatibilised PA6/EVA blends. Further, it was observed that on incorporation of the ionomer the tensile strength also increased significantly. Analysis of the tensile data using predictive theories indicated an enhanced interaction of the dispersed phase and the matrix. SEM studies of cryogenically fractured surfaces indicated a decrease in dispersed phase domain size with the addition of the ionomer, while the impact fractured surfaces of PA6/EVA blends indicated extensive deformation with the formation of rumples indicating increased interfacial adhesion as compared to PA6/EVA blends. An attempt has been made to evaluate the compatibilising efficiency of ionomer in PA6/EVA blends.     

Mechanical properties of blends of nylon 6 with a chemically modified polyolefin

Both tensile and impact properties were measured of a heterogeneous polymer blend system, consisting of nylon 6 and a chemically modified polyolefin, DuPont CXA3095, which is an ethylene-based multifunctional polymer. It was found, from the tensile testing, that the blends exhibited no signs of necking, and the addition of a soft resin (CXA3095) reduced the modulus and the tensile strength of nylon 6, whereas the percent elongation at break went through a minimum. When 20 wt % of CXA3095 was added to nylon 6, the impact strength was increased approximately three times. When the factors describing the interfacial adhesion were incorporated, the existing models for predicting the tensile modulus of blends were found to describe the experimental data rather well. In order to help explain the mechanical behavior observed, photomicrographs were taken of the fracture surfaces, using a scanning electron microscope.     

Polystyrene-graft-acrylic acid as compatibilizer of polystyrene/nylon 6,6 blends

Preliminary investigations to study the feasibility of using polystyrene grafted with acrylic acid to blend polystyrene (PS) and nylon 6,6 (N66) have been done. The graft copolymer (PS-g-AA) was synthesized by reacting polystyrene with acrylic acid in the presence of a free radical initiator using the solid phase graft copolymerization technique. Binary blends of N66/PS and N66/PS-g-AA were synthesized by melt mixing. The formation of a (PS-g-AA)-co-N66 copolymer during the blend preparation has been desired. The blend morphologies were observed by scanning electron microscopy (SEM). Significant reductions in the domain sizes of the dispersed minor phase were observed when PS-g-AA instead of PS was incorporated into the blend. The tensile properties of the blends were investigated. The belnds containing PS-g-AA were found to be stiffer (higher modulus) and stronger (higher tensile strength) as compared to the blends containing PS. These results are due to the better miscibility and adhesion between nylon 6,6 and the graft copolymer. The results of the rheological measurement of these blends further supports the above result and also indicates an increase in the molecular weight distribution (MWD) of the blend when polystyrene was replaced by the graft copolymer. This increase in the MWD of the compatibilized blend can be attributed to above assumed copolymer formation between the graft copolymer and nylon 6,6 due to the reaction between the carbonyl group of the acrylic acid and the amide and the terminal amine groups of nylon 6,6.     

EVA-g-MAH的制备及在聚合物共混相容中的应用

采用溶液接枝法合成得到乙烯-乙酸乙烯酯接枝马来酸酐聚合物（EVA-g-MAH）,利用核磁共振仪和红外光谱仪对产物进行分子链结构分析,结果表明：马来酸酐已成功接枝在EVA主链与酯基相连的叔碳原子上。通过调节马来酸酐（MAH）与EVA中乙酸乙烯酯（VA）单元的投料比,得到了不同接枝率（摩尔分数4.87%~12.3%）的产物。以EVA-g-MAH接枝共聚物为相容剂,通过聚合物加工制备了高密度聚乙烯（HDPE）/聚碳酸酯（PC）/EVA-g-MAH共混物,利用SEM对样品脆断面表面形貌进行对比观察,验证了EVA-g-MAH是HDPE/PC共混聚合物的良好相容剂。最后,研究了EVA-g-MAH对尼龙（PA6）/EVA共混物抗冲击强度的影响,当EVA-g-MAH加入质量分数为6%时对共混合金冲击强度提高最大。     

Mechanical properties and morphology of PA6/EVA blends

The mechanical properties of blends of polyamide6 (PA6) and ethylene vinyl acetate (EVA) at a blending composition of 0–50 wt % EVA were studied. The notched Izod impact strength of PA6 increased with the incorporation of EVA, the increase being more than 100% compared to PA6 at 10% EVA. The tensile strength and the tensile modulus of the blends decreased steadily as the weight percent of EVA increased. Analysis of the tensile data using predictive theories indicated the extent of the interaction of the dispersed phase and the matrix up to 20 wt % EVA. SEM studies of the cryogenically fractured surfaces indicated increase in the dispersed phase domain size with EVA concentrations. On the other hand, impact fractured surfaces of PA6/EVA blends indicated debonding of EVA particles, leaving hemispherical bumps, indicating inadequate interfacial adhesion between PA6 and EVA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1593–1606, 2002     

