Search Results (31)

In this study, a poly [ε-caprolactam-co-bis(2-hydroxyethyl) terephthalate] copolymer (P (CL-co-BHET)) was synthesized from para-terephthalic acid (PTA), ethylene glycol (EG), and caprolactam (CL). The crystallization behavior and thermal stability of the copolymer were thoroughly investigated. With the aid of molecular simulation, this study investigated the variation in interchain hydrogen bonding in the copolymer, focusing on the direction and the number of hydrogen bonds. The results revealed a close relationship between the copolymer chain structure, the variation in interchain hydrogen bonding, and the crystallization behavior and thermal stability of the copolymer. The introduction of BHET segments disrupted the regularity of the PA6 backbone and hydrogen bonding, leading to a decrease in the melting point, crystallization temperature, and crystallinity of the copolymer. The thermal stability of the copolymers also decreased, and the crystallization form gradually shifted from the α-crystalline to the γ-crystalline phase. The findings of this study are significant for evaluating the crystallization behavior of polyester amides and for predicting and regulating the properties of polyesteramide polymers. Full article

Background/Objectives: Laurocapram (Azone) attracted attention 40 years ago as a compound with the highest skin-penetration-enhancing effect at that time; however, its development was shelved due to strong skin irritation. We had already prepared and tested an ante-enhancer (IL-Azone), an ionic liquid (IL) with a similar structure to Azone, consisting of ε-caprolactam and myristic acid, as an enhancer candidate that maintains the high skin-penetration-enhancing effect of Azone with low skin irritation. In the present study, fatty acids with different carbon numbers (caprylic acid: C8, capric acid: C10, lauric acid: C12, myristic acid: C14, and oleic acid: C18:1) were selected and used with ε-caprolactam to prepare various IL-Azones in the search for a more effective IL-Azone. Methods: Excised porcine skin was pretreated with each IL-Azone to assess the in vitro skin permeability of antipyrine (ANP) as a model penetrant. In addition, 1,3-butanediol was selected for the skin permeation test to confirm whether the effect of IL-Azone was due to fatty acids and if this effect differed depending on the concentration of IL-Azone applied. Results: The results obtained showed that C12 IL-Azone exerted the highest skin-penetration-enhancing effect, which was higher than Azone. On the other hand, many of the IL-Azones tested had a lower skin-penetration-enhancing effect. Conclusions: These results suggest the potential of C12 IL-Azone as a strong and useful penetration enhancer. Full article

In this study, we successfully realized the hydrolytic ring-opening co-polymerization of ε-caprolactam (CPL) and lysine derivative. A novel antibacterial modified polyamide 6 with a branched structure was obtained after the quaternization of the co-polymers. The co-polymers exhibited a significant increase in zero shear viscosity, melt index and storage modulus at the low frequency region. The quaternized co-polymers displayed thermal properties different from pure PA6 and good mechanical (tensile) properties. The antibacterial activity of the quaternized co-polymers depends on the quaternary ammonium groups’ incorporated content. At 6.2 mol% incorporation of quaternary ammonium groups, the strong antibacterial activity has been introduced to the co-polymers. As the quaternary ammonium groups approached 10.1 mol%, the antibacterial polymers demonstrated nearly complete killing of Staphylococcus aureus (Gram positive) and Escherichia coli (Gram negative). The above research results provided a new approach for the study of high-performance nylon. Full article

In this study, a novel branched polyamide 6 has been synthesized via the hydrolytic ring-opening co-polymerization of ε-caprolactam (CPL) and α-Amino-ε-caprolactam (ACL). The NMR characterization proves the existence of a branched chain structure. The rheological test determines that there is a remarkable increase in the melt index (MFR), zero shear rate viscosity, and storage modulus in the low-frequency region. The shear-thinning phenomenon becomes more obvious. The thermal properties tested by differential scanning calorimetry (DSC) show that the melting point and crystallinity of co-polymers decrease with the incorporation of ACL. However, the crystal structure of the samples only exhibits a slight change. When the ACL content in the feed is 1 wt%, the tensile strength and fracture elongation rate of the co-polymers show a significant enhancement. Full article

