Polymerization of lactams, 87. Block copolymers of poly(ϵ-caprolactam) and polybutadiene prepared by anionic polymerization. Part I: Preparation and properties

The effect of the polymerization conditions on the properties of poly(?-caprolactam)-polybutadiene block copolymers prepared by polymerization casting through anionic polymerization of ?-caprolactam initiated with potassium salt of ?-caprolactam in the presence of α,ω-dihydroxy-polybutadiene and isocyanates or their blocked derivatives as functionalizing agents was investigated. The influence of the content of telechelic polybutadiene, its molecular weight, type of diisocyanate, and polymerization temperature on the fundamental mechanical properties of the prepared materials and on the polymerization rate was evaluated.     

阻燃材料测试与表征方法简述

本文简单介绍了几种常用的阻燃材料测试和表征方法。随着阻燃科学的发展，出现了新一代的阻燃测试仪器一锥形量热仪，它能够较好地评价阻燃材料的真实燃烧行为。同时，多种测试方法的结合使用可以更为准确地评价材料的阻燃性能及分析其阻燃机理。     

Depolymerization of nylon 6: Some kinetic modeling aspects

Depolymerization reactions of nylon 6 [poly(?-caprolactam)] have been modeled based on an existing mechanism for reversible polymerization reactions. The method of moments proposed by Min has been used together with kinetic and equilibrium constants for polymerization reactions to simulate depolymerization reactions. Simulation results thus obtained for batch and semibatch processes compare well with the corresponding experimental results.     

Highly flame‐retardant polyurethane foam based on reactive phosphorus polyol and limonene‐based polyol

Polyurethane foams are in general flammable and their flammability can be controlled by adding flame‐retardant (FR) materials. Reactive FR have the advantage of making strong bond within the polyurethane chains to provide excellent FR over time without compromising physico‐mechanical properties. Here, phenyl phosphonic acid and propylene oxide‐based reactive FR polyol was synthesized and used along with limonene based polyol for preparation of FR polyurethanes. All the obtained foams showed higher closed cell content (above 96%). By the addition of FR–polyol, the compressive strength of the foams showed 160% increment which could be due to reactive nature of FR–polyol. Moreover, 1.5 wt % of phosphorus (P) content reduced the self‐extinguishing time of the foam from 81 (28% weight loss) to 11.2 s (weight loss of 9.8%). Cone test showed 68.6% reduction in peak heat release rate along with 23.4% reduction in thermal heat release. The change in char structure of carbon after burning was analyzed using Raman spectra which, suggests increment in the graphitic phase of the carbon over increased concentration of phosphorus. It can be concluded from this study that phosphorous based polyol could be blended with bio‐based polyols to prepare highly FR and superior physico‐mechanical rigid polyurethane foams. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46224.     

Au@Ag core-shell nanoparticles: efficient all-plasmonic Fano-resonance generators

Fano resonances (FR) in strongly coupled systems like a metallic dimer arise due to the coupling between the spectrally localized surface plasmon resonance (SPR) of a noble metal nanoparticle and the continuum of interband transitions of the other. Since its discovery in Au-Ag dimers, several plasmonic structures have been proposed as candidates for obtaining Fano resonances. However, most of them either are difficult to synthesize or do not generate FR signal of adequate intensity. In this paper we demonstrate that simple Au@Ag core-shell nanoparticles with typical shell thickness below 5.0 nm, which can be synthesized through a common citrate reduction method, have a Fano resonance easily detectable in the far-field.     

Improving the pore structure and adsorption properties of industrial active carbons

The paper describes the possibility of improving the pore structure and adsorption properties of industrial active carbons (AC) by means of their modification with ɛ-caprolactam (CL). Application of ɛ-caprolactam (a product of large-scale organic synthesis) as a modifying substance allows the targeted regulation of the specific surface area and volume of AC mesopores, while the conditions of modification change the chemical composition of the surface of carbon adsorbents and, as a result, their adsorption properties. The process of modification includes three stages. The first is the adsorption of CL from aqueous solution and heating at 300°C in the presence of atmospheric oxygen. The second is carbonization in an argon flow at 900°C, and the third is the vapor-gas activation of the resultant adsorbents at 900°C. Each stage is followed by determining the parameters of the pore structure by N₂ adsorption and the adsorption parameters with respect to benzene, iodine, aqueous solutions of ɛ-caprolactam, and copper sulfate (CuSO₄). When modifying the carbonized samples with an initial ɛ-caprolactam content of 2%, we observe the growth of mesopores over 100% of volume, relative to AG-OV-1 original industrial activated carbon. Depending on the stage of modification, an increase in adsorption is observed, relative to the AG-OV-1 original carbon: benzene adsorption rises by 50%, the adsorption of iodine from aqueous solution rises by 20%, the adsorption of ɛ-caprolactam from aqueous solution grows by more than 30%, and the adsorption of copper(II) ions rises by more than 70%. The procedure for the production of the described modified adsorbent has no rivals abroad; it is protected by a patent and can be used in industry. It is possible to use inexpensive industrial carbons as the original material. The procedure allows the production of carbon adsorbents with predetermined structural and adsorption properties.     