Mechanical and transport properties of coextruded films

Two-layer films were produced by using the blown-film coextrusion apparatus constructed in our laboratory. For this study, we have produced films of the following combinations: (1) LDPE/CXA 3095; (2) LDPE/Plexar 3; (3) LDPE/EMA; (4) nylon 6/LDPE; (5) nylon 6/CXA 3095; (6) nylon 6/Plexar 3; (7) nylon 6/EMA. Tensile properties of the coextruded films were measured with an Instron testing machine, and correlated to processing variables, namely, takeup ratio and blowup ratio. From tensile property measurements, we have found that both the ultimate tensile strength and the tensile modulus of coextruded films follow the additivity rule with respect to the volume fraction of the individual components. With the films produced, we also conducted dynamic mechanical measurements with the aid of a Rheovibron Dynamic Viscoelastometer DDV-II, and attempted to test the Zorowski–Murayama theory to determine the adhesion characteristics of the coextruded films. Furthermore, permeability of the coextruded films to gases (namely, N₂, O₂, and CO₂) was measured by using a pressure differential apparatus constructed in our laboratory. We have found that the permeability of composite films follows the inverse additivity rule, i.e., the reciprocal of the permeability of composite film is given by the sum of the reciprocals of the permeabilities of the individual layers.     

Toughening effects of ethylene–vinyl acetate copolymers with different vinyl acetate content and viscosity on nylon 1010 blends

Nylon 1010 blends with ethylene–vinyl acetate copolymer (EVA) and maleated ethylene–vinyl acetate (EVA‐g‐MAH) were prepared through melt blending. The vinyl acetate (VA) content and viscosity of EVA significantly affected the notched impact strength of nylon/EVA/EVA‐g‐MAH (80/15/5) blends. The nylon/EVA/EVA‐g‐MAH blends with high notched impact strength (over 60 kJ/m²) were obtained when the VA content in EVA ranged from 28 to 60 wt%. The effect of VA content on the notched impact strength of blends was related to the glass transition temperature for EVA with high VA content and crystallinity for EVA with low VA content. For nylon blends with EVA with the same VA content, low viscosity of EVA led to high notched impact strength. Fracture morphology of nylon/EVA/EVA‐g‐MAH (80/15/5) blends showed that blends with ductile fracture behavior usually had large matrix plastic deformation, which was the main energy dissipation mechanism. A relationship between the notched impact strength and the morphology of nylon/EVA/EVA‐g‐MAH (80/15/5) blends was well correlated by the interparticle distance model. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

原位增容HDPE／PET共混体系反应挤出形态结构的研究

通过扫描电镜照片（ＳＥＭ）研究了ＨＤＰＥ／ＰＥＴ共混体系在双螺杆反应挤出过程中,共混合金冲击断面的形态特征。结果表明,增容剂ＥＶＡ或ＥＡＡ均对ＨＤＰＥ／ＰＥＴ共混体系具有一定的增容作用;使分散相颗粒减小,且变得较为均匀,两相界面变得模糊,界面粘结力增强。其中,ＥＡＡ的增容效果优于ＥＶＡ。在此增容的基础上,选用有机化合物Ｄ作为催化剂,在熔融加工的过程中,使ＰＥＴ与ＥＶＡ或ＥＡＡ发生酯交换或酸－酯交换反应,生成ＰＥＴ－ＥＶＡ或ＰＥＴ－ＥＡＡ接枝共聚物,达到了原位增容ＨＤＰＥ／ＰＥＴ共混体系的目的,从而进一步改善了体系的相容性,共混体系的力学性能也得到了有效的提高     

Mercapto‐modified copolymers in polymer blends. II. The compatibilization of NBR/EVA blends

Ethylene‐vinyl acetate (EVA) copolymer functionalized with mercapto groups (EVALSH) has been used as compatibilizing agent in nitrile rubber/EVA blends. The tensile strength and elongation at break of the system were measured as a function of the EVALSH content and blend composition. The compatibilization affects the mechanical properties of these blends. The highest improvement of the tensile strength has been achieved in the composition range corresponding to the co‐continuous phase morphology. The co‐continuity of these blends has been studied by both dissolution studies and scanning electron microscopy. The addition of EVALSH as an interfacial modifier did not change the region of co‐continuity but influences the percolation threshold for both dispersed nitrile rubber phase and dispersed EVA phase. From optical microscopy and differential scanning calorimetry analysis, it is possible to assume that the functionalized EVALSH copolymer affects the crystallization of the EVA phase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 193–202, 2001     

Morphology and properties of PBT/nylon 6/EVA‐g‐MAH ternary blends prepared by reactive extrusion

Morphology and properties of poly(butylene terephthalate) (PBT)/nylon 6 (PA6)/EVA‐g‐MAH ternary blends were investigated. The blends were prepared in a corotating, intermeshing, twin‐screw extruder. The incorporation of maleic anhyride (MAH) grafted onto ethylene‐vinyl acetate copolymer (EVA) (EVA‐g‐MAH) in the PBT/PA6 binary blends decreased the tensile and flexural strength but increased the impact strength, while the mechanical properties of the PBT/PA6 blends were decreased with increasing PA6 content regardless of the presence or absence of the EVA‐g‐MAH. The morphology studies of the ternary blends showed gross phase separation. The rheological properties of the ternary blends suggested that excessively high reactivity between amine end groups of PA6 and MAH grafted onto EVA makes the compatibility between PBT and PA6 worse, although EVA‐g‐MAH was expected to work as a compatibilizer for PBT/PA6 blends. The degree of reactivity between functional groups in PBT, PA6, and EVA‐g‐MAH was also examined by investigating the effect of blending sequence on the properties of the ternary blends.     

