Nylon-6/liquid natural rubber blends prepared via emulsion dispersion

Nylon-6 is widely used as engineering plastic because it is easy to process, high tensile properties, resistant to chemical and abrasion. However, poor impact strength at low temperature makes it limitedly used in some applications. Nylon-6/liquid natural rubber (LNR) blends were prepared via emulsion dispersion with composition of 100nylon-6/0LNR, 95nylon-6/5LNR, 90nylon-6/10LNR, 85nylon-6/15LNR, 80nylon-6/20LNR and 75nylon-6/25LNR. Nylon-6 was dissolved in a 2,2,2-trifluoroethanol and chloroform mixture (1:1 TFE/CHCl₃) and emulsified with hexadecyltrimethylammonium bromide (HTAB). LNR was dispersed into the nylon-6 emulsion to form homogeneous nylon-6/LNR emulsions and the emulsions were de-emulsified with methanol, filtered and dried. High impact behaviour was achieved at 85nylon-6/15LNR composition. DSC thermogram indicated a single glass transition temperature, T _g and SEM images showed no phase separation between blend components implying homogeneous blends were obtained.     

Studies on Impact Toughening and Thermal Properties of Nylon-6/LDPE-g-MAH Blends

Polyamide (PA)-6 is an engineering thermoplastic. It finds its application in electrical, mechanical, and automotive parts due to its very high processing and excellent barrier properties to oils. Unfortunately, Nylon-6 (Ny6) is relatively high priced, has poor impact strength, particularly when notched, and poor dimensional stability as well as poor barrier properties to moisture, which limits its applicability. On the other hand, due to low cost, low coefficient of friction, lightweight, high strength, high barrier properties to moisture, good optical properties, and ease of processing, low density polyethylene (LDPE) is an ideal material to incorporate with Polyamide-6 for film, container, and many engineering applications. The present study deals with the preparation of Nylon-6 and modified LDPE (MLDPE) blends, varying the MLDPE concentration from 0 to 50 wt%. The objective of this study is to find the effect of maleic-anhydride grafted low-density polyethylaene on various mechanical properties such as tensile, impact, and flexural properties of Nylon-6. There is a decrease in tensile and flexural properties, the notched Izod impact strength increased greatly when the MLDPE content was 20%. It includes the study the effect of MLDPE on thermal properties and morphological properties of Nylon-6. The morphology of PA/MLDPE blends showed dispersed particle in the polymeric matrix.     

Polymer matrix degradation and color formation in melt processed nylon 6/clay nanocomposites

Nylon 6 nanocomposites based on various quaternary alkyl ammonium organoclays were prepared by melt processing using a twin screw extruder. Dilute solution viscosity techniques were used to evaluate the level of polymer molecular weight degradation experienced during nanocomposite compounding; whereas colorimeter techniques were used to document color formation. In general, a significant reduction in nylon 6 matrix molecular weight was observed, which is believed to stem, in part, from reaction(s) between the surfactant of the organoclay and the polyamide chains. The level of degradation depends on both the type of nylon 6 material used and the surfactant chemistry in the organoclay. For a given organoclay, nanocomposites based on high molecular weight nylon 6 materials experience more matrix degradation, as well as color formation, than those based on low molecular weight materials; this is believed to arise from increased exposure of the organoclay surface to the nylon 6 owing to increased platelet exfoliation. Different organoclays lead to different levels of polymer degradation and color formation, depending upon the level of unsaturation present in the organic surfactant; the higher the number of double bonds the greater the degradation and the deeper the color formation. The primary mechanism of degradation is believed to be thermo-oxidative. Melt mixing of nylon 6 with model compounds, long-chain alkenes, shows that the same mode of degradation i.e. via double bonds can be replicated. In addition to unsaturation effects, the presence of hydroxyl-ethyl groups, opposed to methyl groups, in the organoclay surfactant, results in more color. Isothermal thermogravimetric analysis (TGA) was conducted on the organoclays to determine if thermal stability was a cause of molecular weight degradation; although, this relationship does not seem to exist, a direction correlation is observed between the organoclay degradation and nanocomposite modulus, or indirectly level of exfoliation. Use of antioxidant was found to reduce the amount of molecular weight loss. All evidence suggests that morphology and physical properties of nanocomposites formed from nylon 6 are not measurably affected by the reactions that lead to molecular weight degradation or color formation.     

