The non-halogen flame retardant epoxy resin based on a novel compound with phosphaphenanthrene and cyclotriphosphazene double functional groups

A novel flame retardant additive hexa-(phosphaphenanthrene -hydroxyl-methyl-phenoxyl)-cyclotriphosphazene (HAP-DOPO) with phosphazene and phosphaphenanthrene double functional groups has been synthesized from hexa-chloro-cyclotriphosphazene, 4-hydroxy-benzaldehyde and 9,10-dihydro-9-oxa-10- phosphaphenanthrene 10-oxide(DOPO). The structure of HAP-DOPO was characterized by Fourier transformed infrared (FT-IR) spectroscopy and ¹H nuclear magnetic resonance (¹H NMR) and ³¹P nuclear magnetic resonance (³¹P NMR). The additive HAP-DOPO was blended into diglycidyl ether of bisphenol-A (DGEBA) to prepare flame retardant epoxy resins. The flame retardant properties and thermal properties of the epoxy resins cured by 4, 4′-Diamino-diphenyl sulfone (DDS) were investigated from the differential scanning calorimeter (DSC), the thermogravimetric analysis (TGA), UL94 test, the limiting oxygen index (LOI) test and Cone calorimeter. Compared to traditional DOPO-DGEBA and ODOPB-DGEBA thermosets, the HAP-DOPO/DGEBA thermosets have higher T_gs at the same UL94 V-0 flammability rating for their higher crosslinking density and have higher char yield and lower pk-HRR at same 1.2 wt.% phosphorus content which confirm that HAP-DOPO has higher flame retardant efficiency on thermosets. The scanning electron microscopy (SEM) results shows that HAP-DOPO in DGEBA/DDS system obviously accelerate formation of the sealing, stronger and phosphorus-rich char layer to improve flame retardant properties of matrix during combustion.     

THERMAL DEGRADATION AND FLAME RETARDANCY OF CALCIUM ALGINATE FIBERS

Calcium alginate fibers were prepared by wet spinning of sodium alginate into a coagulating bath containing calcium chloride.The thermal degradation and flame retardancy of calcium alginate fibers were investigated with thermal gravimetry(TG),X-ray diffraction(XRD),limiting oxygen index(LOI) and cone calorimeter(CONE).The results show that calcium alginate fibers are inherently flame retardant with a LOI value of 34,and the heat release rate(HRR),total heat release(THR),CO and CO_2 concentrations during ...     

Preparation, characterization and curing properties of epoxy-terminated poly(alkyl-phenylene oxide)s

A series of dihydroxyl telechelic poly(alkyl-phenylene oxide)s (1) have been synthesized by oxidative polymerization of alkylphenols with various aromatic diols using manganese or copper amine catalysts. The novel telechelic derivatives (1) were epoxidized with epichlorohydrin yielding a series of new epoxidized poly(alkyl-phenylene oxide)s (EPPO, 2) and the structures, properties were studied by nuclear magnetic resonance spectroscopy (NMR), differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA) and gel permeation chromatography (GPC). The 1:1 blends of diglycidyl ether of bisphenol-A (DGEBA) with EPPO resins were cured with three curing agents and the effects of chemical structure change on thermal property of the curing matrixes were discussed. Incorporation of EPPOs to DGEBA epoxy system resulted in a significant increase in its glass transition temperature (T_g), thermal stability and flame resistance. The T_g values and char yields arising from a DDM-cured epoxy resin are usually higher than those of dicyandiamide (DICY) or 2-methylimidazole (2-MI) analogues and the reactivity of epoxy blends with three curing agents presents an increase in the order of 2-MI, DDM and DICY. In general, the tetramethylbisphenol-A (TMBPA)-derived polymer exhibits the lowest T_g, char yield and dielectric constant among PPO derivatives whereas the biphenol polymers usually results in higher T_g and char yield due to its rigid rod structure.     

