Application of glycidol in synthesis of oligoetherols with perhydro‐1,3,5‐triazine ring

A new method of preparation of oligoetherols containing perhydro‐1,3,5‐triazine rings from isocyanuric acid and an excess of glycidol, alkylene carbonates, or oxiranes is presented. The course of reaction was studied at various molar ratios of glycidol to isocyanuric acid. The structure of the products was established, and some physical properties were measured. The oligoetherols were demonstrated to be useful substrates for polyurethane foams of enhanced thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Application of products of reaction between melamine and glycidol as substrates for oligoetherols and polyurethane foams containing 1,3,5‐triazine rings

Hydroxyalkyl derivatives of melamine were obtained by addition of melamine to glycidol. These derivatives were then used to obtain multifunctional oligoetherols by reaction with oxiranes and alkylene carbonates. The structure and properties of the oligoetherols were studied in detail. The oligoetherols were then used to obtain polyurethane foams of enhanced thermal stability. The foams showed marked thermal resistance at 200 °C. The beneficial feature of the obtained foams was their increased compression strength after thermal exposure. © 2013 Society of Chemical Industry     

Oligoetherols Obtained from Uric Acid,Glycidol, and Alkylene Carbonates and Their Use to Obtain Polyurethane Foams of Enhanced Thermal Resistance

A new method of preparation of oligoetherols containing purine rings from uric acid and an excess of glycidol and alkylene carbonates was presented. The course of reaction was studied at various molar concentrations of glycidol. The structure of the products was established, and some physical properties were measured. The oligoetherols were demonstrated to be useful substrates for rigid polyurethane foams of enhanced thermal stability.     

Bifunctional oligoetherols with carbazole ring

A new synthetic method for bifunctional oligoetherols with carbazole ring was presented. 9‐(2,3‐Epoxypropyl)carbazole was obtained from carbazole and epichlorohydrine. The epoxide ring opening occurred upon the consecutive reaction with ethylene glycol to give the semiproduct well soluble in ethylene oxide and propylene oxide and reactive toward these epoxides at temperatures above 60–90°C to form oligoetherols. Structure of these oligoetherols and their physical properties and application for synthesis of linear polyurethanes were studied in details. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Oligoetherols and polyurethane foams obtained from melamine diborate

The method of synthesis of oligoetherols with 1,3,5-triazine ring and boron was established. The obtained oligoetherol is suitablse to obtaining polyurethane foams (PUFs) of enhanced thermal resistance and diminished flammability. The obtained PUFs can stand long term thermal exposure at 175 °C. The PUFs annealed at 150 and 175 °C showed improved compressive strength in comparison with not exposed to heating.     

Preparation and characterization of water‐blown polyurethane foams from liquefied cornstalk polyol

Polyurethane foams were prepared from the liquefied cornstalk polyol, which was obtained by the liquefaction of cornstalk in the presence of polyhydric alcohols using sulfuric acid as catalyst. The advisable liquefaction reaction conditions were selected by investigating their influences on the properties of liquefied cornstalk polyol, taking account of the requirement for the preparation of appropriate polyurethane foams. The influences of the contents of catalysts, water, surfactant, and isocyanate on the properties of polyurethane foams were also discussed, and feasible formulations for preparing cornstalk‐based polyurethane foams were proposed. The results indicated that the foams prepared from such liquefied cornstalk polyol exhibited excellent mechanical properties and thermal properties, and could be used as heat‐insulating materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Application of reactive solvents of melamine for synthesis of polyetherols with perhydro‐1,3,5‐triazine rings

The application of reactive solvents (RSs), namely hydroxymethyl derivatives of acetone for digestion of isocyanuric acid, which is insoluble in most organic solvents except for DMSO, makes the substrate available for further conversions. At this step, the incorporation of perhydro‐1,3,5‐triazine ring into RS takes place. The obtained solutions were used for synthesis of polyetherols containing perhydro‐1,3,5‐triazine rings in reaction with oxiranes: ethylene and propylene oxides. The polyetherols were then used to obtain foamed polyurethanes with enhanced thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and chemical reactions of rigid cross‐linked poly(vinyl chloride) foams modified by epoxy compounds