Polybenzoxazines (PBzs) are advanced forms of phenolic resins that possess many attractive properties, including thermally induced self-curing polymerization, which produces void-free polymer products without any by-product formation. They also possess a high T_g (glass transition temperature) and thermal stability, but the produced materials are brittle in nature, due to which the final form of their application is very difficult. Hence, in this paper, an attempt has been made to overcome the brittleness of PBz by blending it with epoxy and ε-caprolactam (CPLA) to produce free-standing PBz/Epoxy/PCLA (polycaprolactam) films. The curing process between the three components (i.e., Bzo, epoxy, and caprolactam) was monitored using differential scanning calorimetric (DSC) analysis. The results show that there is no appreciable shift in curing the exotherm observed, except a slight shift in the curing process. However, the heat liberated during the exotherm (ΔH) decreases drastically from 121 to 84 J/g, indicating that the content of benzoxazine is very important as it is involved in the polymerization process through oxazine ring-opening. The morphological studies analyzed using SEM and AFM analyses indicate that there was no observable phase separation up to 30 wt.% of CPLA loading, whereas a higher CPLA content of 50 wt.% causes agglomeration and leads to distinctive phase separation. Moreover, the thermal stability of the composite film, PBz/Epoxy/PCLA30, is also increased with a 10% degradation temperature, T₁₀, of 438 °C, when compared with an PBz/Epoxy film. From the obtained results, it is evident that the formation of a composite film through the melt blending process could produce a tough and thermally stable film without sacrificing individual properties. Full article

In order to adjust the properties of polyamide 6 (PA6) and expand its application, a new strategy of introducing an aromatic imide structure into the PA6 chain through the random copolymerization method is reported. The diimide diacid monomer was first synthesized by the dehydration and cyclization of pyromellitic dianhydride and 6-aminocaproic acid before it reacted with 1,6-hexamethylene diamine to form poly(amide imide) (PAI) salt, and finally synthesized PA6/PAI random copolymers containing an aromatic imide structure by the random copolymerization of ε-caprolactam and PAI salt. The introduction of an aromatic imide structural unit into the PA6 chain could have a great influence on its properties. As the content of PAI increases, the crystallinity (X_c) and melting temperature (T_m) of the PA6/PAI random copolymer gradually decrease, but its glass transition temperature (T_g) increases obviously. When the PAI content is 20 wt%, the copolymer PA6/PAI-20 has the best comprehensive performance and not only has high thermal stabilities but also excellent mechanical properties (high strength, high modulus, and good toughness) and dielectric properties (low dielectric constant and dielectric loss). Moreover, these properties are significantly superior to those of PA6. Such high-performance PA6 random copolymers can provide great promise for the wider applications of PA6 materials. Full article

Lysine is a key raw material in the chemical industry owing to its sustainability, mature fermentation process and unique chemical structure, besides being an important nutritional supplement. Multiple commodities can be produced from lysine, which thus inspired various catalytic strategies for the production of these lysine-based chemicals and their downstream applications in functional polymer production. In this review, we present a fundamental and comprehensive study on the catalytic production process of several important lysine-based chemicals and their application in highly valued polymers. Specifically, we first focus on the synthesis process and some of the current industrial production methods of lysine-based chemicals, including ε-caprolactam, α-amino-ε-caprolactam and its derivatives, cadaverine, lysinol and pipecolic acid. Second, the applications and prospects of these lysine-based monomers in functional polymers are discussed such as derived poly (lysine), nylon-56, nylon-6 and its derivatives, which are all of growing interest in pharmaceuticals, human health, textile processes, fire control and electronic manufacturing. We finally conclude with the prospects of the development of both the design and synthesis of new lysine derivatives and the expansion of the as-synthesized lysine-based monomers in potential fields. Full article

It is highly expected to develop a simple and effective method to reinforce polyamide 6 (PA6) to enlarge its application potential. This is challenging because of frequently encountered multi-component phase separations. In this paper, we propose a novel method to solve this issue, essentially comprising two steps. Firstly, a kind of poly (amide-block-aramid) block copolymers, i.e., thermotropic liquid crystalline polymer (TLCP)-polyamide 6 (TLCP-PA6), that contains both rigid aromatic liquid crystal blocks, and flexible alkyl blocks were synthesized. It is unique in that TLCP is chemically linked with PA6, which is advantageous in excellent chemical and physical miscibility with the precursors of monomer casting polyamide 6 (MCPA6), i.e., ε-caprolactam. Secondly, such newly synthesized block copolymer TLCP-PA6 was dissolved in the melting ε-caprolactam, and followed by in situ polymerization to obtain composite polymer blends, i.e., MCPA6/TLCP-PA6. The thermodynamic, morphological, and crystalline properties of MCPA6/TLCP-PA6 can be easily manipulated by tailoring the loading ratios between TLCP-PA6 and ε-caprolactam. Especially, at the optimized condition, such MCPA6/TLCP-PA6 blends show an excellent miscibility. Systematic characterizations, including nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), differential scanning calorimeter (DSC), and polarizing optical microscope (POM), were performed to confirm these statements. In view of these results, it is anticipated that the overall mechanical properties of such PA6-based polymer composites will be satisfactory, which should enable applications in the modern plastic industry and other emerging areas, such as wearable fabrics. Full article