Novel high phosphorus content phosphaphenanthrene-based efficient flame retardant additives for lithium-ion battery

The novel phosphate derivatives of phosphaphenanthrene with high-density phosphorus were synthesized and used as flame retardant additives for Li-ion batteries. The structures of compounds were characterized by ¹H NMR, ¹³C NMR, ³¹P NMR, FT-IR, and HR-MS. The excellent thermal stability of compounds was ascertained by thermogravimetric analysis and differential scanning calorimetry. The compounds were added to conventional electrolytes as flame retardant additives and evaluated their ionic conductivity, electrochemical stability, self-extinguishing properties, and combustion performance. The results showed that the compound containing higher phosphorus content has efficient flame retardant properties.     

Preparation of cellulosic fibers with biological activity by immobilization of trypsin on periodate oxidized viscose fibers

In this study, a biologically active fibrous material was designed by immobilizing trypsin on viscose fibers. The viscose yarn was first oxidized with sodium periodate to produce aldehyde groups and then employed as a support for subsequent immobilization of trypsin through bovine serum albumin. The oxidation by sodium periodate caused changes in the chemical and physical properties of the modified yarn samples, which were evaluated by determining the aldehyde group content, fineness and tensile strength of yarn. The viscose fibers oxidized under the most severe conditions (0.4 % NaIO₄, 360 min) exhibited the maximum amount of introduced aldehyde groups (1.284 mmol/g), but also the highest decrease in tensile strength. The trypsin activity was assayed with N-α-benzoyl-DL-arginine p-nitroanilide hydrochloride, whereas the amount of bound trypsin was determined by Bradford method. Trypsin immobilized on oxidized viscose yarn retained 97.3 and 83.8 % of the initial activity over 60 days of storage at 4 and 25 °C, respectively, and remained firmly attached to the carrier. The potential application of obtained bioactive fibers is in the treatment of wounds.     

Enantiopure isoplagiochin C by directed deracemization through axis-to-axis chirality transfer

Isoplagiochin C 1 was prepared for the first time in enantiopure form from synthetic racemic material, using a novel stereochemical concept. This macrocyclic bisbibenzyl contains two biaryl axes. Of these, axis A is configurationally stable by its fixation within the macrocyclic framework, while axis B is stereochemically unstable. By diesterification of rac-1 with enantiopure (P)-1,1′-binaphthyl-2,2′-dicarboxylic acid, axis B is locked in its P-configuration, thus allowing the resolution and separate saponification of dilactones (P_A,P_B,P)-3 and (M_A,P_B,P)-3 to give the pure enantiomers of 1. This concept permits recycling of any undesired enantiomer of 1 by thermal equilibration of the respective diastereomer of 3.     

Compressibility and thermal expansion coefficients of nanocomposites with amorphous and crystalline polymer matrix

Clay-containing polymeric nanocomposites (CPNC) with polystyrene (PS) or polyamide-6 (PA-6) matrix were studied within T = 300-600 K and P = 0.1-190 MPa. From the Pressure-Volume-Temperature (PVT) data the derivatives: compressibility, κ, and thermal expansion coefficient, α, were computed as functions of T, P and clay content, w. Dependence of these coefficients on P and T were significantly different for the amorphous PS than for the semi-crystalline PA-6. In the PS plots of κ and αvs.T the presence of secondary transitions, T_β/T_g ≈ 0.9 ± 0.1 and T_c/T_g = 1.2 ± 0.1, were detected and the clay effect at low T was prominent, affecting the physical aging. The isobaric values of α = α(T) were characterized by nearly T-independent values in the glassy and molten phase, connected by a large transitory region stretching from the ambient pressure values of T_g to T_c; this region was even more prominent in κ = κ(T). The derivative properties of PA-6 based CPNC were distinctly different. Here, the isobaric κ = κ(T) followed the same dependence on both sides of the melting zone, while the isobaric α = α(T) dependencies were dramatically different for the solid and molten phase; at T < T_mα linearly increased with T, after melting its value sharply decreased, and then at T > T_m (depending on w and P) either increased or decreased with T. Interpretation of the behavior in the melt and glass is based on the Simha-Somcynsky (S-S) cell-hole theory while that of the semicrystalline state on the Midha-Nanda-Simha-Jain (MNSJ) cell theory. In spite of the nonequilibrium conditions below the main transition point, T_g or T_m, the theories well predict the observed dependencies.     

