Compatibilizing effect of ethylene–propylene–diene grafted maleic anhydride terpolymer on the blend of polyamide 66 and thermal liquid crystalline polymer

Polyamide 66–thermal liquid crystalline polymer (PA66/TLCP) composites containing 10 wt% TLCP was compatibilized by ethylene–propylene–diene‐grafted maleic anhydride terpolymer (MAH‐g‐EPDM). The blending was performed on a twin‐screw extrusion, followed by an injection molding. The rheological, dynamic mechanical analysis (DMA), thermal, mechanical properties, as well as the morphology and FTIR spectra, of the blends were investigated and discussed. Rheological, DMA, and FTIR spectra results showed that MAH‐g‐EPDM is an effective compatibilizer for PA66/TLCP blends. The mechanical test indicated that the tensile strength, tensile elongation, and the bending strength of the blends were improved with the increase of the content of MAH‐g‐EPDM, which implied that the blends probably have a great frictional shear force, resulting from strong adhesion at the interface between the matrix and the dispersion phase; while the bending modulus was weakened with the increase of MAH‐g‐EPDM content, which is attributed to the development of the crystalline phase of PA66 hampered by adding MAH‐g‐EPDM. POLYM. COMPOS., 27:608–613, 2006. © 2006 Society of Plastics Engineers     

Effects of extensional flow on properties of polyamide‐66/poly(2,6‐dimethyl‐1,4‐phenylene oxide) blends: A study of morphology,mechanical properties,and rheology

In this study, polyamide‐66/poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PA66/PPO) blends with high viscosity ratio were processed by a self‐designed triangle‐arrayed triple‐screw extruder (TTSE, which simulates extensional flow) and a commercial twin‐screw extruder (TSE), respectively. Furthermore, in order to improve the mechanical properties of the immiscible PA66/PPO blends, PPO‐grafted maleic anhydride (PPO‐g‐MA) and styrene–ethylene–butylene–styrene (SEBS) block copolymer were used. The mechanical properties, phase morphology, and rheological properties of both binary PA66/PPO blends and toughened PA66/PPO/PPO‐g‐MA blends were comprehensively investigated to compare the above mentioned two processing method. Samples processed with TTSE exhibited better mechanical properties than the TSE‐processed blends. The morphologies of the blends were examined by scanning electron microscopy, exhibiting smaller particles sizes and narrower particle size distributions, which were attributed to the significant effects of extensional flow in TTSE. The toughening mechanism of compatibilized blends was investigated through morphology analysis, dynamic mechanical, and rhelogical analysis. Thus, TTSE with an extensional effect was proved to be efficient in the blending of high viscosity ratio polymers. POLYM. ENG. SCI., 57:1090–1098, 2017. © 2016 Society of Plastics Engineers     

Effect of blending sequence on the morphology and properties of polyamide 6/EPDM‐g‐MA/epoxy blends

The ternary blends of polyamide 6/maleated ethylene‐propylene‐diene rubber/epoxy (PA6/EPDM‐g‐MA/EP) were prepared by a twin‐screw extruder with four different blending sequences. With the variation of blending sequence, the ternary blends presented distinct morphology and mechanical properties because of different interactions induced by various reactive orders. The addition of epoxy could increase the viscosity of the PA6 matrix, but a considerably larger size of the dispersed rubber phase was observed while first preblending PA6 with epoxy followed by blending a premix of PA6/EP with EDPM‐g‐MA, which was attested by rheological behaviors and SEM observations. It was probably ascribed to the fact that the great increase of the interfacial tension between the matrix and rubber phase aroused a great coalescence of rubber particles. The presence of epoxy in the rubber phase reduced the rubber's ability to cavitate so that the toughening efficiency of the EPDM‐g‐MA was decreased. The results of mechanical testing revealed that the optimum blending sequence to achieve balanced mechanical properties is blending PA6, EPDM‐g‐MA, and epoxy simultaneously in which the detrimental reactions might be effectively suppressed. In addition, thermal properties were investigated by TG and DSC, and the results showed that there was no distinct difference. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the Processing and Mechanical Properties of In Situ Composite Materials of Thermoplastics with Thermotropic Liquid Crystalline Polymers

