Search

Coupling in situ generated intermediates with other substrates/intermediates is a viable approach for diversifying product outcomes of catalytic reactions involving two or multiple reactants. Cyclohexanone oxime is a key precursor for caprolactam synthesis (the monomer of Nylon‐6), yet its current production uses unsustainable carbon sources, noble metal catalysts, and harsh conditions. Herein, we report the first work to synthesize cyclohexanone oxime through electroreduction of phenol and hydroxylamine. The Faradaic efficiency reached 69.1 % over Cu catalyst, accompanied by a corresponding cyclohexanone oxime formation rate of 82.0 g h−1 gcat−1. In addition, the conversion of phenol was up to 97.5 %. In situ characterizations, control experiments, and theoretical calculations suggested the importance of balanced activation of water, phenol, and hydroxylamine substrates on the optimal metallic Cu catalyst for achieving high‐performance cyclohexanone oxime synthesis. Besides, a tandem catalytic route for the upgrading of lignin to caprolactam has been successfully developed through the integration of thermal catalysis, electrocatalysis, and Beckmann rearrangement, which achieved the synthesis of 0.40 g of caprolactam from 4.0 g of lignin raw material. [ABSTRACT FROM AUTHOR]

The inhomogeneous dispersion caused by carbon nanotube (CNT) agglomeration in composites still needs to be explored, though mechanical properties of the polymer materials can be improved significantly if CNTs were added as a reinforcement. In this work, to explore an effective way to solve the agglomeration problem of CNTs within polycaprolactam (Nylon66), a functionalization strategy to enhance the intermolecular interaction between the caprolactam (CPL) unit molecule and (7,3) single-walled carbon nanotube (SWCNT) was investigated theoretically at the molecular level. Molecular moving behavior and intermolecular interaction energy indicate that the surface functionalization, especially with the –NH2 group, is an effective way to strengthen the interaction between CPL and (7,3) SWCNTs, which highlights the key role of controlled surface functionalization of CNTs in improving its dispersion degree in polycaprolactam. This can be explained by a small interfacial charge-transfer amount, which occurs from the occupied valence band maximum of (7,3) SWCNTs to the occupied highest occupied molecular orbital of the CPL molecule. In this case, the dipole moment of involved molecules plays an important role in the interfacial interaction strength and then increased intermolecular interaction between CPL and functionalized (7,3) SWCNTs, especially incorporating the –NH2 group with larger dipole moment, can be understood. Our results for the functionalization effects on the physical adsorption behavior of organic molecules around (7,3) SWCNTs can provide more useful information for further design and optimization of a SWCNT-based reinforcement. [ABSTRACT FROM AUTHOR]

Nylon nanocomposites were prepared by in‐situ ring‐opening polymerization to overcome the problem of poor properties due to the uneven dispersion of the nanoparticles by the traditional melt blending. This high‐performance polyamide 6 (PA6) nanocomposites with high dispersion and strong interface was prepared by grafting PA6 onto the surface of cellulose nanocrystals (CNC). The micromorphology, mechanical, crystalline and thermal properties of the composites were also investigated. Firstly, the hydroxyl group on the surface of CNC reacted with the para isocyanate of toluene diisocyanate (TDI), and the remaining ortho isocyanate was blocked by caprolactam to prepare CNC grafted with caprolactam (CNC‐g‐CL). Then CNC‐g‐CL was used as an activator to prepare cellulose nanocrystal grafted with polyamide 6 (CNC‐g‐PA6) composites by the ring‐opening polymerization of caprolactam on the CNC. The effects of different reaction temperatures, solvent amounts and molar ratios on the grafting rate of CNC‐g‐CL were investigated. The results showed that the highest grafting rate of CNC‐g‐CL with 66.7% was achieved at a reaction temperature of 45°C, 0.1 g/mL CNC in toluene, and a molar ratio of 6 for TDI/CNC. Further, different CNC‐g‐PA6 composites prepared from different CNC content and activator content were explored. For CNC‐g‐PA6 composites, CNC was uniformly dispersed in the PA6 matrix and had a good compatibility with the matrix. CNC exhibited significant reinforcement in the composites with a tensile strength of up to 108 MPa. In addition, the glass transition temperature of CNC‐g‐PA6 was increased to 92°C, which significantly improved the heat resistance of the new composites. Highlights: Effects of reaction condition of CNC and TDI on DSTDI and DSCL were studied.Effects of CNC and activator content on CNC‐g‐PA6 properties were studied.CNC is uniformly dispersed in PA6 with average particle size less than 1 micron.The nylon matrix was significantly strengthened by the addition of CNC.The addition of CNC significantly improved the heat resistance of the composites. [ABSTRACT FROM AUTHOR]

