TLCPa对PA 6/PA 66相容性及结晶行为的影响

采用溶液共混法制备了聚酰胺6(PA 6)／聚酰胺66(PA 66)/热致聚酰胺液晶(TLCPa)共混物,分析了TLCPa对PA 6／PA 66相容性及结晶行为的影响。差示扫描量热法分析表明,TLCPa的加入改善了PA 6和PA 66之间的相容性,PA 6／PA 66共混物结晶受到抑制;傅里叶变换红外光谱研究表明,TLCPa和PA 6、PA 66分子间形成了大量的分子间氢键,是TLCPa改善共混物相容性的主要原因;广角X射线衍射分析表明,TLCPa的加入没有影响共混物的晶型结构,当w(TLCPa)大于10％时,共混物的结晶度明显下降。     

Fractionated crystallization of dispersed PA6 phase of PP/PP‐g‐MAH/PA6 blends

Fractionated crystallization behavior of dispersed PA6 phase in PP/PA6 blends compatibilized with PP‐g‐MAH was investigated by scanning electron microscopy (SEM), differential scanning calorimeter (DSC), polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD) in this work. The lack of usual active heterogeneities in the dispersed droplet was the key factor for the fractionated crystallization of PA6. The crystals formed with less efficient nuclei might contain more defects in the crystal structures than those crystallized with the usual active nuclei. The lower the crystallization temperature, the lesser the perfection of the crystals and the lower crystallinity would be. The fractionated crystallization of PP droplets encapsulated by PA6 domains was also observed. The effect of existing PP‐g‐MAH‐g‐PA6 copolymer located at the interface on the fractionated crystallization could not be detected in this work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3742–3755, 2004     

Morphology and mechanical properties of polyamide‐6/K resin blends

Mechanical properties and morphological studies of compatibilized blends of polyamide‐6 (PA‐6)/K resin grafted with maleic anhydride (K‐g‐MAH) and PA‐6/K resin/K‐g‐MAH were investigated as functions of K resin/K‐g‐MAH and dispersed phase K resin concentrations, and all the blends were prepared using twin screw extruder followed by injection molding. Scanning electron microscopy (SEM) were used to assess the fracture surface morphology and the dispersion of the K resin in PA‐6 continuous phase, the results showing extensive deformation in presence of K‐g‐MAH, whereas, uncompatibilized PA‐6/K resin blends show dislodging of K resin domains from the PA‐6 matrix. Dynamic mechanical thermal analysis (DMTA) test reveals the partially miscibility of PA‐6 with K‐g‐MAH, and differential scanning calorimetry (DSC) results further identified that the introduction of K‐g‐MAH greatly improved the miscibility between PA‐6 and K resin. The mechanical properties of PA‐6/K resin blends and K‐g‐MAH were studied through bending, tensile, and impact properties. The Izod notch impact strength of PA‐6/K‐g‐MAH blends increase with the addition of K‐g‐MAH, when the K‐g‐MAH content adds up to 20 wt %, the impact strength is as more than 6.2 times as pure PA‐6, and accompanied with small decrease in the tensile and bending strength less than 12.9% and 17.5%, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and properties of PET/PA-6/E-44 blends

Polymer blends incorporating poly (ethylene terephthalate) (PET), polyamide-6 (PA-6), and a reactive compatibilizer (low molecular weight bisphenol-A epoxy resin—E-44) were prepared with the following E-44 weight percent concentrations: 0, 0.3, 0.6, 1, 3, 5, and 10. The samples was studied by a scanning electron microscope (SEM), a polarizing microscope (PLM), dynamic mechanical thermal analysis (DMTA), wide-angle X-ray diffraction (WAXD), a differential scanning calorimeter (DSC), infrared spectroscopy (IR), and mechanical testing. SEM and PLM showed noticeable changes in both the amorphous region and the crystalline region of the blends. The changes indicated better compatibility between the dispersed phase (PA-6) and the matrix (PET), which was further confirmed by the DMTA test. The WAXD showed that PET and PA-6 crystallized separately and no cocrystallite was found. The melting and crystallization data, obtained by DSC, suggested that the crystallization of the blend was blocked, although the hindered mechanism for the effect of E-44 on PET was different from that on PA-6. The notched impact strength and flexural strength of the PET/PA-6 blends were significantly improved when the content of E-44 was 5 wt % (improved about 500 and 400%, respectively). IR was used to study the reaction among E-44, PET, and PA-6. The result indicated that the grafting reaction and the crosslinking reaction occurred during melt blending. The obvious increase of mechanical properties and the reinforcing and toughening effect were attributed to the formation of the crosslinking net in the blend. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1505–1515, 1998     