By blending thermoplastics (TPs)—polycarbonate (PC) and polyethersulfone (PES)—with thermotropic liquid crystalline polymers (TLCPs)—KU9221 and KU9231—and then extruding the blends to form fibers, the in situ reinforcing characteristics were studied. The injection experiment of blends was compared with the extrusion experiment. According to the experimental results, in situ reinforcing characteristics of these processes were analyzed theoretically. These researches have come to some important conclusions. TLCP domains can be transformed to form fibers that are oriented in the direction of flow during processing; these TLCP microfibers result in improved mechanical properties of the TP/TLCP blends. The extruding flow is more effective in orienting TLCP domains and results in better in situ reinforcement than that of injection molding, and the extruded fibers have better mechanical properties. The mechanical properties of the blend fibers are improved greatly with increasing tensile ratio of melt drawing and the content of TLCPs.     

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.     

Effect of maleic anhydride grafted polybutadiene on the compatibility of polyamide 66/acrylonitrile‐butadiene‐styrene copolymer blend

The addition of maleic anhydride grafted polybutadiene (PB‐g‐MAH) can greatly improve the compatibility of polyamide 66 (PA66)/acrylonitrile‐butadiene‐styrene copolymer (ABS) blends. Unlike the commonly used compatibilizers in polyamide/ABS blends, PB‐g‐MAH is compatible with the ABS particles' core phase polybutadiene (PB), rather than the shell styrene‐acrylonitrile (SAN). The compatibility and interaction of the components in the blends were characterized by Fourier transform‐infrared spectra (FTIR), Molau tests, melt flow index (MFI), dynamic mechanical analyses (DMA), and scanning electron microscopic (SEM) observations. The results show that PB‐g‐MAH can react with the amino end groups in PA66 while entangle with the PB phase in ABS. In this way, the compatibilizer anchors at the interface of PA66/ABS blend. The morphology study of the fracture sections before and after tensile test reveals that the ABS particles were dispersed uniformly in the PA66 matrix and the interfacial adhesion between PA66 and ABS was increased significantly. The mechanical properties of the blends thus were enhanced with the improving of the compatibility. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

埃洛石纳米管对聚酰胺66/热致液晶原位复合材料性能及微观形态的影响

采用熔融共混方法制备了埃洛石纳米管（HNTs）／聚酰胺66（PA66）／热致液晶聚合物（TLCP）原位混杂复合材料,研究了其结晶性能、动态力学性能及微观形态,并提出了相对结晶度的概念。差示扫描量热法分析（DSC）表明：HNTs能促进PA66的结晶并提高晶体的完善程度;随着HNTs含量的增加,体系的相对结晶度逐渐提高;动态力学性能分析（DMA）表明：复合材料的储能模量及损耗模量均随着HNTs含量的增加而显著升高当HNTs含量为40 ％（质量分数,下同）时,复合材料的储能模量及损耗模量分别提高了188％、190 ％;扫描电子显微镜（SEM）显示,TLCP及HNTs均能在基体中均匀分散,且TCLP能较好地沿纤维轴方向取向、成纤。     

Improvement of the processability of poly(ether ketone ketone) by the addition of a thermotropic liquid crystalline polymer

The addition of a thermotropic liquid crystalline, wholly aromatic copolyester, TLCP, improved the melt processability of poly(ether ketone ketone), PEKK. The tensile strength and modulus of the blends also improved with increasing TLCP, but the elongation at break decreased significantly. The blends were phase‐separated, but the polymers were partially miscible as evident from shifts of the glass transition temperature (T_g) of each component towards that of the other component in the blend. Similarly, the melting points (T_m) of both components were depressed by blending. When the crystallization temperature was above T_m of the TLCP, the PEKK crystallization rate in the blend was slower than for the pure material, while crystallization was faster when the temperature was below T_m of the TLCP. Polym. Eng. Sci. 44:541–547, 2004. © 2004 Society of Plastics Engineers.     