Hexamethylenediamine (HMDA), a crucial precursor of nylon-66, can be synthesized from caprolactam (CPL) via a two-step route involving CPL ammoniation and 6-aminocapronitrile (ACN) hydrogenation. Based on theoretical calculations and experimental screening, mesoporous alumina was selected which served as a highly active and cost-efficient catalyst for CPL ammoniation, catalysing the ring-opening of amides by C–N bond breakage and subsequent amide dehydration to nitrile. A 57.9% CPL conversion and 98.3% ACN selectivity were achieved at 320 °C with stability over 480 hours. The subsequent hydrogenation of ACN using the commercial RANEY® Ni catalyst yielded 100% HMDA, requiring milder conditions and half the hydrogen compared to adiponitrile processes. Overall, this research highlights a green HMDA production pathway, employing CPL as a feedstock. [ABSTRACT FROM AUTHOR]

The preparation of caprolactam (CPL) from biomass as raw material is a very hot topic of current concern. In this paper, a new way to synthesize CPL from 5-hydroxymethylfurfural (HMF) was proposed, and the catalytic reaction of cyclization of the intermediate 6-hydroxycaproamide (6-HCM) was studied to provide a basis for the synthesis of bio-based CPL. A bimetallic catalyst, Ru–Co/TiO2, was prepared using the impregnation method and characterized using XRD, XPS, H2-TPR, and TEM. The investigation delves into the impact of various parameters, including metal loading, choice of solvent, solvent ratio, catalyst dosage, and reaction time, on the yield of the final product. The findings demonstrate a significant synergistic effect between Ru and Co in the bimetallic Ru5Co6/TiO2 catalyst, leading to improved catalytic performance. Under the optimized reaction conditions (250 °C, 1 MPa N2, 1,4-dioxane: NH3·H2O = 2:1 as the solvent ratio), the conversion rate of 6-HCM reaches 99.0%, with CPL yield of 62.2%. [ABSTRACT FROM AUTHOR]

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The authors investigate a new reagent—modified water-soluble polymer of polyvinyl caprolactam (PVCL)—as a collector in flotation of gold-bearing sulfide ore. Modified PVCL is obtained by solid-phase modification of poly(N-vinyl caprolactam) by thiourea. The electron scan and laser microscopy identified adsorption of PVCL at gold grains applied artificially to the surface of polished sections of pyrite. It is found that PVCL facilitates selective aggregation of gold-bearing minerals from fine slime, and more than 99% of gold goes from fine slime to sand at the content of 3.54 g/t. The use of PVCL together with butyl potassium xanthate (PVCL 30 g/t, BPX 200 g/t) in flotation of finely ground gold-bearing ore from the Olimpiada deposit improved the quality of the concentrate: gold content increased from 19.9 to 29.5 g/t and gold recovery increased from 81 to 95%. The joint application of modified PVCL and BPX results in the gold recovery higher by 14%, concentrate quality improved 1.5 times and in the gold content of tailings reduced to 0.15 g/t. [ABSTRACT FROM AUTHOR]

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Valerolactam is a monomer used to manufacture high-value nylon-5 and nylon-6,5. However, the biological production of valerolactam has been limited by the inadequate efficiency of enzymes to cyclize 5-aminovaleric acid to produce valerolactam. In this study, we engineered Corynebacterium glutamicum with a valerolactam biosynthetic pathway consisting of DavAB from Pseudomonas putida to convert L-lysine to 5-aminovaleric acid and β-alanine CoA transferase (Act) from Clostridium propionicum to produce valerolactam from 5-aminovaleric acid. Most of the L-lysine was converted into 5-aminovaleric acid, but promoter optimization and increasing the copy number of Act were insufficient to significantly improve the titer of valerolactam. To eliminate the bottleneck at Act, we designed a dynamic upregulation system (a positive feedback loop based on the valerolactam biosensor ChnR/Pb). We used laboratory evolution to engineer ChnR/Pb to have higher sensitivity and a higher dynamic output range, and the engineered ChnR-B1/Pb-E1 system was used to overexpress the rate-limiting enzymes (Act/ORF26/CaiC) that cyclize 5-aminovaleric acid into valerolactam. In glucose fed-batch culture, we obtained 12.33 g/L valerolactam from the dynamic upregulation of Act, 11.88 g/L using ORF26, and 12.15 g/L using CaiC. Our engineered biosensor (ChnR-B1/Pb-E1 system) was also sensitive to 0.01-100 mM caprolactam, which suggests that this dynamic upregulation system can be used to enhance caprolactam biosynthesis in the future.