LCP与PA66共混物的DSC分析与相容性研究

用溶液共混的方法制备热致聚酯酰胺液晶（LCP）和尼龙66（PA－66）共混物,用DSC、POM、WAXD等手段对共混物进行了表征。DSC和POM研究结果表明,LCP与PA－66之间有较好的相容性,LCP能在PA－66中较均匀分散,LCP的加入影响了PA－66的熔融和结晶行为,少量的LCP有利于PA－66的结晶,WAXD结果表明,LCP掺入了PA－66的结晶过程、形成共晶。     

In-Situ Reaction Influenced Polyamide 11 Crystallization in Polymer Blends

Two kinds of polymer blends, Polyamide 11(PA11)/Styrene maleic anhydride (SMA) and Polyamide 11/Ethylene vinyl acetate-g-maleic anhydride (EVA-g-MAH), were prepared to study PA11 component crystallization in them. PA11/SMA blends were employed to characterize the in-situ reaction between anhydride group and amine termination of PA11. FT-IR and Solid-state ¹³C NMR indicate that PA11-g-SMA graft polymer was in-situ formed at the interface during polymer blending process. DSC measurements show that SMA and EVA-g-MAH decrease the crystallinity and melting point of PA11 component. WAXD illustrates that PA11 crystalline transit from the original δ′ form to α form in the blends. The in-situ reactant also leads to decreased glass transition temperature substantiated by DMA measurements. These graft copolymers are expected to impede the effective packing of PA11 molecules to form crystal as well as changing the crystal pattern way.     

Study on the thermal behaviors and the morphology in PVP and nylon 6 blends

In this report, polyamides were solution blended in the formic acid with poly(vinyl pyrrolidone)(PVP), an amorphous polar polyamide. The thermal behaviors and morphological change in the blends of Nylon 6 (PA6) and PVP were investigated in details via WAXD, DSC, FT‐IR and POM methods. The equilibrium melting temperatures for PA6 in the blends were estimated based on the linear and nonlinear Hoffman‐Weeks (LHW and NLHW) extrapolative methods. With increasing the mass ratio of PVP to PA6, T_m (melting temperature) and T_c (crystallization temperature) of PA6 in blends both decreased as well as that of the spherulite size of PA6. The interaction mode between PVP and PA6 was investigated by FT‐IR spectroscopy, and the spectral changes indicated that the carbonyl groups of PVP had formed hydrogen bonding with the N? H groups of PA6 molecules in the molten state, which resulted in the variation of the morphology and thermal behaviors. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚酰胺6/丙烯酸酯橡胶共混物热性能和结晶行为研究

采用熔融共混法制备了聚酰胺6/环氧型丙烯酸酯橡胶(PA6/ACM)共混物,并通过差示扫描量热仪(DSC)、X射线衍射仪(XRD)和偏光显微镜(PLM)对PA6/ACM共混物的热性能和结晶行为及晶体形貌进行了研究。结果表明,随着ACM含量的增加,共混物的融熔温度(Tm)和结晶温度(Tc)均略有下降;由于环氧型ACM的加入,PA6的晶型也由γ晶型转化为 α晶型,且随着橡胶加入量的增加,结晶度逐渐降低,晶粒逐渐变小,结晶也越来越不完善;共混物的缺口冲击强度明显提高。     

Investigations on the formation of composites by injection molding of PA6 and different grafted polypropylenes and their blends