Hydrogen bond interactions are important for nylon fibers, which improve its mechanical properties and crystallization behavior, while hindering the movement and orientation of the molecular chain during the drawn process. In this study, hexamethylene adipamide was used as the second monomer in copolymerization with ε-caprolactam to obtain copolyamide 6/66 (CoPA), and high-tenacity fibers with a maximum value up to 8.0 cN/dtex were achieved by a multi-step drawn and thermal setting process. Results show that the hexamethylene–adipamide ratio affected the draw ratio (DR) of the as-spun fiber, on the tenacity of final high-performance fiber, and on crystalline. Both DR and tenacity showed evident increases with the hexamethylene–adipamide ratio up to 6% in CoPA and then changed smoothly. However, XRD and DSC results illustrate a decreased tendency with regard to crystallinity. The attenuated in-site total reflection Fourier transform infrared (ATR-FTIR) spectra were used to study the hydrogen bond interaction between the C=O group and N–H group and the crystal form of the fiber. Results show that the copolymerization destroyed the regularity of the main chain of CoPA and reduces the interaction of interstrand hydrogen bonds, facilitating the formation of the γ-crystalline form in as-spun fibers, fulfilling the transition from the γ to α crystalline form during the fiber-drawing step because of the release of the C=O group and N–H group from the hydrogen bond interaction at an elevated temperature close to the molten temperature of CoPA, and then reforming during the thermal-setting step which soiled the crystalline and improved the tenacity of the fiber. The copolymerization with a homologous monomer regulates the hydrogen bond interaction, fulfills the high drawn ratio and high tenacity fiber, and provides a new route for high-performance fiber preparation using traditional fiber formation of polymers. Full article

Contaminants of emerging concern (CECs) are compounds of diverse origins that have not been deeply studied in the past which are now accruing growing environmental interest. The NOR-Water project aimed to identify the main CECs and their sources in the water environment of Northern Portugal–Galicia (located in northwest Spain) transnational region. To achieve these goals, a suspect screening analytical methodology based on the use of liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) was applied to 29 sampling sites in two campaigns. These sampling sites included river and sea water, as well as treated wastewater. The screening was driven by a library of over 3500 compounds, which included 604 compounds prioritized from different relevant lists on the basis of the persistency, mobility, and toxicity criteria. Thus, a total of 343 chemicals could be tentatively identified in the analyzed samples. This list of 343 identified chemicals was submitted to the classification workflow used for prioritization and resulted in 153 chemicals tentatively classified as persistent, mobile, and toxic (PMT) and 23 as very persistent and very mobile (vMvP), pinpointing the relevance of these types of chemicals in the aqueous environment. Pharmaceuticals, such as the antidepressant venlafaxine or the antipsychotic sulpiride, and industrial chemicals, especially high production volume chemicals (HPVC) such as ε-caprolactam, were the groups of compounds that were detected at the highest frequencies. Full article

To move toward eco-sustainable and circular composites, one of the most effective solutions is to create thermoplastic composites. The strong commitment of world organizations in the field of safeguarding the planet has directed the research of these materials toward production processes with a lower environmental impact and a strong propensity to recycle the polymeric part. Under its chemical properties, Nylon 6 is the polymer that best satisfies this specific trade-off. The most common production processes that use a thermosetting matrix are described. Subsequently, the work aimed at investigating the use of thermoplastics in the same processes to obtain comparable performances with the materials that are currently used. Particular attention was given to the in situ anionic polymerization process of Nylon 6, starting from the ε-caprolactam monomer. The dependencies of the process parameters, such as temperature, time, pressure, humidity, and concentration of initiators and activators, were therefore investigated with reference to the vacuum infusion technique, currently optimized only to produce thermosetting matrix composites, but promising for the realization of thermoplastic matrix composite; this is the reason why we chose to focus our attention on the vacuum infusion. Finally, three production processes of the polymeric matrix and glass fiber composites were compared in terms of carbon footprint and cumulative energy demand (CED) through life-cycle assessment (LCA). Full article