尼龙6超韧化研究进展

介绍了超韧尼龙6的最新研究进展.主要介绍了几种超韧尼龙6的制备方法,其中马来酸酐接枝聚烯烃弹性体与尼龙6-无机纳米复合材料共混,能得到刚性、强度和韧性综合性能较好的超韧尼龙.     

Structure and properties of tailor‐made poly(ethyl acrylate)/clay nanocomposites prepared by in situ atom transfer radical polymerization

An in‐depth study was carried out on the structure and properties of a series of poly(ethyl acrylate)/clay nanocomposites prepared by in situ atom transfer radical polymerization (PNCIs) with well‐defined molecular weights and narrow molecular weight distributions. Wide‐angle X‐ray diffraction and transmission electron microscopy studies revealed an exfoliated clay morphology, whereas conventional solution blending generated an intercalated structure. The storage moduli of the PNCIs showed a moderate increase over that of the neat polymer [poly(ethyl acrylate)]. The sample containing 4 wt % clay (PNCI4, where the number following PNCI indicates the weight percentage of clay) exhibited the highest improvement (31.9% at 25°C). In PNCIs, the β‐transition temperature showed a remarkable decrease (by 175% in PNCI4) along with a shift toward higher temperatures. This indicated the probability of the anchoring of the ? OH group of the clay layers to the >C?O group of the pendant acrylate moiety, which was also confirmed by Fourier transform infrared analysis. Rheological measurements indicated a significant increase in the shear viscosity [by 9% in PNCI2, 15% in PNCI4, and 6% in the poly(ethyl acrylate)/clay nanocomposite with 2 wt % clay prepared by solution blending]. The PNCIs registered enhanced thermal stability, as indicated by the shift in the peak maximum temperature (388 and 392°C for the neat polymer and PNCI4, respectively) and a decrease in the rate of degradation (by 3.5% in PNCI2, 10.2% in PNCI4, and 49.3% in PNCI6). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of nylon-6 with semi-or wholly-aromatic polyamides

In this study, flexible Nylon-6 was reinforced by semi-or wholly-aromatic polyamides; poly(m-phenylene isophthalamide) (PmIA), poly(4,4′-diphenylmethane terephthalamide) (PMA), and poly(4,4′-diphenylsulfone terephthalamide) (PSA). Various high molecular weight block copolyamides were synthesized by solution polymerization using p-aminophenylacetic acid (p-APA) as a coupling agent. Their thermal properties have shown that the block copolyamides exhibit higher T_g and T_m, and better thermal stability than those of Nylon-6, especially PmIA modified Nylon-6. The order of their thermal properties of aromatic modified Nylon-6 copolyamides is PmIA > PMA > PSA. Moreover, the T_g and T_m of multiblock copolyamides are higher than those of triblock copolyamides. From the wide-angle X-ray diffraction pattern, it is found that the triblock copolyamides have two diffraction peaks, i.e., 2θ = 20.5° and 24°. However, the multiblock has only one peak at 2θ = 20°, indicating a different crystal structure for multiblock copolyamides. For the mechanical properties, it is found that the multiblock copolyamides have a more significant reinforcing effect than the triblock copolyamides. Also, the order of the physical properties of aromatic modified Nylon-6 copolyamides, such as tensile strength, is PmIA > PMA > PSA, but for the elongation PSA > PMA > PmIA.     