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     

Melt rheology and elasticity of natural rubber—ethylene–vinyl acetate copolymer blends

The melt rheology of blends of natural rubber (NR) and ethylene–vinyl acetate copolymer (EVA) has been studied with reference to the effects of blend ratio, cross-linking systems, shear stress, and temperature. When EVA formed the dispersed phase, the viscosity of the blends was found to be a nonadditive function of the viscosities of the component polymers at lower shear region, i.e., a positive deviation was observed. This behavior has been explained based on structural buildup of dispersed EVA domains in the continuous NR matrix. The effect of the addition of silica filler on the flow characteristics of the blends has been investigated. The melt elasticity parameters such as die swell, principal normal stress difference, recoverable shear strain, and elastic shear modulus of NR–EVA blends were also evaluated. © 1993 John Wiley & Sons, Inc.     

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.     

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     

Rubber toughened polyamide 6: The influences of compatibilizer on morphology and impact properties

In this study, styrene-(ethylene-co-butylene)-styrene (SEBS) triblock copolymer (Kraton G-1652) was modified with maleic anhydride (MA). The maleated SEBS was used as compatibilizer for the blends of Nylon 6 (PA6) and SEBS. The morphology and impact strength of the blends were measured as functions of concentration and MA graft ratio of maleated SEBS. The compatibility and fracture mechanism of the blends were evaluated from the SEM micrographs of the xylene-etched surfaces and of fractured surfaces. Some of the blends exhibited an impact strength up to about 30 fold greater than neat PA6. The fracture involved both both cavitation and shear yielding. The mechanism of compatibilization of maleated SEBS in the ternary components blends was proposed.     

新型尼龙／聚烯烃相容剂EVALM的合成及表征

通过一种可控制的非均相水解方法制备了部分水解的乙烯／醋酸乙烯共聚物－ＥＶＡＬ。得到的ＥＶＡＬ中醋酸乙烯（ＶＡ）基团的水解度可以通过溶用及反应的温度、时间来控制,而且水解溶剂的后处理比较简单,有利于连续化生产及环境保护。将ＥＶＡＬ在苯溶液中进行马来酸酐接枝,得到一种新型的尼龙／聚烯烃相容剂马来酸酐接枝部分水解的乙烯／醋酸乙烯共聚物（ＥＶＡＬＭ）,其中马来酸酐的接枝率也可以接枝反应时间来控制。通过Ｍｏ     

共混工艺对SMAH增容ABS/PA6共混物形态和力学性能的影响

以(苯乙烯/马来酸酐)共聚物(SMAH)为增容剂,研究了共混工艺对(丙烯腈/丁二烯/苯乙烯)共聚物/尼龙6(ABS/PA6)共混物聚集态结构和力学性能的影响。结果表明,ABS与PA6直接共混时相容性差;加入增容剂SMAH后,分散相尺寸变小且易均匀分散,显著改善了ABS/PA6共混物的力学性能。当ABS为连续相、PA6为分散相时,共混物的聚集态结构强烈地受共混工艺的影响,(ABS/SMAH)/PA6共混物的分散相尺寸最小、力学性能最优;当PA6为连续相、ABS为分散相时,共混物的聚集态结构基本不受共混工艺的影响。     

Morphology—properties relationships in binary polyamide 6/rubber blends: Influence of the addition of a functionalized rubber

The modification of an amorphous random ethylene-propylene rubbery copolymer (EPM) has been accomplished by solution grafting of maleic anhydride molecules promoted by radical initiators, The resulting EPM-g-succinic anhydride (EPM-g-SA) and EPM have been used to obtain binary polyamide 6/EPM or polyamide 6/EPM-g-SA and ternary polyamide 6/EPM/EPM-g-SA blends by melt mixing. The formation of an EPM-g-PA6 graft copolymer during the blend preparation has been assumed. Different blend morphologies were observed by scanning electron microscopy (SEM) according to the nature and content of the rubber used. The tensile mechanical properties and the impact behavior of the prepared blends were investigated and correlated with the SEM analysis of the fracture surfaces. Binary and ternary blends containing 20 percent by weight of total rubber show a significant improvement of the impact properties at low temperature (?20°C) when the rubber is partly or entirely EPM-g-SA. In the case of PA6/EPM-g-SA (80/20) blend these results are related to the presence of rubbery domains of very small size strongly adherent to the PA6 matrix. In the case of 80/10/10 ternary blends, a much more complicated overall morphology is observed. Such morphology is characterized by the presence of large EPM domains, likely containing some EPM-g-PA6 graft molecules acting as an interfacial agent, and domains of EPM-g-PA6 of smaller size strongly adherent to the matrix as in the previous case.