A novel method to prepare semi‐interpenetrating polymer network rigid cross‐linked poly(vinyl chloride) (c‐PVC) foams with improved shear toughness in the absence of anhydride components is reported. The cross‐linked network structure in the c‐PVC foams was composed of polyurea network modified by epoxy structure. The cellular morphology was characterized by scanning electron microscopy. Tensile, compressive, and shear properties of the foams were studied. The obtained c‐PVC foams showed high shear properties compared with the comparative samples with the same density and cellular morphology. Possible reactions during the preparation of c‐PVC foams were studied by means of Fourier transform infrared spectrometry and nuclear magnetic resonance measurements through the model experiments. The results showed that allophanate structure resulting from the reaction between isocyanate compounds and epoxy compounds formed in the molding step, which was included into the final cross‐linked network in the cross‐linking step. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40567.     

Preparation and cell morphology of ethylene‐vinyl acetate copolymer (EVA)/wood‐flour foams with low density

The main objective of this study is to obtain ethylene‐vinyl acetate copolymer (EVA)/wood‐flour foams with low density (< 0.2 g/cm³) using chemical blowing agent. Stearic acid was used as a compatibilizer to improve not only the compatibility between wood‐flour and EVA but also the compatibility between moisture and EVA in this study. The effects of wood‐flour content on the density and mechanical properties of EVA/wood‐flour foams were studied. Also, the effects of content of stearic acid on the cell morphology of EVA/wood‐flour foams were investigated. The shape of EVA/wood‐flour foams with 20% wood‐flour content becomes more uniform with increasing content of stearic acid. The most stabilized shape of the foams is obtained with 5 wt % stearic acid content. The density of EVA/wood‐flour foams with 20% wood‐flour and 5 wt % stearic acid is 0.11 g/cm³. With increasing content of stearic acid, more gas remains in the EVA matrix and consequently, average cell size and density increase. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40894.     

The effect of different palm oil‐based bio‐polyols on foaming process and selected properties of porous polyurethanes

Rigid polyurethane foams were successfully prepared by blending up to 70 wt% of two different palm oil‐based bio‐polyols with a petrochemical polyether polyol. The bio‐polyols were synthesized by epoxidation–oxirane ring‐opening process using water (PP102) and diethylene glycol (PP147), respectively. Due to the high viscosity of both bio‐polyols the reactive mixture was heated to start the foaming reaction at about 50 °C. Under these conditions, the gelling reactions speed up as the amount of PP147 increases but slow down to a great extent when PP102 is used. The thermal conductivity of modified foams is higher and the closed cell content lower compared to reference ones, even when the bio‐foams present a lower apparent density. However, all foams exhibit reduced water absorption, excellent dimensional stability and better thermal stability at temperatures up to 400 °C than the control foam. Conversely, their mechanical and dynamic mechanical properties become poorer as the PP147 concentration increases and even more so if PP102 is used instead. PP147 foams containing up to 50% bio‐polyol could be used as a green replacement of petroleum‐based ones in applications where excellent behaviour in compression (the most affected properties) is not fundamental, with the additional advantages of reduced density and increased content of bio‐derived components. © 2017 Society of Chemical Industry     

Resol‐type phenolic resin from liquefied phenolated wood and its application to phenolic foam