Synthesis and properties of phosphorus polyesters with systematically altered phosphorus environment

Monomers with phosphorus-containing substituents were incorporated into aromatic-aliphatic polyesters to develop polymeric halogen-free flame retardants as additives for poly(butylene terephthalate) (PBT). They were built into the polyester backbone of PBT substituting 1,4-butane diol as monomer by phosphorus-containing aromatic-aliphatic diols. Starting from 10-(2,5-bis(2-hydroxyethoxy)phenyl)-9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO-HQ-GE), the chemical structure of the phosphorus monomers was systematically varied resulting in new polymers with diphenyl phosphine oxide substituents and bridged phosphine oxide units. The polymers were prepared by transesterification polycondensation in the melt in lab-scale as well as in a 2.4 l-autoclave. The properties of the polyesters were determined and compared to the DOPO-based polyester with respect to the achieved molar mass and polydispersity, solid state structure, glass transition temperature, thermal stability and combustion behavior.It was found that the different phosphorus substituents lead to different glass transition temperatures. The polymers containing bridged phosphorus structural units showed higher glass transition temperatures T_g and resulted in higher char yields after thermal decomposition. Both phosphine oxide structures showed only one-step decomposition with a shoulder at the end of the step. In contrast, two separate steps were observed in the polyesters with DOPO-substituents. The results indicated that the phosphorus polyesters under discussion are suitable to adjust the flame retarding mechanism.     

Molecular simulation of the glass transition of polyphosphazenes

Molecular dynamics simulation (NPT ensemble) has been used to obtain specific volume as a function of temperature for four polyphosphazenes. From these results, the volumetric glass transition temperature has been determined as the temperature marking the discontinuity in slope of the V–T simulation data. The molecular mechanics force field used in this study was COMPASS (Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies) which has been extensively parameterized and validated for phosphazenes in a previous communication. The polyphosphazenes include poly[bis(2,2,2-trifluoroethoxy)phosphazene] (PTFEP) and three isomers of poly(dibutoxyphosphazene)—poly[bis(n-butoxy)phosphazene] (PnBuP), poly[bis(iso-butoxy)phosphazene)] (PiBuP), and poly[bis(sec-butoxy)phosphazene] (PsBuP). In all cases, there was reasonable agreement between experimental results and values of density and T_g obtained from the simulations. In the case of PnBuP, two different methods for amorphous cell building are compared to explore the relationship between the state of equilibration and the T_g obtained from simulation.     

Synthesis and properties of Fe0.83V1.17O4

Thermal properties of the organic–inorganic bicontinuous nanocomposites prepared via in situ two-stage polymerization of various silanes, epoxy, and amine monomers are investigated, and the impact of filler content and its organic compatibility on thermal stability of these nanocomposites is studied. Two series of epoxy–silica nanocomposites, namely, EpSi-A and EpSi-B containing 0–20 wt% silica, are synthesized. An epoxy–silane coupling agent is employed to improve the organic compatibility of silica in EpSi–B nanocomposites. The composites synthesized via two-stage polymerization are characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric (TG) analysis. DSC and TG/differential thermogravimetric results reveal substantially high glass transition (T _g) and excellent thermal stability of the bicontinuous nanocomposites as compared with pristine epoxy polymer. Both T _g and thermal properties, however, considerably vary depending on the organic compatibility of the nanocomposites. Significantly higher decomposition temperatures are recorded in case of EpSi-B nanocomposites owing to the chemical links between the epoxy and silica phases. Kinetic studies also show relatively higher activation energies of pyrolysis for EpSi-B nanocomposites.     

Facile, one-pot synthesis of phosphinate-substituted bisphenol A and its alkaline-stable diglycidyl ether derivative

A new phosphinate-substituted bisphenol A, 1,1-bis(4-hydroxyphenyl)-1-(6-oxido-6H-dibenz <c,e> <1,2> oxaphosphorin-6-yl)ethane (1), was prepared by a facile, one-pot procedure. In addition, a reaction mechanism for the preparation of (1) was proposed. Based on (1), a diglycidyl ether derivative (2) was prepared and cured by commercially-available curing agents. The structures of (1-2) were confirmed by IR, high-resolution mass, 1-D and 2-D NMR spectra. Properties such as glass transition temperature, coefficient of thermal expansion, thermal decomposition temperature, and flame retardancy of the resulting thermosets were evaluated and compared with those of the thermosets of diglycidyl ether of bisphenol A. The resulting epoxy thermosets show high T_g, low thermal expansion, good thermostability and excellent flame retardancy.     