An interconnected sponge structure and porous surface poly (acrylonitrile-co-methyl acrylate) (P(AN-MA)) microfiltration membranes (MF) were fabricated via thermally induced phase separation (TIPS) by using caprolactam (CPL), and acetamide (AC) as the mixed diluent. When the ternary system was composed of 15 wt.% P(AN-MA), 90 wt.% CPL, and 10 wt.% AC and formed in a 25 °C air bath, the membrane exhibited the highest water flux of 8107 L/m2·h. The P(AN-MA) membrane contained hydrophobic groups (-COOCH3) and hydrophilic groups (-CN), leading it to exhibit oleophobic properties underwater and hydrophobic properties in oil. The membrane demonstrates efficient separation of immiscible oil/water mixtures. The pure water flux of the petroleum ether/water mixture measured 870 L/m2·h, and the pure oil flux of the petroleum tetrachloride/water mixture measured 1230 L/m2·h under the influence of gravity. Additionally, the recovery efficiency of diluents through recrystallization was 85.3%, significantly reducing potential pollution and production costs. [ABSTRACT FROM AUTHOR]

Copyright of Low-Carbon Chemistry & Chemical Engineering is the property of Low-Carbon Chemistry & Chemical Engineering Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Upcycling biodegradable polyester waste into value-added chemicals can not only avoid CO2 emissions but also achieve sustainable carbon recycling. Herein, we report a one-pot catalytic process to deconstruct polycaprolactone into 6-aminocaproic acid (EACA) and caprolactam (CPL), two monomers of nylon-6, using aqueous ammonia and Ru catalysts. No additional hydrogen is required, and the total yield of EACA and CPL could reach 90.2% using a ternary catalyst, Ru/CeO2/RGO, at 140 °C. It is verified that 6-hydroxyhexanoic acid and 6-hydroxyhexanoamide are the initial intermediates resulting from polycaprolactone decomposition, which undergo dehydrogenation, amination and re-hydrogenation to transform into EACA and 6-aminohexanoamide over the Ru catalyst. The hydrolysis of 6-aminohexanoamide produces EACA, and the reverse reaction between dehydration of EACA and hydrolysis of CPL results in their coexistence. The protocol demonstrated here provides a novel route to recycle polycaprolactone to valuable chemicals. [ABSTRACT FROM AUTHOR]

Caprolactam is in high demand in the new materials industry as a monomer for nylon and polyamides. Although the schemes of traditional processes such as hydroxylamine production (hydroxylamine sulphate oxime process, hydroxylamine phosphate oxime process, nitric oxide reduction process) and cyclohexanone production were still involved in the caprolactam production industry, the modern technical adaptations achieved higher atomic utilisation and higher selectivity. In this review, the basic traditional schemes for the production of caprolactam are for the first time presented. The modern technical adaptation, the rectification dehydrogenation of the by-product cyclohexane in cyclohexanone production, was highlighted to achieve an increase in atomic utilisation from 78 % to 98 %. The higher selectivity achieved with membrane separation resulted in a conversion of cyclohexanone of > 99.6 % and a selectivity of cyclohexanone oxime of > 99.5 %. In addition, the progress of the catalysts used in the modern technical adaptation was briefly discussed. This review highlights the modern process with atom economy and high selectivity.

Deep eutectic solvents (DESs) provide a greener approach to reduce the toxicity of ionic liquids (ILs) when altering the behaviour of polymers. DESs have extraordinary properties such as high solubilising abilities, easy preparation, low volatility, good thermal stability, and cost effectiveness, making them suitable for wider applications in biomedical research. DESs can be used for modulating the behaviour of thermo-responsive polymers (TRPs) to provide successful hybrid functionality very near or at room temperature to achieve better stability. The current study is an attempt to achieve this and demonstrates that the presence of choline chloride : lactic acid, 1 : 2 (CC : LA), betaine : lactic acid, 1 : 2 (BET : LA), proline : lactic acid, 1 : 1 (PRO : LA) and urea : lactic acid, 1 : 2 (U : LA) as DESs can change the performance of a thermoresponsive polymer poly(N-vinylcaprolactam) (PVCL). The thermoresponsive behaviour of PVCL was investigated in this study using a variety of techniques, including steady-state fluorescence, Fourier-transform infrared (FTIR) spectroscopy, and UV-visible spectroscopy. Additionally, the LCST values of PVCL were also examined by temperature dependent dynamic light scattering (DLS) which showed a regular decrease in the presence of DES. Dynamic light scattering was also used to better understand the PVCL's aggregation behaviour in the DES environment. Our results show that DESs are generally ionic or polar protic in nature and that they promote hydrophobic interactions among the biopolymeric chains by providing a hydrophobic environment and significantly promoting the hydrophobic collapse of PVCL. It was observed in this study that the structure of DESs plays a major role in altering the lower critical solution temperature (LCST) of PVCL. Our results shows that U:LA provides the least hydrophobic environment due to its polar nature and that BET:LA exerts the most pronounced extent. The intramolecular hydrogen bonding interactions among urea molecules lead to its lower interactions with the surrounding PVCL polymer and the absence of hydrogen bonding in the betaine moiety favours the intermolecular interactions with PVCL and results in a more prominent decrease in the LCST values of the polymer. All DESs successfully modulated the LCST of PVCL through the exclusion of water molecules around the polymer and thus facilitated faster agglomeration. Notably, the LCST of BET:LA reached 27 °C. This study provides us with a new approach for drug carrier applications. [ABSTRACT FROM AUTHOR]