Polymer components capable of self-healing can rapidly be manufactured by injecting the monomer (ε-caprolactam), activator and catalyst mixed with a small amount of magnetic nanoparticles into a steel mould. The anionic polymerisation of the monomer produces a polymer component capturing magnetic nanoparticles in a dispersed state. Any microcracks developed in this nanocomposite component can be healed by exposing it to an external alternating magnetic field. Due to the magnetocaloric effect, the nanoparticles locally melt the polymer in response to the magnetic field and fill the cracks, but the nanoparticles require establishing a network within the matrix of the polymer through effective dispersion for functional and uniform melting. The dispersed nanoparticles, however, affect the degree of crystallinity of the polymer depending on the radius of gyration of the polymer chain and the diameter of the magnetic nanoparticle agglomerates. The variation in the degree of crystallinity and crystallite size induced by nanoparticles can affect the melting temperature as well as its mechanical strength after testing for applications, such as stimuli-based self-healing. In the case of in situ synthesis of the polyamide-6 (PA6) magnetic nanocomposite (PMC), there is an opportunity to alter the degree of crystallinity and crystallite size by optimising the catalyst and activator concentration in the monomer. This optimisation method offers an opportunity to tune the crystallinity and, thus, the properties of PMC, which otherwise can be affected by the addition of nanoparticles. To study the effect of the concentration of the catalyst and activator on thermal properties, the degree of crystallinity and the crystallite size of the component (PMC), the ratio of activator and catalyst is varied during the anionic polymerisation of ε-caprolactam, but the concentration of Fe₃O₄ nanoparticles is kept constant at 1 wt%. Differential Scanning Calorimetry (DSC), Fourier-transform infrared spectroscopy (FTIR), XRD (X-ray diffraction) and Thermogravimetric analysis (TGA) were used to find the required concentration of the activator and catalyst for optimum properties. It was observed that the sample with 30% N-acetyl caprolactam (NACL) (with 50% EtMgBr) among all of the samples was most suitable to Rapid Prototype the PMC dog-bone sample with the desired degree of crystallinity and required formability. Full article

Nylon/saponite nanocomposites were synthesized and characterized. The nanocomposites were prepared by means of a fast, efficient, low cost, and environmentally friendly method. All of the tested preparations resulted in the pre-designed nanocomposites. To this end, delaminated saponites were directly synthesized to be used as a filler in a polymer matrix formed by nylon-6 by the in situ intercalation polymerisation of an ε-caprolactam monomer without the use of surfactants or other organic reagents to organophilise the clay, thus avoiding the drawbacks of contamination. The efficiency of the preparation method increased, and significant savings were achieved in terms of both energy reaction time, savings of 60% and 70%, respectively, by using microwave radiation as an energy source during the synthesis of the nanocomposites. In addition, given that the method that was followed avoids the use of contaminating organophilic agents, it is important to highlight the savings in reagents and the fact that there was zero environmental contamination. Full article

The epithelial–mesenchymal transition (EMT) of cancer cells is a crucial process in cancer cell metastasis. An Aquimarina sp. MC085 extract was found to inhibit A549 human lung cancer cell invasion, and caprolactin C (1), a new natural product, α-amino-ε-caprolactam linked to 3-methyl butanoic acid, was purified through bioactivity-guided isolation of the extract. Furthermore, its enantiomeric compound, ent-caprolactin C (2), was synthesized. Both 1 and 2 inhibited the invasion and γ-irradiation-induced migration of A549 cells. In transforming growth factor-β (TGF-β)-treated A549 cells, 2 inhibited the phosphorylation of Smad2/3 and suppressed the EMT cell marker proteins (N-cadherin, β-catenin, and vimentin), as well as the related messenger ribonucleic acid expression (N-cadherin, matrix metalloproteinase-9, Snail, and vimentin), while compound 1 did not suppress Smad2/3 phosphorylation and the expression of EMT cell markers. Therefore, compound 2 could be a potential candidate for antimetastatic agent development, because it suppresses TGF-β-induced EMT. Full article