Syntheses of intrinsically flame-retardant polyamide 6 fibers and fabrics

In this study, flame-retarded polyamide 6 (FR-PA6) was prepared via the direct co-condensation of ε-caprolactam with two different organophosphorus compounds in a typical melt-polymerization process. Polymer microstructures, especially the incorporation of the phosphorus-containing comonomers, as well as the thermal and physical properties of the resulting copolyamides have been studied in detail. The phosphorus-modified PAs have a P-content of 0.10–0.30 wt %, possess high relative viscosities of 2.2–2.4 and good thermal stability. FR-PA6 multifilaments were prepared by melt spinning and show tensile strengths up to 40 cN/tex and tenacities up to 0.5 GPa. Knitted fabrics of FR-PA6 exhibit high limiting oxygen index values around 35%. Due to the very low phosphorus content, there is no impairment of the material properties of PA6. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47829.     

Antimony polymers. III. Flame retardant behavior of chloroprene and natural rubber vulcanizates with antimony polymer

The antimony-containing polymer of bisphenol-A (BPA) and triphenyl antimony dinitrate was used as a flame retardant (FR) for chloroprene rubber (CR) and natural rubber (NR). The flame retardancy of this additive was monitored by the limiting oxygen index (LOI) measurements of the rubber vulcanizates and compared with that for antimony trioxide used as a FR additive. The thermogravimetric analysis (TGA) of the vulcanizates has also been studied. A structure flammability relationship has been established. The effect of this FR additive on physical properties of the vulcanizates undergoing heat aging and solvent leaching has also been evaluated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 927–935, 1998     

Thermal polymerization of a brominated flame retardant in a glass‐fiber‐reinforced polypropylene—quantitative analysis

Pentabromobenzylacrylate (PBBA) is a possible candidate for use as a fire retardant (FR) in polypropylene (PP) composites. While PBBA imparts FR properties to the PP composite, it also affects adversely its mechanical properties. The FR may undergo thermal polymerization or grafting to the PP chains during processing. To study the effect of the different forms of FR (monomer, polymerized, or grafted) on composite properties, we have quantified the extent of FR polymerization and extent of grafting onto the PP chains. Fourier transform infrared microscopy was used in this work to determine the extent of polymerization and the spatial distribution of the FR. The latter was found to be homogeneous throughout the composite. Thermal polymerization of the FR during extrusion is varied mainly by the addition of an antioxidant. The grafting process of the FR onto PP depends on the degree of thermal polymerization, and therefore on the addition of antioxidant. The limiting value for grafting achieved at full polymerization is ～10% w/w. The grafted FR was found to have a significant effect on PP crystallinity, and hence it is expected to affect the mechanical properties as well. Bromine analysis indicates the FR has reacted with filler surfaces as well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1506–1515, 2003     

<Emphasis Type="Italic">In vivo</Emphasis> measurement of the redox state

As part of an aerobic life, we oxidize a large pool of biomolecules to obtain chemical energy. During this process, several intermediates are formed; some are chemically unstable and are referred to as free radicals (FR). FR tend to react quickly with their surrounding biological environment; depending on the nature of the molecule attacked, different reactions can occur, i.e., lipid peroxidation, protein oxidation, or DNA oxidation products. As aerobic life has evolved, antioxidant defense systems against FR have developed. When an imbalance between production of FR (oxidants) and defese systems against them (antioxidants) happens, a situation of oxidative stress occurs. This can lead to irreversible biochemical changes, with subsequent tissue damage and disease. Establishing the involvement of FR in the pathogenesis of a disease has been difficult because of the lack of sensitie and specific methodology to detect them. No ideal biomarkers for in vivo FR-induced damage are available as yet. However, some reliable indices of FR formation are now available, and in some pathologic conditions, evidence is accumulating to show that FR damage might play a functional role. The task for the near future will be to try to simplify the analytical methodology and elucidate the molecular mechanisms underlying the formation, disposition, and kinetics of FR marker molecules.     