It has been a long‐term challenge to synthesize intrinsically flame retardant polyamide 6 (FRPA6) with high‐molecular weight. In this work, through the ring‐opening polymerization of caprolactam initiated by 9,10‐dihydro‐10‐[2,3‐di(hydroxycarbonyl)propyl]‐10 phosphaphenanthrene‐10‐oxide (DOPO‐ITA), intrinsically flame retardant PA6 with high‐molecular weight was successfully prepared. Its chemical structure, thermal stability, mechanical and combustion properties, as well as the retarding mechanism were thoroughly characterized in detail. The FRPA6 containing 3.0% retardant could achieve a V‐0 rating with an LOI value of 31.2%. An interesting phenomenon was observed during V‐0 tests. The melt drip slowly extended downward to form a long strip after moving fire, which was in favor of its heat release in a short time, thereby effectively prevented it from igniting the cotton. That is, a facile method to prepare intrinsically high‐efficiency fire retardant polymer via ring opening and polycondensation was proposed. [ABSTRACT FROM AUTHOR]

Beckmann rearrangement has been quite successful in the preparation of many medicinally potent scaffolds. In synthetic organic chemistry, the Beckmann rearrangement is quite popular, caprolactam is synthesized from cyclohexanone oxime on a large scale for Nylon‐6 production. The function of numerous catalysts and media in the Beckmann rearrangement has been discussed in depth in this review. In the last 20 years, Beckmann rearrangement catalysis has evolved from a potentially hazardous to a more environmentally friendly catalyst, as a result of greater usage. Catalytic performance and synthetic performance of various catalytic systems have been re‐evaluated in the present review article. [ABSTRACT FROM AUTHOR]

Caprolactam is in high demand in the new materials industry as a monomer for nylon and polyamides. Although the schemes of traditional processes such as hydroxylamine production (hydroxylamine sulphate oxime process, hydroxylamine phosphate oxime process, nitric oxide reduction process) and cyclohexanone production were still involved in the caprolactam production industry, the modern technical adaptations achieved higher atomic utilisation and higher selectivity. In this review, the basic traditional schemes for the production of caprolactam are for the first time presented. The modern technical adaptation, the rectification dehydrogenation of the by-product cyclohexane in cyclohexanone production, was highlighted to achieve an increase in atomic utilisation from 78 % to 98 %. The higher selectivity achieved with membrane separation resulted in a conversion of cyclohexanone of > 99.6 % and a selectivity of cyclohexanone oxime of > 99.5 %. In addition, the progress of the catalysts used in the modern technical adaptation was briefly discussed. This review highlights the modern process with atom economy and high selectivity. [ABSTRACT FROM AUTHOR]

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

In this study, a modified torque rheometer is used to investigate the volatilization behavior of monomer and oligomers in polyamide-6 (PA6) melt under dynamic film–forming conditions with negative pressure. The surface renewal model is employed to simulate the volatilization behavior. The effects of actual processing factors and simulation results on the volatilization behavior of monomer and oligomer are analyzed comparatively. It is found that the monomer and oligomers removal rate increase continuously with increasing temperature, residence time, and rotational speed. And, the cyclic dimer, which is extremely harmful to spinning, can be removed. It is found that the removal of monomer and oligomers continued to increase with increasing temperature, residence time, and spinning speed. Moreover, cyclic dimers, which are extremely harmful to spinning, are also removed. Additionally, it is discovered that the polycondensation reaction of PA6 results in an increase in the molecular weight and viscosity at lower temperatures (250 °C), while a higher temperature (270 °C) and shear rate (150 r/min) cause a reduction in viscosity and molecular weight. [ABSTRACT FROM AUTHOR]

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Catalytic hydrodeoxygenation (HDO) is a promising route to upgrade bio‐oils from plants or pyrolysis to basic chemicals. KA‐oil (cyclohexanol/‐one) is an example of a highly valuable feedstock for the industrial synthesis of caprolactam and perlon, which can potentially be produced via a completely sustainable route. This work investigates the alkaline promoter effects on Ni‐based catalysts for the selective HDO of lignin surrogate guaiacol using mesoporous Ni/MgO and co‐impregnated Ni‐MgO/SiO2 catalysts. Due to preferred demethoxylation by alkaline oxides and their accumulation on nickel corners, responsible for dehydration, conversion, and selectivity for KA‐oil rise. Furthermore, influences of operating parameters are investigated and optimized by design of experiments (DoE), while long‐term stability (24 h) and water resistance remain high. In a final proof of concept, the application of Ni‐CaO/SiO2 was the most promising material (U=93 %, S=86 %), demonstrating a sustainable route from lignin‐based bio‐oil to produce a bulk commodity for caprolactam synthesis. [ABSTRACT FROM AUTHOR]