Mechanical properties and linear infrared dichroism of thin films of polyurethane nanocomposites

Morphological, mechanical, and Fourier transform infrared dichroic investigations were performed on neat polyurethane (PU) polymer matrix and PU+CaCO₃ nanocomposite thin films to determine how the nanofiller influenced the mechanical properties. The measurements were performed on strips that were cut from the prepared films in parallel and perpendicular directions with respect to the direction of film preparation. Optical microscopy of PU and the PU+CaCO₃ nanocomposite revealed the strain‐induced transition from a continuous spherulitic morphology to a fiberlike structure. The stress–strain behavior of the neat PU and PU+CaCO₃ nanocomposite films showed significant differences at large strain regimes. The experimental results suggest that the mechanical properties were strongly related to the orientational behavior of the separated phases. The orientation of the hard and soft segments was analyzed by the orientation function calculated from the IR absorbances. A correlation between the orientations of segments, tensile properties, and hardness of the investigated polymer films was established. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

High-modulus fibres of nylon-6 prepared by a dry-spinning method

Nylon-6 filaments with tensile strengths at break up to 1 GPa and initial moduli in the range of 16 to 19 GPa have been produced by dry-spinning of solutions of nylon-6 in cosolvent mixtures of formic acid and chloroform followed by hot-drawing at 200°C–240°C. Tensile strengths and elastic moduli of the nylon-6 fibres were strongly dependent on the draw ratio, on the molecular weight of the polymer, on the polymer concentration in the spinning solution and on concentration of nonsolvent in the spinning solution. At high concentrations of nonsolvent in the spinning solution, the as-spun fibres of nylon-6 were composed of ball-like structural units, formed possibly due to the liquid-liquid phase separation in the polymer/solvent/nonsolvent ternary system. Formation of ball-like structures reduced the ultimate mechanical properties of hot-drawn fibres of nylon-6.     

分子复合型尼龙—6合金材料的研究进展

本文概述了分子复合型尼龙－６合金材料的发展及最新研究动态，介绍了近十几年来国内外和种典型尼龙－６分子复合的制备、结构与性能、增强机理，预示了分子复合型尼龙－６合金材料的开发前景。     

Grafting of Nylon-6, 6 on Cellulose Acetate

Graft polymers of Nylon-6, 6 on cellulose acetate were obtained by successive alternate controlled addition of adipoyl chloride followed by 1,6-hexane diamine to the potassium alkoxide derivative of cellulose diacetate in tetrahydrofuran. The graft polymers were fractionated and isolated from homopolymer fractions. Their Nylon-6, 6 content increased upon increasing the monomer concentration.     

Rheological,crystal structure,barrier, and mechanical properties of PA6 and MXD6 nanocomposite films

In this study, rheological, crystal structure, barrier, and mechanical properties of polyamide 6 (PA6), poly(m‐xylene adipamide) (MXD6) and their in situ polymerized nanocomposites with 4 wt % clay were studied. The extent of intercalation and exfoliation as well as type of crystals, crystallinity, and thermal transitions were investigated using X‐ray diffraction (XRD) and differential scanning calorimetry (DSC), respectively. Dynamic rheological measurements revealed that incorporation of nanoclay significantly increases complex viscosity of MXD6 nanocomposites at low frequencies, which was related to the formation of a nanoclay network and exchange reaction between MXD6 chains. The comparative study of dynamic characteristics (G′ (ω) and G″ (ω)) for aliphatic and aromatic polyamide nanocomposites with their neat resins as well as the relaxation spectra for both polymer systems confirmed the possibility of the aforementioned phenomena. Although, the crystallinity of MXD6 films was lower as compared to PA6 films, the permeability to oxygen was more than 5 times better for the former. Incorporating 4 wt% clay enhanced the barrier property, tensile modulus, and yield stress of PA6 and MXD6 nanocomposite films in both machine and transverse directions without sacrificing much puncture and tear resistances. The PA6‐based films showed higher tear and puncture strength as compared to MXD6 films. POLYM. ENG. SCI., 54:2617–2631, 2014. © 2013 Society of Plastics Engineers     