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     

热致液晶高分子与尼龙共混改性进展

综述了近几年来热致液晶聚合物（ＴＬＣＰ）与尼龙（ＰＡ）共混改性的新进展，简要介绍了ＴＬＣＰ的加入对ＰＡ的熔融和结晶行为、粘度、形态结构以及力学性能等的影响，并阐述了增容技术在共混改性中的重要性以及影响ＴＬＣＰ成纤的主要因素。     

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     

Effect of processing history on the morphology and properties of polypropylene/thermotropic liquid crystalline polymer blends

Preparation, morphology, and mechanical properties were studied of blends of a thermotropic liquid crystalline polymer (TLCP) with two different grades of polypropylene, one with and one without overlap in processing temperatures, using two different blending methods. The highly viscous grade (PP-1) was of sufficient thermal stability to be blended with the TLCP (Vectra A950) in a single-screw extruder with an Egan mixing section on the screw. The low viscous grade (PP-2) could not be processed at the same temperature as the TLCP because of degradation. Its blends were, therefore, prepared by a special coextrusion technique, i.e. feeding the two components from two separate extruders to a Ross static mixer. In both methods drawing of the extrudate is necessary to obtain satisfactory mechanical properties. The PP-1/TLCP blends had to be extruded twice in order to obtain proper mixing. The morphology of these blends ranges from a pronounced skin-core morphology at low extrudate draw ratio (DR = 3) to a high-aspect ratio fiber/matrix morphology at high draw ratio (DR = 15). The morphology of the PP-2/TLCP blends was always a high-aspect ratio fiber/matrix morphology even at low draw ratios. The TLCP fibers were generated in this coextrusion process under conditions where the viscosity of the dispersed phase was higher than the viscosity of the matrix. Breakup experiments demonstrate that fibers of a thickness of approximately 1 μm disintegrate into droplets within a few seconds at temperatures above the melting point of the TLCP. This is probably the cause of the skin-core morphology obtained with single-screw extrusion. Tensile modulus and strength of all blends increase with extrudate draw ratio. The deformation of the TLCP phase in the drawn blends is less than affine, probably because of slip between the phases. The moduli of the PP-1/TLCP blends as a function of the draw ratio can be described well by a modified Halpin-Tsai equation taking into account both changes in aspect ratio and molecular orientation of the TLCP fibers. The level of reinforcement in the PP-2/TLCP blends is lower than expected, probably because of the low temperature of drawing. This demonstrates a limitation of the coextrusion process: blending at temperatures that are too low reduces mechanical properties.     

A study on the use of phenoxy resins as compatibilizers of polyamide 6 (PA6) and polybutylene terephthalate (PBT)

In this study we investigated the potential of phenoxy resins as compatibilizers in the blending of two high‐volume engineering thermoplastics—polyamide 6 (PA6) and polybutylene terephthalate (PBT), in an effort to establish the usefulness of blending as a method of recycling of mixed plastic wastes. It was found that phenoxy resins formed miscible blends with PBT, formed grafted copolymers with PBT through ester exchange reactions, and—though formed immiscible blends with PA6—produced energetic interactions in the form of hydrogen bonding with PA6. The ternary blend systems of 70 parts PA6, 30 parts PBT, and respectively 5, 10, and 30 parts phenoxy resins, all by weight, revealed at two‐phase nature—PA6 as the continuous phase and miscible blends of PBT and phenoxy resins as the dispersed phase—and were found to be stable to phase coarsening by annealing with mechanical properties at least as good as those of the component polymers.     

Manipulating the phase morphology in PPS/PA66 blends using clay

By adding a small amount of clay into poly(p‐phenylene sulfide) (PPS)/polyamide 66 blends, the morphology was found to change gradually from sea–island into cocontinuity and lamellar supramolecular structure, as increasing of clay content. Clay was selectively located in the PA66 phase, and the exfoliated clay layers formed an edge‐contacted network. The change of morphology is not caused by the change of volume ratio and viscosity ratio but can be well explained by the dynamic interplay of phase separation between PPS and PA66 through preferential adsorption of PA66 onto the clay layers and through layer–layer repulsion. This provides a means of manipulating the phase morphology for the immiscible polymer blends. The mechanical and tribological properties of PPS/PA66 blends with different phase morphologies (different clay contents) were studied. Both tensile and impact strength of the blends were found obviously increased by the addition of clay. The antiwear property was greatly improved for the blends with cocontinuous phase form. Our work indicates that the phase‐separating behavior of polymer blends contained interacting clay can be exploited to create a rich diversity of new structures and useful nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