Block polymers from isocyanate-terminated intermediates. IV. Properties of cured butadiene–ε-caprolactam block polymers

Butadiene–ε-caprolactam block polymers containing a high proporation of 1,2 units in the butadiene-segments were synthesized and physical properties were measured on the cured copolymers. Flexural strength and impact resistance both increase regularly with increasing ε-caprolactam content in peroxide cured copolymers. This behavior is explained by the higher values of flexural modulus and impact resistance for poly(ε-caprolactam) compared with peroxide-cured polybutadiene resins. Copolymers reinforced with silica showed higher heat distortion temperatures but lower impact resistance than corresponding unfilled samples. Arrhenius plots of flexural properties at various test temperatures were linear. Both flexural modulus and strength decreased regularly with increasing test temperature. Flexural properties of filled copolymers were relatively unaffected by heat aging up to 204°C for several weeks, however, dramatic decreases in these properties were noted in a matter of days when heat aging was done at 260–316°C. These results are explained by the rapid degradation of poly(ε-caprolactam) above its melting point. Block polymers whose butadiene segments contained a high proportion of 1,4 units were also synthesized. These copolymers were elastomeric when cured with either sulfur or peroxide.     

Modification of polyamide 6 with hycar ATBN

The preparation of block copolymers from 6-caprolactam and a liquid amine terminated butadiene-acrylonitrile copolymer Hycar ATBN 1300X21 having higher notched impact strength than ordinary poly(6-caprolactam) was studied. In the polymerization of 6-caprolactam initiated by an adduct of phosphoric acid with 6-caprolactam the influence of initiator concentration (0– 50 mol-%) and Hycar ATBN 1300X21 concentration (0–5 wt.-%) in the polymerization charge, of polymerization time (4 – 72 h) and of temperature (200–280°C) on the 6-caprolactam conversion and on the properties of the copolymers formed were followed. Notched impact strength of the block copolymers prepared under optimized conditions was as high as 13.5 kJ·m^?2.     

Kinetic investigation and regularities during the synthesis of Poly(ε-caprolactam-co-ε-caprolactone) and Poly(ε-caprolactam-co-δ-valerolactone) biodegradable copolymers

Summary Large diversity of tailor-made poly[(ε-caprolactam)-co-(ε-caprolactone)] P[(CLA)-co-(CLO)] and poly[(ε-caprolactam)-co-(δ-valerolactone)] P[(CLA)-co-(VLO)] copolymers have been obtained via activated anionic polymerization of ε-caprolactam (CLA) with sodium caprolactam (NaCL) as a basic initiator. In the present study several poly(ε-caprolactones) (PCLOs) and poly(δ-valerolactone) polyols were employed as effective bifunctional polymeric activators (PACs) and suitable comonomers of CLA. The obtained poly(esteramides) PEAS were isolated and their structure was confirmed by the ¹H NMR and FTIR spectroscopy. The influence of the molecular weight and type of the PACs, the CLA/PAC ratio and polymerization conditions on the conversion, intrinsic viscosity and polymerization kinetic was explored. The results demonstrated that the use of the PACs reduces the polymerization time to several minutes and polymerization process proceeds without induction period at low energy of activation and high yield of copolymers. Evaluation of the PACs activity and the activation energy confirmed that the PACs are highly active compounds efficient to CLA features modification.     

磷化酚醛树脂的合成及其阻燃性能研究

以苯酚,三氯氧磷(POCl3),热塑性酚醛树脂(FR)为原料,三乙胺(Et3N)为缚酸剂合成了一种新型的含磷阻燃剂-磷化酚醛树脂(FR-P),采用红外光谱(FT IR),核磁共振磷谱(31PNMR),电感耦合等离子体发射光谱(ICP)及热重分析(TG)对聚合物的结构及热性能进行了表征,探讨了合成中的各因素对反应的影响,得出了最佳的合成工艺条件,并将合成的化合物用于PC的阻燃,采用热分析法、极限氧指数法(LOI)对阻燃体系的热性能和阻燃性能进行了表征,并与PC/FR阻燃体系进行了比较。研究结果表明,FR-P在高温下的热稳定性和成炭性与FR相比有较大的提高,它能促进PC热降解时成炭,使PC的热分解速率降低,当FR-P添加量为15%时,阻燃体系的LOI达31%,且通过UL94V-1级测试,其阻燃效果远远好于FR。     

Powdered poly(ethylene terephthalate)

The influence of the conditions of preparation on the properties of powdered poly(ethylene terephthalate) was followed from the point of view of its specific surface. The powdered poly(ethylene terephthalate) prepared by reprecipitation from the melt of 6-caprolactam has a porous and structured surface, and consequently, also a large specific surface in comparison with the powedered poly(ethylene terephthalate) prepared by mechanical milling. The specific surface value is influenced by the cooling rate of the initial homogeneous melt of poly(ethylene terephthalate)-6-caprolactam, by the concentration of poly(ethylene terephthalate) in this melt and by its molecular weight, by the water temperature at the extraction of 6-caprolactam from the tough mixed melt, by the drying temperature of the powdered poly(ethylene terephthalate), and by the content of residual 6-caprolactam in the powdered product. In the examined area, the specific surface value of the powdered poly(ethylene terephthalate) prepared by reprecipitation from the melt of 6-caprolactam ranged from 10 to 110 m²·g^?1.     