尼龙6超韧化

介绍了国外在尼龙６超韧化改性研究领域中的最新进展。主要介绍几经龙６共混物及其增韧的机理。     

Influence of molecular weight and molecular weight distribution on the tensile properties of amorphous polymers

Tensile property data for polystyrene samples of varying polydispersity are correlated with various parametric measures of molecular weight. Traditional measures of molecular weight, such as M?_n, M?_w, and M?_z, are shown to be unable to account for the variation of tensile properties with molecular weight. However, a new molecular weight parameter, termed the failure property parameter, is able to provide a single relationship between tensile strength and the parameter for both the broad and narrow distribution polymers. The form of this parameter is consistent with its having origins in the view that it is the entanglement network in an amorphous polymer that provides the observed strength properties. Specifically for polystyrene, the failure property parameter results indicate that material below 60,000 molecular weight does not contribute to polymer strength. Although the results of this investigation are specifically for polystyrene, the arguments used to develop the failure property parameter are not dependent on polymer chemical structure. Consequently, we believe that both the concepts and definition of this new parameter are applicable to all amorphous polymers.     

Orientation and structure development in melt-spun Nylon-6 fibres

A network model is applied to describe the deformation behaviour of melt-spun Nylon-6 fibres obtained at different spinning and drawing conditions. The network draw ratio is determined from analysis of true stress-strain curves and correlated with fibre orientation. From this analysis it appears that the deformation behaviour of Nylon-6 fibres adheres to a pseudo-affine mechanism. The results are discussed in terms of the semicrystalline nature of Nylon-6 fibres. By means of on-line birefringence measurements, wide angle X-ray scattering (WAXS) and solid-state NMR, it is shown that the crystalline and amorphous phases in Nylon-6 respond in a different way to network deformation. In the spin line, an affine (rubber-like) deformation mechanism is observed and this rubber-like network behaviour is transferred to the amorphous phase. After winding and conditioning of the spun fibres, a crystalline phase with relatively high orientation is formed which deforms according to a pseudo-affine mechanism upon further stretching.     

Chain extension of polyamide 6/organoclay nanocomposites

Thermal degradation of polyamide 6 (PA6)/organoclay nanocomposites is a serious impediment to wider applications of these nanocomposites. In this study, a solution is proposed based on the well‐established use of chain extenders. As in PA6, thermal degradation, in the absence of moisture, produces broken polymer chains with amide end groups, a chain extender with anhydride functionalities, known to be strongly reactive with amide groups, was used to reconnect the chains. Experiments conducted using a laboratory twin‐screw extruder were first checked, through transmission electron microscopy observations, to have produced good organoclay intercalation and exfoliation into PA6. Following from this, samples with the chain extender added were produced and characterized. The data obtained were conclusive in the effectiveness of the chain extender: for the chain extended nanocomposites, there is an enhancement in the value of the complex viscosity by 7 times and in the storage modulus by 88 times, while the tensile modulus increased by 57% compared with the neat PA6. The nonchain extended nanocomposite achieved in comparison an enhancement of 2 times the value of the complex viscosity and 19 times the storage modulus while the tensile modulus increased by 53% compared to the neat PA6. These data provide conclusive proof on the rationale that anhydride functionalities should be sought when developing chain extenders for PA6 nanocomposites. POLYM. ENG. SCI., 59:1233–1241 2019. © 2019 Society of Plastics Engineers     

Synthesis and characterization of polyesteramides having short Nylon-6 segments in the main chains through polycondensation and chain extension