Hexaethylene glycolic vinyl imidazolium (hexaEGVIM) was supported on N-vinyl caprolactam via covalent bonds through simple copolymerization to form poly caprolactam-supported hexaethylene glycol-substituted imidazolium salts (PCLS-hexaEGIM). The resulting heterogeneous PCLS-hexaEGIM promoter was active, selective, and stable for aliphatic nucleophilic substitution reactions using alkali metal salts. The alkali metal salts dramatically enhanced the reactivity of this heterogeneous catalyst with easily isolable higher product yields, reducing the formation of by-products. Therefore, nucleophilic fluorination and other substitution reactions can act as highly efficient catalysts in various sulfonyloxyalkanes and haloalkanes with regard to their corresponding fluorinated products. [ABSTRACT FROM AUTHOR]

Here we report some results on a 3 steps benzene caprolactam process via amination, aniline Hydroxymation and Beckmann rearrangement. The amination proceeds with hydroxylamine trifluoroacetate, with 97% of conversion and selectivity of 90%, catalyzed by V compounds. We achieve 98% of conversion and 95% of selectivity in the hydroxymation of aniline in the presence of hydroxylamine trifluoroacetate, sulfonic resin and Pd/C. While in the absence of the resin, hydrogenation of hydroxylamine trifluoroacetate occurs readily to the ammonium salt. The reaction occurs likely by the exchanged hydroxylamine and the aniline reduction intermediate. The use of hydroxylamine trifluoroacetate, instead of the chloride, favors the sustainability of the process by avoiding the ammonium chloride formation. The absence of salt except those derived from the trifluoroacetic acid allows a complete reuse of the trifluoroacetic acid and the only byproduct is ammonium nitrate obtained by resin regeneration. Beckmann rearrangement of the so produced cyclohexanone oxime occurs easily after diethyl ether evaporation and additions of a solution trifluoroacetic acid acetonitrile in high yield and selectivity. New three steps caprolactam process via benzene amination and aniline hydrogenation. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Donghua University (Natural Science Edition) is the property of Journal of Donghua University (Natural Science) Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Synthesis of cyclohexanone oxime via the cyclohexanone‐hydroxylamine process is widespread in the caprolactam industry, which is an upstream industry for nylon‐6 production. However, there are two shortcomings in this process, harsh reaction conditions and the potential danger posed by explosive hydroxylamine. In this study, we presented a direct electrosynthesis of cyclohexanone oxime using nitrogen oxides and cyclohexanone, which eliminated the usage of hydroxylamine and demonstrated a green production of caprolactam. With the Fe electrocatalysts, a production rate of 55.9 g h−1 gcat−1 can be achieved in a flow cell with almost 100 % yield of cyclohexanone oxime. The high efficiency was attributed to their ability of accumulating adsorbed hydroxylamine and cyclohexanone. This study provides a theoretical basis for electrocatalyst design for C−N coupling reactions and illuminates the tantalizing possibility to upgrade the caprolactam industry towards safety and sustainability. [ABSTRACT FROM AUTHOR]

Furfurylated wood has many advantages, such as decay resistance, dimensional stability, hardness, etc. However, furfurylation increases the brittleness and decreases the flexural resistance of wood, which greatly limits its application. Therefore, caprolactam (CPL) is incorporated with furfuryl alcohol (FA) to improve the performance of furfurylated wood. In this study, an FA and CPL combinational modifier was used to treat masson pine (Pinus massoniana Lamb.) earlywood and latewood. The synergistic interaction of both components with the wood cell walls was systematically evaluated via microstructural, chemical, and thermal analysis using scanning electron microscopy (SEM), infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectrometry (XPS), and differential scanning calorimetry (DSC). The SEM images showed that polymerized modifiers were distributed in tracheids, ray cells, and pits, with a higher degree of distribution in latewood tissues. The FA-CPL co-treatment led to the highest degree of distribution in cell cavities as well as of cell wall swelling. The results of the weight percentage gain (WPG) of modified wood agreed with the SEM findings that the FA-CPL co-treatment could more effectively increase the WPG than individual modification. The results of FTIR and XPS revealed that FA and CPL might chemically bind with each other as well as react with lignin and hemicellulose in the cell walls during the curing process. In addition, the interactions between modifiers and cell walls were slightly different for earlywood and latewood. DSC analysis indicated that the wood hygroscopicity decreased and the thermal stability improved after modification. [ABSTRACT FROM AUTHOR]

Caprolactam is an important polymer precursor to nylon traditionally derived from petroleum and produced on a scale of 5 million tons per year. Current biological pathways for the production of caprolactam are inefficient with titers not exceeding 2 mg/L, necessitating novel pathways for its production. As development of novel metabolic routes often require thousands of designs and result in low product titers, a highly sensitive biosensor for the final product has the potential to rapidly speed up development times. Here we report a highly sensitive biosensor for valerolactam and caprolactam from Pseudomonas putida KT2440 which is >1000× more sensitive to an exogenous ligand than previously reported sensors. Manipulating the expression of the sensor oplR (PP_3516) substantially altered the sensing parameters, with various vectors showing Kd values ranging from 700 nM (79.1 μg/L) to 1.2 mM (135.6 mg/L). Our most sensitive construct was able to detect in vivo production of caprolactam above background at ∼6 μg/L. The high sensitivity and range of OplR is a powerful tool toward the development of novel routes to the biological synthesis of caprolactam.