A Dual‐Targeting Octaguanidine–Doxorubicin Conjugate Transporter for Inducing Caspase‐Mediated Apoptosis on Folate‐Expressing Cancer Cells

An efficient synthetic framework was assembled (G8‐FKE‐FA‐Dox), consisting of a lysosome‐targeting octaguanidine molecular transporter with a cathepsin B (cath B)‐specific peptide substrate, folic acid, and the potent chemotherapeutic drug doxorubicin (Dox). Because the folate receptor (FR) and cath B are overexpressed in malignant cells, this transporter conjugate successfully executed lysosome‐mediated transport of Dox to FR‐positive tumor cells, illustrating this framework as an excellent targeted drug delivery system (TDDS). G8‐FKE‐FA‐Dox was shown to exhibit selective toxicity toward FR‐overexpressing cancer cells, with an IC₅₀ value superior to that of the USFDA‐approved Lipodox^TM and proportional to that of free Dox via selective induction of apoptosis by the activation of caspases 8, 9, and 3. This TDDS was observed to be nontoxic to red blood cells and lymphocytes at neutral pH. Furthermore the tumor‐targeting dissemination pattern of this system was revealed by monitoring the in vivo biodistribution of the carrier (G8‐FKE‐FA‐FL) in normal and FR‐overexpressing tumor‐bearing mice.     

High-Throughput Screening of Fouling-Release Properties: An Overview

Marine biofouling of ship hulls has significant cost, performance and environmental implications. Due to environmental concerns associated with traditional antifouling paints that mitigate fouling with the use of biocides, increasing research and development efforts have been made on fouling-release (FR) coatings. FR coatings do not actively deter settlement of marine organisms, but, instead, mitigate biofouling by minimizing the strength of adhesion. Ideally, an FR coating will allow the fouling community to be removed by simply running the vessel at relatively high speed. Traditional methods for characterizing FR properties involve immersion of relatively large samples in the ocean and waiting months for enough fouling to occur to enable reliable measurements to be made. To greatly enhance research and development relative to FR coatings, a combinatorial/high-throughput workflow was developed that includes a suite of FR laboratory assays involving marine bacteria, microalgae, and live, adult barnacles. The novel high-throughput FR measurement systems have been shown to allow for rapid screening of FR characteristics of miniaturized coating samples arranged in an array format.     

Modification of alkali silicate solutions by organic reagents and investigation of the properties of the final products

Alkali silicate solutions are modified by organic reagents, i.e., monomers (acrylic acid, N,N′-meta(ortho)-phenylene-bismaleimide, and ε-caprolactam), and the ED-20 epoxy resin oligomer. Dispersed organosilicate products are obtained, and their structure and physicochemical properties are investigated. It is demonstrated that the developed materials can be used as fillers for composites     

Improving the flame-retardant property of bottle-grade PET foam made by reactive foam extrusion

Upcycling of low intrinsic viscosity (IV) poly(ethylene terephthalate) (PET) grades, such as bottle- or recycled grades, by a reactive foam extrusion process, provides an appropriate alternative to high pricing, high IV grades commonly used for foaming applications. However, the drawback of bottle-grade PET foams is its flame retardant (FR) performance. In this study, pyromellitic dianhydride was used as a chain extender to foam bottle-grade PET. The influence of different FRs, containing halogenated (HFR) and four different phosphorous-based types, on the processability and final foam properties was investigated. HFR showed better processability to achieve proper foams with fine morphology compared to P-based FRs, where the FR content was adjusted between 2 and 5 wt%. However, HFR exhibited lower FR performance by cone calorimeter testing compared to the P-based FRs and the commercial reference foam Kerdyn. Nonetheless, all of the FRs can only improve the time to ignition of the neat PET foams while the other values depend on the specific type of FR. In addition, all FR foams have improved mechanical properties more than twice in comparison to the neat PET foam.     

ε-Caprolactam polymerization in presence of polyhedral oligomeric silsesquioxanes (POSS)

Polyhedral oligomeric silsesquioxanes (POSS) have been covalently linked to polyamide 6 (PA6) chains with the aim of synthesizing hybrid organic/inorganic polymer materials. The synthesis has been achieved by in situ polymerization of ε-caprolactam (CL) in presence of increasing amounts of POSS molecules, using two polymerization mechanisms (hydrolytic and anionic). The latter method has been carried out by three different approaches, in order to get PA6 samples characterized by various morphologies and content of structural defects: (i) quasi-adiabatic bulk polymerization; (ii) isothermal bulk polymerization; (iii) quasi-isothermal suspension polymerization. The products obtained have been characterized in term of structure, morphology, thermal properties and molecular mass.