A Nylon-6 oligomer (PrePA) was synthesized by ring-opening polymerization from ε-caprolactam with 2-amino-ethanol under the catalysis of H₃PO₃. Polyesteramide prepolymers (PrePEAs) having amide content from 10 to 60 mol% were prepared through melt polycondensation from adipic acid, 1,4-butanediol and the PrePA. Chain extension of PrePEAs was carried out at 200 °C using 2,2′-(1,4-phenylene)-bis(2-oxazoline) and carbonylbiscaprolactamate as combined chain extenders. The chain-extended polyesteramides (ExtPEAs) with intrinsic viscosity up to 0.61 dL/g were synthesized. The ExtPEAs were characterized by FT-IR and ¹H NMR spectra, differential scanning calorimetry, wide angle X-ray scattering, thermogravimetric analysis and tensile test. The results showed that the ExtPEAs mainly crystallized in the Nylon-6 crystallites. ExtPEAs had T_g from −46.71 to 4.28 °C, T_m from 106.69 to 139.92 °C, thermal stability with initial decomposition temperature over 339 °C, tensile strength up to 30.89 MPa and stain at break higher than 797.1%. These ExtPEAs were strong, thermally stable and tough thermoplastic polymers.     

Rheology of a low‐filled polyamide 6/montmorillonite nanocomposite

The rheological properties of a polyamide 6/clay nanocomposite with a low loading of clay (1 wt %) were studied. Linear viscoelastic measurements in oscillatory and steady shear with small strain amplitudes were carried out. The nanocomposite exhibited a higher elastic modulus, viscous modulus, and complex viscosity than neat polyamide 6 during dynamic and steady shear tests. Moreover, the addition of clay resulted in a reduction of the critical strain amplitude, an increase of the loss angle, and a reduction of the frequency at the intersection of the elastic and viscous moduli. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

消除尼龙-6黄粒子

黄粒子严重影响了尼龙-6切片质量,分析了黄粒子产生的原因及解决措施.     

Effect of silane functionalized alumina on poly(vinyl butyral) nanocomposite films: Thermal,mechanical, and moisture barrier studies

In this work, a hybrid‐polymer nanocomposite film, based on polyvinyl butyral/amino‐silane functionalized nano alumina, was fabricated by melt processing. The calcium degradation measurements suggest the functionalized nanocomposite films exhibit higher resistance towards moisture penetration as compared to the neat alumina loaded films. Thermal stability, mechanical strength, and contact angle studies of the composites were also conducted to evaluate the performance of the functionalized alumina loaded films. These nanocomposite films were encapsulated over Al/P3HT/ITO Schottky structured device. The changes observed in the current density of the devices to the applied voltage before and after accelerated aging conditions are presented. The nanocomposite with functionalized alumina films exhibits 50% change in current density, which is superior to that attained with neat and non‐functionalized films. POLYM. COMPOS., 35:1426–1435, 2014. © 2013 Society of Plastics Engineers     

Properties of polypropylene/layered-silicate nanocomposites and melt-spun fibers

Polypropylene (PP)/layered-silicate organoclay nanocomposites and their fibers were prepared by melt compounding and melt spinning, respectively, in the presence or absence of compatibilizer (PP-based maleic anhydride compatibilizer) to examine the effects of the organoclay dispersion and rheological behavior on the internal structure and tensile properties of the nanocomposite fibers. The compatibilized nanocomposites showed solidlike plateau behavior and strain hardening due to a three-dimensional network structure in the shear and uniaxial elongational flows. The tensile properties of the nanocomposite fibers were reduced compared with those of the pure PP fibers because some of the layered silicates were present as partially aggregated forms and the molecular weight of the compatibilizer was lower than that of the pure PP matrix. It was also found that the tenacity of the nanocomposite fiber increased and then decreased as the compatibilizer content increased because the compatibilizer affected the internal structure of the nanocomposite fibers. The positive effect of the compatibilizer was to generate a more effective exfoliated structure of organoclay in the polymer matrix. The negative effect was that the melt-spun nanocomposite fiber had a lower molecular weight than the pure PP fiber because the compatibilizer had a lower molecular weight. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008