Copyright of Corrosion & Protection in Petrochemical Industry is the property of Corrosion & Protection in Petrochemical Industry Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

In this work, glass fiber reinforced polyamide 6 (GF/PA6) composites were fabricated by vacuum bagging (VB) process. An experimental platform for VB process of continuous fiber reinforced polyamide 6 composites was constructed in combination with the in-situ polymerization characteristics of caprolactam. The differences in properties such as crystallinity, reaction conversion rate and mechanical properties of the composites produced by the two infusion strategies were investigated. The results showed that the composites fabricated by isothermal infusion had high crystallinity and good internal homogeneity. Compared with isothermal infusion, the mechanical properties of composites fabricated by non-isothermal infusion were higher. At a curing temperature of 150 °C, the mechanical properties of the composite were enhanced at the outlet than the inlet. Flexural strength and ILSS had been improved by 13.2% and 16.3%, respectively. The flexural strength and flexural modulus were 273.7 MPa and 14.2 GPa, respectively. ILSS of the composites reached a maximum value of 47.3 MPa at 170 °C. [ABSTRACT FROM AUTHOR]

The effects of compound plasticizer urea/caprolactam (UC) on the diffusion behavior of water in mixtures with poly(vinyl alcohol) (PVA) were studied using a Molecular Dynamics (MD) simulation method. Five simulation models of PVA composites with different plasticizer contents were constructed to investigate the variation of the intermolecular interaction as well as the diffusion behavior of water molecules. Results showed that the predominant interaction between the functional groups of UC and PVA consisted of hydrogen bonds. As the plasticizer content increased, diffusion coefficients of water in PVA systems increased due to the comparably weak diffusion resistance. It was also found that the rotation of the PVA chains and the small molecules became faster with increasing UC content, and the relaxation time became shorter. [ABSTRACT FROM AUTHOR]

Stimuli-responsive hydrogels are one type of smart hydrogel, which can expand/contract in water according to changes in the surrounding environment. However, it is difficult to develop flexible shapeshifting behaviours by using a single hydrogel material. This study exploited a new method to utilise single and bilayer structures to allow hydrogel-based materials to exhibit controllable shape-shifting behaviours. Although other studies have demonstrated similar transformation behaviours, this is the first report of such smart materials developed using photopolymerised N-vinyl caprolactam (NVCL)-based polymers. Our contribution provides a straightforward method in the fabrication of deformable structures. In the presence of water, the bending behaviours (vertex-to-vertex and edge-to-edge) were achieved in monolayer squares. By controlling the content and combination of the NVCL solutions with elastic resin, the bilayer strips were prepared. The expected reversible self-bending and self-helixing behaviours were achieved in specific types of samples. In addition, by limiting the expansion time of the bilayer, the layered flower samples exhibited predictable self-curving shape transformation behaviour in at least three cycles of testing. These structures displayed the capacity of self-transformation, and the value and functionality of the produced components are reflected in this paper. [ABSTRACT FROM AUTHOR]

Polylactic acid is a polyester polymer, which is recyclable and renewable as well. Membrane made of polylactic acid is acquiring attention nowadays due to its superior properties and versatility in application. This review primarily explains various synthesis routes of polylactic acid membrane and its applications. Sometimes, in membrane synthesis, polylactic acid is used with some other copolymers such as caprolactam, ethylene glycol to obtain the required functionality or property for its specific application. Some copolymers that find it helpful with polylactic acid for membrane synthesis are also discussed here with its specificity and enhanced properties. In this review, precise and detailed PLA membrane structure and its degradation mechanism is discussed. [ABSTRACT FROM AUTHOR]

Smart PVCL‐based nanogels for photosensitizers were prepared following the thermo precipitation methodology. PVCL‐based imprinted and non‐imprinted NGs are reported with different percentages of N,N′‐methylenebisacrylamide (BIS) as crosslinker agent. Zn(II)phthalocyanine (ZnPc) is employed as a model photosensitizer and incorporated as a template molecule for imprinted NGs or it loads post‐synthesis for non‐imprinted NGs. In order to analyze the chemical structure, NGs were characterized using infrared microscopy. Hydrodynamic diameter was determined by dynamic light scattering. The phase transition temperature was measured by UV–vis spectroscopy. The phase transition temperature and Dh values were regulated by the percentage of crosslinker and the presence of the photosensitizer as a template or post‐synthesis load. In all cases, the yields were acceptable and the smart nanodevices were stable. [ABSTRACT FROM AUTHOR]