Effect of Modifying Additives on the Sintering and Properties of SiC/SiC<Subscript>w</Subscript> Ceramic Composite Material

Spark plasma sintering and hot compaction methods were used to obtain experimental samples of a composite material of the SiC?SiC_w system with various modifying additives (AlN, B₄C, HfB₂, Y₂O₃, Al₂O₃, Si₃N₄). The effect of the modifying additives on the sintering process, physicomechanical, and thermal properties of the ceramic composite material was examined. The introduction of the modifying additives lowered the sintering temperature of silicon carbide produced by the hot compaction method by 200°C and that formed with spark plasma spark sintering by 300?450°C as compared with the sintering temperature of silicon carbide without additives.     

Similarity examination of truncated virial equation of state correspondence to linear isothermal regularity (LIR) by applying square-well (SW) potential

Linear isotherm regularity works very well for fluids at high densities, and it has been shown that it is compatible with the EOSs based on statistical–mechanical theory. On the other hand, at low densities, the first few terms of virial EOS have the most contribution to express the deviations from ideal behavior. For finding similarities between dense and dilute states, experimental p–v–T data of 14 fluids (He, Ne, Ar, Kr, H₂, O₂, N₂, CO, NH₃, CH₃OH, CH₄, C₂H₄, C₂H₆ and C₃H₈) are examined. Comparing the thermal dependencies of the attraction and repulsion terms (A and B) of the LIR with the second and third virial coefficients (B ₂ and B ₃) in liquid and supercritical regions (0.7 < T _r < 3.0) shows a remarkable similarity. Square-well potential is applied to examination and comparison of theoretical results with experimental results. It is shown that in liquid and supercritical regions, (1) the short-range potential governs among particles in dense fluids, and the long-range interactions become important in the less dense fluid, (2) similar to Boyle temperature, T _B, in dilute state, there is a temperature as T′_B (in dense fluids) that the attractive forces and the repulsive forces acting on the dense-fluid particles balance out; thus, probably there is a maximum σ (molecular diameter) at nearly 2T _c (T′_B), and (3) in the liquid and supercritical regions (0.7 < T _r < 3.0), in the first-order approximation, there are no significant interactions higher than triple interactions in dense-fluid particles.     

Effect of gamma irradiation on linear low density polyethylene/magnesium hydroxide/sepiolite composite

Radiation crosslinking is generally used to improve the thermo-mechanical properties of the composites. A study has been carried out to investigate the effect of gamma radiation on the thermo-mechanical properties of linear low density polyethylene containing magnesium hydroxide (MH) and sepiolite (SP) as non-halogenated flame retardant additives. The developed composites are irradiated at different doses upto maximum of 150 kGy. Infrared spectra of the irradiated composites reveal the reduction in the intensity of O-H band with increase in the absorbed doses, thus indicates a distinct structural change in MH at higher doses. The thermogravimetric analysis results of unirradiated and composites irradiated at low doses (≤75 kGy) show two steps weight loss, which is changed to single step at higher doses with lower thermal stability. The melting temperature (T_m) and crystallization temperature (T_c) of irradiated composites are lowered with irradiation whereas Vicat softening temperature (VST) is increased. The increasing trend in gel content with increase in the absorbed dose confirms the presence of crosslinked network. The mechanical properties, results show significant improvement in the modulus of irradiated composites. The results also confirm that MH gradually loses its OH functionality with irradiation.     