Blends of different types of polypropylenes (PP) with polyamide 6 (PA6) were produced by extrusion. The PPs used were a PP homopolymer, a maleic anhydride‐grafted homopolymer, and an acrylic acid‐grafted homopolymer. The blends were characterized by DSC measurements, selective extraction, infrared spectroscopy, REM microscopy, melt rheology, and their mechanical properties. Three types of interactions in the blends as well as in two‐component composites mold by the core‐back process could be identified. Blends of PP with PA6 were not compatible, and two‐component bars could not be produced. Blends of PPgAA and PA6 were made compatible during reactive extrusion. Two‐component bars could be produced only with a blend containing 50 wt % PA6. The composite formation was based on the interdiffusion of PA6 in both components and the reactive compatibilization in the blends. Blends of PPgMAn were also compatibilized during reactive extrusion. The composite formation on two‐component injection molding was based on two mechanisms: the interdiffusion at sites, where PA6 chains of both the components came into contact, and an interfacial reaction, where PPgMAn and PA6 came into contact. The interfacial reaction was supported by the high mobility of the first component at the temperature of the melt of the second component. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2992–2999, 2006     

Miscibility,crystallization, and mechanical properties of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)/ poly(butylene succinate) blends

Naturally amorphous biopolyester poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3/4HB) containing 21 mol % of 4HB was blended with semi‐crystal poly(butylene succinate) (PBS) with an aim to improve the properties of aliphatic polyesters. The effect of PBS contents on miscibility, thermal properties, crystallization kinetics, and mechanical property of the blends was evaluated by DSC, TGA, FTIR, wide‐angle X‐ray diffractometer (WAXD), Scanning Electron Microscope (SEM), and universal material testing machine. The thermal stability of P3/4HB was enhanced by blending with PBS. When PBS content is less than 30 wt %, the two polymers show better miscibility and their crystallization trend was enhanced by each other. The optimum mechanical properties were observed at the 5–10 wt % PBS blends. However, when the PBS content is more than 30 wt %, phase inversion happened. And the two polymers give lower miscibility and poor mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Multiple melting and partial miscibility of ethylene‐vinyl acetate copolymer/low density polyethylene blends

Multiple melting behaviors and partial miscibility of ethylene‐vinyl acetate (EVA) copolymer/low density polyethylene (LDPE) binary blend via isothermal crystallization are investigated by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). Crystallization temperature T (°C) is designed as 30, 50, 70, 80°C with different crystallization times t (min) of 10, 30, 60, 300, 600 min. The increase of crystallization temperature and time can facilitate the growth in lateral crystal size, and also the shift of melting peak, which means the completion of defective secondary crystallization. For blends of various fractions, sequence distribution of ethylene segments results in complex multiple melting behaviors during isothermal crystallization process. Overlapping endothermic peaks and drops of equilibrium melting points of LDPE component extrapolated from Hoffman–Weeks plots clarify the existence of partial miscibility in crystalline region between EVA and LDPE. WAXD results show that variables have no perceptible influence on the predominant existence of orthorhombic crystalline phase structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Experimental study of the miscibility of ABS/PC polymer blends and investigation of the processing effect

In the challenging prospect of developing new materials by mixing different polymers to reach a synergetic performance, the present research focuses on the study of the miscibility of two polymers: The acrylonitrile butadiene styrene (ABS) composed of a dispersed elastomeric (polybutadiene rubber) polymer embedded in a SAN thermoplastic matrix, and the polycarbonate (PC). It shall be noted that obtaining miscible polymer blends is often a difficult task because of the large size of their molecular chains and the high interfacial tension between the polymer phases. Until now, the most numerous researches developed in this field involve polymer blends obtained by compatibilization techniques in order to improve the interfacial adhesion between initial polymers. The aim of this work is to study the miscibility between ABS and PC. First, two different methods were used to mix the polymers: the twin‐screw extrusion and the dissolution in a common solvent tetrahydrofuran (THF). Then, physicochemical, microscopic observation and rheological characterization were performed on samples of mixtures obtained by both extrusion processing and dissolution method. The measurement of glassy transition temperature (T_g) by differential scanning calorimetry measurements (DSC) and dynamical mechanical thermal analysis (DMTA) have shown a partial miscibility between the two polymers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44975.     