The supply, demand and price trend of caprolactam industry in China in recent 5 years are studied. In 2021, the domestic caprolactam production capacity is 5 580 kt, the output is about 4 060 kt, the imports is about 106 kt, the exports is about 3.6 kt, and the apparent consumption is about 4 160 kt. The price trend of caprolactam is mainly affected by cost and supply and demand structure. It is estimated that the domestic caprolactam production capacity is expected to reach 8 790 kt, and the market competition will further intensify by 2026. It is suggested that the industry should effectively strengthen caprolactam technology investment and technological innovation, coordinate the development plans and policies of caprolactam and PA6 chips industry, enhance the value of sulfur in ammonium sulfate and strengthen the promotion of PA6 products. [ABSTRACT FROM AUTHOR]

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Here, we report the draft genome sequence of Paenarthrobacter sp. CAP02, which metabolizes caprolactam as a sole source of carbon and nitrogen. This bacterium was isolated from Dane County Landfill Site No. 2 in Madison, WI, USA., Competing Interests: The authors declare no conflict of interest.

Caprolactam is a crucial chemical intermediate, but its wastewater treatment process generates a significant amount of caprolactam-containing sludge. This study represented the first exploration of the effects of alkaline hydrothermal technology on the cracking and transformation of substances in this sludge. The cracking effect of caprolactam-containing sludge during hydrothermal treatment increased with rising reaction temperature and longer reaction time. With NaOH dosage in hydrothermal treatment increasing from 0 to 2 wt%, the volatile suspended solids (VSS) removal rate of the sludge increased from 44.5% to 74.8%, soluble chemical oxygen demand (SCOD) in the cracking liquid increased from 12772 mg/L to 22976 mg/L, and ammonia nitrogen concentration increased from 398.0 mg/L to 851.2 mg/L. However, the addition of Ca(OH) 2 did not significantly affect the changes of sludge suspended solids, VSS and SCOD concentration, but increased the leaching of ammonia nitrogen (up to 745.0 mg/L). This was due to the secondary flocculation of Ca 2+ , which rebound with dissolved non-proteinaceous organic matter. Increasing temperature, reaction time, and alkaline dosage all enhanced the fluorescence intensity of dissolved organic matter (DOM). Moreover, higher reaction temperature and alkaline dosage reduced the proportion of proteinaceous products in DOM while increasing the proportions of fulvic acids, soluble microbial metabolites, and humic acid-like substances. The study provided crucial theoretical support for engineering application of this technology., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Furfurylated wood has many advantages, such as decay resistance, dimensional stability, hardness, etc. However, furfurylation increases the brittleness and decreases the flexural resistance of wood, which greatly limits its application. Therefore, caprolactam (CPL) is incorporated with furfuryl alcohol (FA) to improve the performance of furfurylated wood. In this study, an FA and CPL combinational modifier was used to treat masson pine (Pinus massoniana Lamb.) earlywood and latewood. The synergistic interaction of both components with the wood cell walls was systematically evaluated via microstructural, chemical, and thermal analysis using scanning electron microscopy (SEM), infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectrometry (XPS), and differential scanning calorimetry (DSC). The SEM images showed that polymerized modifiers were distributed in tracheids, ray cells, and pits, with a higher degree of distribution in latewood tissues. The FA-CPL co-treatment led to the highest degree of distribution in cell cavities as well as of cell wall swelling. The results of the weight percentage gain (WPG) of modified wood agreed with the SEM findings that the FA-CPL co-treatment could more effectively increase the WPG than individual modification. The results of FTIR and XPS revealed that FA and CPL might chemically bind with each other as well as react with lignin and hemicellulose in the cell walls during the curing process. In addition, the interactions between modifiers and cell walls were slightly different for earlywood and latewood. DSC analysis indicated that the wood hygroscopicity decreased and the thermal stability improved after modification.

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

We have developed a method for synthesizing novel helical amide derivatives. Nucleophilic primary amines were inserted into benzo-fused 2,2′-biphenoquinones to form helical amides containing seven-membered rings. When optically pure primary amines were used in this reaction, a mixture of two amide diastereoisomers was obtained and separated into diastereomerically pure products by high-performance liquid chromatography. In contrast, the reaction of enantiomerically pure benzo-fused 2,2′-biphenoquinones with achiral aliphatic primary amines afforded enantiomerically pure helical amides with stereospecificity and retention of configuration. [ABSTRACT FROM AUTHOR]