PA66/TLCP/HNTs纳米管复合材料的制备与性能

采用熔融共混方法制备了尼龙(PA)66/热致液晶聚合物(TLCP)/埃洛石纳米管(HNTs)复合材料,研究了其热性能、微观形态及力学性能.结果表明,当TLCP的质量分数为4%、HNTs的质量分数为15%时,复合材料的综合性能最佳.其拉伸强度、拉伸弹性模量、弯曲强度及弯曲弹性模量相比纯PA66分别提高了30.4%、76.9%、34.4%、91.7%.熔体的加工流动性得到改善,PA66/TLCP/HNTs复合材料的吸水性能明显降低.少量的TLCP有利于提高PA66/TLCP复合材料的结晶性能和熔融温度;HNTs的加入能提高复合材料的结晶温度,与基体有较好的界面结合;TLCP及HNTs能在基体中均匀地分散,TLCP在PA66/TLCP/HNTs复合材料中形成微纤结构,且沿纤维轴方向取向.     

Reduced graphene oxide (RGO)-induced compatibilization and reinforcement of poly(vinylidene fluoride) (PVDF)–thermoplastic polyurethane (TPU) binary polymer blend

Compatible blends of nonreactive thermoplastic fluoropolymer, poly(vinylidene fluoride) (PVDF) and thermoplastic polyurethane (TPU) at 70/30 weight ratio, were prepared by utilizing the unique structural feature of reduced graphene oxide (RGO). Here, RGO acts as a compatibilizer as well as a reinforcing filler. RGO interacts with both polymers and reduces the interfacial tension between them, leading to compatibilization. RGO content in the blends was varied from 0 to 0.5 wt %, and the best result was found at 0.3 wt % loading. Excellent compatibilization between PVDF and TPU was established by mechanical, morphological, and thermal property studies. Chemical interaction between the RGO/TPU and RGO/PVDF was proved by FTIR–ATR study. With the incorporation of 0.3 wt % RGO, tensile strength, Izod impact strength, and elongation at break of the blend were increased by 42%, 83%, and 43%, respectively. FESEM and AFM images of blends without loading of filler after etching out of TPU phase show nonuniformly distributed hole morphology. RGO-containing blend has shown much finer and uniformly distributed holes that confirm improved compatibility between the two incompatible polymers. RGO also improves the thermal stability of the compatible blends considerably. At 0.3 wt % loading, the onset of thermal degradation increased by about 10 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47010.     

热致液晶聚合物共混改性聚酰胺的研究进展

综述了近几年来热致性液晶聚合物(TLCP)与聚酰胺(PA)共混改性的研究进展,以及TLCP的加入对PA的熔融和结晶行为、粘度、形态结构以及力学性能方面的影响,并阐述了增容技术在共混改性中的重要性。     

Polyblends containing a liquid crystalline polymer

Polyblends of a liquid crystalline thermotropic polymer (LCP) and an amorphous polyamide (PA) were prepared by melt blending. The blends' rheological behaviour was found to be very different from that of the individual components and very significant viscosity reductions were observed for blends consisting of only 5% LCP. The blends viscosity was always much lower than that of the parent polymers. The tensile mechanical behaviour of LCP/PA blends is very similar to that of polymeric composites. The blends' two phase morphology was found to be affected by their compositions. The LCP phase changed gradually with increasing LCP content from ellipsoidal particles to rod-like and fibrillar structure. A good interphase adhesion was observed.     

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

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

Thermal stability,flame retardance,and mechanical properties of polyamide 66 modified by a nitrogen–phosphorous reacting flame retardant

Flame‐retardant polyamide 66 (PA66) was prepared by the polymerization between PA66 prepolymer and N‐benzoic acid (ethyl‐N‐benzoic acid formamide) phosphamide (NENP). Compared with the pure PA66, the flame‐retardant PA66 exhibited better thermal stability, as indicated by thermogravimetric analysis results. The limiting oxygen index was 28% and the UL‐94 test results of the flame‐retardant PA66 indicated a V‐0 rating when the content of the NENP prepolymer was 5 wt %. The flammability and flame‐retardant mechanism of PA66 were also studied with cone calorimetry and scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, respectively. The mechanical properties results show that the flame‐retardant PA66 resin had favorable mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43538.