Influence of in situ compatibilization on in situ formation of low‐density polyethylene/polyamide 6 blends by reactive extrusion

Low‐density polyethylene/polyamide 6 (LDPE/PA6) blends were in situ formed by reactive extrusion, in which in situ polymerization of ε‐caprolactam (CL) and in situ copolymerization of maleic anhydride grafted low‐density polyethylene (LDPE‐MA) and CL took place simultaneously. The latter reaction could be considered as in situ compatibilization, and the influence of in situ compatibilization on the morphologies, thermal properties, and rheological behaviors of the blends was investigated in this work. Scanning electron microscopy showed that the in situ compatibilization could dramatically reduce the dispersed phase sizes and narrow the size distribution. The thermal properties indicated that in differential scanning calorimetry (DSC) cooling scans, fractionated crystallization of the PA6 component was observed in all cases and was promoted with increasing the amount of LDPE‐MA. The DSC second heating scans showed the in situ compatibilization could stimulate the formation of the less stable γ‐crystalline form of PA6 in the blends. Dynamic rheological experiments revealed the in situ compatibilization had enhanced the viscosity, storage modulus, and loss modulus of the blend and reduce the corresponding slope values of the storage modulus and loss modulus. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Biodegradable blends of high molecular weight poly(ethylene oxide) with poly(3‐hydroxypropionic acid) and poly(3‐hydroxybutyric acid): a miscibility study by DSC,DMTA and NMR spectroscopy

The miscibility of high molecular weight poly(ethylene oxide) blends with poly(3‐hydroxypropionic acid) and poly(3‐hydroxybutyric acid) (P(3HB)) has been investigated by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and high‐resolution solid state ¹³C nuclear magnetic resonance (NMR). The DSC thermal behaviour of the blends revealed that the binary blends of poly(ethylene oxide)/poly(3‐hydroxypropionic acid) (OP blends) were miscible over the whole composition range while the miscibility of poly(ethylene oxide)/poly(3‐hydroxybutyric acid) blends (OB blends) was dependent on the blend composition. OB blends were found to be partly miscible at the middle P(3HB) contents (25 %, 50 %) and miscible at other P(3HB) contents (10 %, 75 % and 90 %). Single‐phase behaviour for OP blends and phase separation behaviour for OB blends were observed from DMTA. The results from NMR spectroscopy revealed that the two components in the OP50 blend were intimately mixed on a scale of about 35 nm, while the domain sizes in the OB blend with a P(3HB) content of 50 % were larger than about 32 nm. © 2000 Society of Chemical Industry     

Reactive polytetrafluoroethylene/polyamide compounds. I. Characterization of the compound morphology with respect to the functionality of the polytetrafluoroethylene component by microscopic and differential scanning calorimetry studies

Compounds of electron‐beam‐irradiated polytetrafluoroethylene (PTFE) and polyamide (PA) were produced by reactive extrusion. During extrusion, both a breakdown process of the PTFE agglomerates and a chemical reaction between PTFE and PA took place. The morphology of the compounds was characterized with differential scanning calorimetry using fractionated crystallization, with atomic force microscopy and scanning electron microscopy, and with dynamic light scattering. The particle size of the dispersed PTFE phase decreased as the irradiation dose increased. A simple theoretical model of the breakdown process of PTFE agglomerates was made for the discussion of the development of the observed degree of dispersion. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1308–1316, 2005     

Morphology and Thermal Behavior of MCPA6/SAN Blends Prepared by Anionic Ring-Opening Polymerization of ε-caprolactam

Summary In this article, a series of blends of monomer casting polyamide 6 and styrene-co-acrylonitrile (MCPA6/SAN) were prepared by in situ anionic ring-opening polymerization of ε-caprolactam (CL). Their morphology and thermal behaviors were investigated by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and wide-angle x-ray diffraction (WAXD), respectively. The SAN phase had much finer domain in MCPA6/SAN than that in the polyamide6/SAN (PA6/SAN) blends prepared by melt blending of PA6 and SAN. All the melting and crystallization parameters of MCPA6/SAN blends decreased gradually with the increase of SAN content, while the melting temperature was almost unchanged. These results were due to the hydrolysis reaction of SAN occurred during the anionic polymerization of ε-caprolactam (CL). In addition, WAXD results showed that only α crystal forms existed in the MCPA6/SAN blends.     