Simple and straightforward synthesis of novel enantiopure ionic liquids via efficient enzymatic resolution of (±)-2-(1H-imidazol-1-yl)cyclohexanol

Both enantiomers of enantiopure imidazolium ionic liquids were synthesized by a simple and straightforward procedure from (R,R)- and (S,S)-2-(1H-imidazol-1-yl)cyclohexanol derivatives obtained via lipase-catalyzed resolution. Structural properties and thermal stability of these compounds have been studied to elucidate their potential applications in asymmetric catalysis.     

Monoelemental polymers: Structure and properties

Monoelemental polymers with various chemical constitutions and different spatial structures (linear Te _n , Se _n , and S _n ; planar graphite C _n , black phosphorus P _n , As _n , Sb _n , and Bi _n ; and chemically bonded three-dimensional diamond C _n , B _n , Si _n , and Ge _n ) were considered and categorized as a class of covalent macromolecular compounds. Quantitative expressions relating the thermal (melting point, thermal expansion coefficient, heat conductivity) and elastic (microhardness, bulk compression modulus of elasticity) properties of polymers to the energy of intra-and intermolecular interactions and the equilibrium length of chemical bonds in the crystalline and glassy states are given. A numerical correlation between the spatial structure of polymers and their thermal and elastic properties was obtained. The hypothetical melting point of diamond at normal pressure was calculated as T _f = 3155 K.     

Polymerization and processability of poly(vinyl chloride),

The processability of rigid poly(vinyl chloride) can be improved by adding trichloroethylene as chain-transfer agent, increasing the polymerization temperature, and especially by combining the two effects together. The resulting synergistic interaction is best expressed by an equation of the form, P = (A + B[TCE])e^C/T, where P is thermal plasticity, Ae^C/T is the combined effect of chain transfer to initiator and monomer and termination through combination and disproportionation, and B[TCE]e^C/T represents the chain-transfer action of trichloroethylene.     

Solution-grown crystal of poly[bis(4-isopropylphenoxy)phosphazene]

The structural features of poly[bis(4-isopropylphenoxy)phosphazene] (PB(4-ip)PP) have been studied by electron microscopy, X-ray diffraction and differential scanning calorimetry techniques. Its orthorhombic lattice constants are determined as follows: a = 3,14 nm, b = 1,14 nm, c = 0,992 nm. The space group of this polymer is suggested to be P 2₁2₁2₁–D, and the molecular conformation of the chains possibly to be (trans₃cis)₂. This polymer exhibits a crystal/crystal transition at 86°C below its T(1) transition (120°C). The thermal behavior is similar to the characteristics of poly[bis(p-methoxyphenoxy)phosphazene].     

Physical aspects of charge transfer theory

The possible shapes of the ground (U_I) and first excited (U_II) adiabatic potentials are discussed in connection with the electron transfer problem. If U_I has two minima the electron transfer process is adiabatic, regardless of the value of the gap 2Γ between U_I and U_II; the transfer rate W has the form W = B exp(?E_A/T), the pre-exponential factor B can be influenced by the size of the gap, especially when Γ is small. For the fluctuation model of the medium in the case of purely adiabatic transfer (large Γ) the value of W corresponds to diffusional penetration through the potential barrier. A barrier of arbitrary shape is considered and an expression for W obtained, which matches with the corresponding expression for the “hindered adiabatic” case of small Γ.     

Engineering thermal and mechanical properties of flexible fiber-reinforced aerogel composites

Flexible aerogel was successfully supported onto 4-layer-aligned glass fibers through impregnation, followed by drying at atmospheric pressure. The prepared nanocomposites can achieve a low thermal conductivity of 0.026?W/(m·K), which holds great promising for their use in thermal insulation applications. By choosing different designs of the four fiber layers, in the terms of LLLL, LTLL, LLTT, LTLT, LTTL and LTTT, the laminated structures of aerogel composites can be accordingly controlled. Further microstructure characterization of the composites revealed the homogeneous dispersion of nanoporous structure through the aerogel matrix, as well as highly-aligned fibers to reinforce the structure. Detailed investigation on the thermal and mechanical properties of the prepared fiber-aerogel composites showed that their performances were highly related to the laminated design of fiber layers. The introduction of fibers as the backbone of the aerogel and the suitable design of their laminated structure can greatly improve the mechanical properties of the aerogel composites while maintaining a low thermal conductivity.