Poly(N-vinylamide) derivatives were synthesized to improve the performance of kinetic hydrate inhibitors (KHIs). In this work, we synthesized poly(N-vinylformamide) (PNVF) and poly(N-vinylcaprolactam) (PVCap) by free radical polymerization with several commercial chain transfer agents (CTAs), which afforded a few thousand Mn. The structures of synthesized PNVF and PVCap were then investigated by 1H NMR and MALDI-TOF/MS spectrograms. KHI properties of the synthesized PNVF and PVCap polymers were also evaluated by the high-pressure slow constant cooling KHI test method. Some of the tested polymers showed a better KHI effect than PVCap. [ABSTRACT FROM AUTHOR]

Amyloidosis refers to a group of diseases caused by the deposition of abnormal proteins in tissues. Herein, curcumin was loaded in a nanohydrogel made of poly (vinylcaprolactam) to improve its solubility and was employed to exert an inhibitory effect on insulin fibrillation, as a protein model. Poly (vinyl caprolactam), cross-linked with polyethylene glycol diacrylate, was synthesized by the reversible addition-fragmentation chain transfer method. The release profile of curcumin exhibited a first-order kinetic model, signifying that the release of curcumin was mainly dominated by diffusion processes. The study of curcumin release showed that 78% of the compound was released within 72 h. The results also revealed a significant decline in insulin fibrillation in the presence of curcumin-loaded poly (vinyl caprolactam). These observations confirmed that increasing the ratio of curcumin-loaded poly (vinyl caprolactam) to insulin concentration would increase the hydrogel's inhibitory effect (P-value < 0.05). Furthermore, transmission electron and fluorescence microscopies and Fourier-transform infrared spectroscopy made it possible to study the size and interaction of fibrils. Based on the results, this nanohydrogel combination could protect the structure of insulin and had a deterrent effect on fibril formation. [Display omitted] • A nanohydrogel system based on PVCL was prepared and loaded with curcumin (Cur@PVCL). • Cur@PVCL showed to have a first-order kinetic release profile of curcumin within 72 h. • The mixture of Cur@PVCL with insulin showed to inhibit insulin fibrillation. • Assessment showed that Cur@PVCl could inhibit the conformational changes of insulin. [ABSTRACT FROM AUTHOR]

Biochar-based Fe–Ce bimetallic Fenton-like heterogeneous catalyst was prepared and applied to the degradation of wastewater produced during the synthesis of caprolactam (wastewater-CPL) in the presence of micro-nano bubbles (MNB). The prepared materials were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS), which confirmed the successful loading of Fe and Ce and the formation of Fe2O3 and CeO2. The treatment effects of different reaction systems were compared, indicating that biochar-based catalyst + H2O2 + MNB system had the best treatment effect that the COD removal rate can reach 93.26%. The influencing factors of the system were discussed, and finally it was concluded that the condition of Fe:Ce was 3:1, hydrogen peroxide concentration was 1.2 M, pH was 2, catalyst dosage was 1 g/L, and temperature was 35 ℃. The treatment effects of adding MNB were compared; the treatment effect of MNB + H2O2 on wastewater was about 60% higher than that of H2O2 alone. The reusability of the catalyst was determined, and it was observed that high catalytic performance could be retained after five cycles. Finally, the water quality of the effluent was analyzed, and it was proved that the treatment of wastewater-CPL had a good effect. This study provided a new idea for the treatment of wastewater-CPL. [ABSTRACT FROM AUTHOR]

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of China Synthetic Fiber Industry is the property of Sinopec Baling Petrochemical Company and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The development of a system for the operationally simple, scalable conversion of polyhydroxylated biomass into industrially relevant feedstock chemicals is described. This system includes a bimetallic Pd/Re catalyst in combination with hydrogen gas as a terminal reductant and enables the high-yielding reduction of sugar acids. This procedure has been applied to the synthesis of adipate esters, precursors for the production of Nylon-6,6, in excellent yield from biomass-derived sources.

Photocrosslinkable materials have been frequently used for constructing soft and biomimetic hydrogels for tissue engineering. Although ultraviolet (UV) light is commonly used for photocrosslinking such materials, its use has been associated with several biosafety concerns such as DNA damage, accelerated aging of tissues, and cancer. Here we report an injectable visible light crosslinked gelatin-based hydrogel for myocardium regeneration. Mechanical characterization revealed that the compressive moduli of the engineered hydrogels could be tuned in the range of 5-56 kPa by changing the concentrations of the initiator, co-initiator and co-monomer in the precursor formulation. In addition, the average pore sizes (26-103 μm) and swelling ratios (7-13%) were also shown to be tunable by varying the hydrogel formulation. In vitro studies showed that visible light crosslinked GelMA hydrogels supported the growth and function of primary cardiomyocytes (CMs). In addition, the engineered materials were shown to be biocompatible in vivo, and could be successfully delivered to the heart after myocardial infarction in an animal model to promote tissue healing. The developed visible light crosslinked hydrogel could be used for the repair of various soft tissues such as the myocardium and for the treatment of cardiovascular diseases with enhanced therapeutic functionality.