Thermal behavior and morphology of polyamide 6 based multicomponent blends

The thermal behavior and morphology of multicomponent blends based on PA6, polyamide 6 (PA6)/styrene–acrylonitirle copolymer (SAN), PA6/acrylonitrile–butadiene–styrene terpolymer (ABS), and their compatibilized blends with styrene–acrylonitrile–maleic anhydride copolymer (SANMA) were studied using DSC and SEM. The blends were prepared in a twin‐screw extruder under similar processing conditions, keeping the PA6 content fixed at 50 wt %. It was found that, in all the blends, the second component had a nucleating effect and improved the overall degree and rate of crystallization of PA6, whereas addition of a compatibilizer slightly diminished these effects and resulted in significant changes in the blend morphology. The nucleating effect and consequent changes in the crystallization behavior was attributed to the presence of SAN, which is a common component in all the blends. The T_g of PA6 in the blends with a cocontinuous morphology, due to the connectivity between the phases, is higher than in the blends with a disperse‐type morphology. The compatibilized blends have a lower crystallization rate and nucleation ability with a cocontinuous morphology, whereas the uncompatibilized blends have a higher crystallization rate with a higher nucleation ability and a disperse and/or a coarse cocontinuous morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2753–2759, 2002     

Morphology and thermal behavior of MCPA6/SAN blends prepared by anionic ring‐opening polymerization of ϵ‐caprolactam

In this article, a series of blends of monomer casting polyamide 6 and styrene‐co‐acrylonitrile (MCPA6/SAN) were prepared by in situ anionic ring‐opening polymerization of ?‐caprolactam. Their morphology and thermal behaviors were investigated by means of scanning electron microscope, differential scanning calorimeter, and wide‐angle X‐ray diffraction (WAXD), respectively. The SAN phase had much finer domain in MCPA6/SAN than that in the PA6/SAN blends prepared by melt blending of PA6 and SAN. All the melting and crystallization parameters of MCPA6/SAN blends decreased gradually with the increase of SAN content, while the melting temperature was almost unchanged. These results were due to the hydrolysis reaction of SAN that occurred during the anionic polymerization of ?‐caprolactam. In addition, WAXD results showed that only α crystal forms existed in the MCPA6/SAN blends. In addition, the mechanical property of MCPA6 was improved obviously by incorporating a certain amount of SAN. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1357–1363, 2006     

Biodegradable poly(ethylene succinate) blends and copolymers containing minor amounts of poly(butylene succinate)

Poly(ethylene succinate) (PES), poly(butylene succinate) (PBS), and PES‐rich copolyesters were synthesized using an effective catalyst, titanium tetraisopropoxide. PES was blended with minor amounts of PBS for the comparison. The compositions of the copolyesters and the blends were determined from NMR spectra. Their thermal properties were studied using a differential scanning calorimeter (DSC), a temperature modulated DSC (TMDSC), and a thermogravimetric analyzer. No significant difference exists among the thermal stabilities of these polyesters and blends. For the blends, the reversible curves of TMDSC showed a distinct glass‐rubber transition temperature (T_g), however, the variation of the T_g values with the blend compositions was small. Isothermal crystallization kinetics and the melting behavior after crystallization were examined using DSC. Wide‐angle X‐ray diffractograms (WAXD) were obtained for the isothermally crystallized specimens. The results of DSC and WAXD indicate that the blends have a higher degree of crystallinity and a higher melting temperature than those of the corresponding copolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crystallization behavior of poly(l-lactic acid) affected by the addition of a small amount of poly(3-hydroxybutyrate)

The miscibility, crystallization and subsequent melting behavior in binary biodegradable polymer blends of poly(l-lactic acid) (PLLA) and low molecular weight poly(3-hydroxybutyrate) (PHB) have been investigated by differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and wide-angle X-ray diffraction (WAXD). DSC analysis results indicted that PLLA showed no miscibility with high molecular weight PHB (M_w = 650,000 g mol⁻¹) in the 80/20, 60/40, 40/60, 20/80 composition range of the PHB/PLLA blends. On the other hand, it showed some limited miscibility with low molecular weight PHB (M_w = 5000 g mol⁻¹) when the PHB content was below 25%, as evidenced by small changes in the glass transition temperature of PLLA. The partial miscibility was further supported by changes of cold-crystallization behavior of PLLA in the blends. During the nonisothermal crystallization, it was found that the addition of a small amount of PHB up to 30% made the cold-crystallization of PLLA occur in the lower temperature. Meanwhile, the crystallization of PHB and PLLA was observed in the heating process by monitoring characteristic IR bands of each component for the low molecular weight PHB/PLLA 20/80 and 30/70 blends. The temperature-dependent IR and WAXD results also revealed that for PLLA component crystallization, the disorder (α′) phase of PLLA was produced, and that the α′ phase changed to the order (α) phase just prior to the melting point.