A liquefied wood‐based resol resin was prepared with excellent yield by a reaction of liquefied wood and formaldehyde under alkaline conditions. The effects of various reaction parameters on the extent of the yield of the resol resin, unreacted phenol content, and viscosity were investigated. Milder resol resinification conditions were required as compared to those used in conventional methods. The liquefied wood‐based resol resin was successfully applied to produce phenolic foam using appropriate combinations of foaming agents. Diisopropyl ether with a relatively higher boiling temperature was suitable for the foaming of liquefied wood‐based resol resin. Hydrochloric acid and poly(ethylene ether) of sorbitan monopalmitate were used as a catalyst and a surfactant, respectively. The obtained foams showed satisfactory densities and compressive properties, comparable to those of foams obtained from conventional resol resin. Foams with low density were obtained by the blending of liquefied wood‐based resol resin and conventional resol resin. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 468–472, 2002; DOI 10.1002/app.10018     

Comparing Different Synthesis Procedures for Carbide‐Derived Carbon‐Based Structured Catalyst Supports

Different approaches were analyzed to combine the tuneable micropore structure of carbide‐derived carbons with a foam‐like secondary porosity. The resulting structured catalyst supports were characterized in detail and applied in the model reaction of ethene hydrogenation. Preparation methods studied were dip‐coating using polytetrafluoroethylene as binder on cellular metal structures, a chemical vapor deposition coating of the metal structures with thin carbide layers and subsequent conversion to carbide‐derived carbon, and the partial or full conversion of carbide foams to carbon/carbide composites. For the binder method, optimal parameters for stable slurry preparation as well as for calcination of the slurry were obtained. It could further be demonstrated that the conversion of carbide foams into carbon/carbide composites leads to an appreciation between decreasing mechanical strength and increasing specific surface area.     

New foamed plastic based on polyetherols obtained from 6‐aminouracil,ethylene carbonate,and propylene oxide

Polyetherols with 1,3‐pyrimidine ring including both oxyethylene and oxypropylene groups were obtained in reactions of 6‐aminouracil with ethylene carbonate and propylene oxide. The structure of the products was analyzed by spectral methods. Some physical properties of polyetherols were investigated. The polyetherols were used as polyol components to obtain polyurethane foams. Some properties of the foams such as apparent density, absorption of water, linear dimensions stability, thermal resistance, and compression strength were investigated. The foams obtained show an improved thermal stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of 2‐oxazoline‐benzoxazine compound and its polymer

A novel 2‐oxazoline‐benzoxazine (POB) was synthesized with 2‐(hydroxylphenyl)‐2‐oxazoline, 1,3,5‐triphenylhexahydro‐1,3,5‐triazine and paraformaldehyde. The chemical structure of the monomer was confirmed by FTIR, ¹H‐NMR, ¹³C‐NMR, and MS. The curing behavior of the monomer was studied by DSC and FTIR, and the ring opening reaction of the monomer was found to occur from 187.5°C. The results of DMA and TGA demonstrated that the thermal properties of polymer for POB monomer (P‐m) are better than polymer for POB precursor (P‐p), because that the oligomer in benzoxazine precursor decreased the perfection of the polymer's network structure; it was also found that the thermal properties of P‐m and P‐p are much better than the common polybenzoxazine and the composite material of benzoxazine and 2‐oxazoline. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci , 2008.     

Branched phenyl‐s‐triazine moieties to enhance thermal properties of phthalonitrile thermosets

Heat‐resistant materials have made tremendous progress in marine, aerospace and microelectronic fields. Herein, a new class of phthalonitrile resins, branched poly(biphenyl ether triphenyl‐s‐triazine) phthalonitriles, were successfully synthesized via a two‐step, one‐pot reaction, on the basis of 2,4,6‐tris(4‐fluorophenyl)‐1,3,5‐triazine and 4,4′‐biphenol. 4,4′‐Diaminodiphenylsulfone was employed to facilitate the curing reaction, and successful realization of curing behavior was concluded from rheological and differential scanning calorimetric studies, indicating the obtained resins possess favorable processability. The relationship between concentration of reactants and properties of the resins was systematically studied. After thermal curing, the E‐glass fiber‐reinforced composite, prepared with a concentration of reactants of 0.15 g mL^?1, shows an admirable glass transition temperature of 480 °C and commendable thermal stability with 5% weight loss temperature in nitrogen of 563 °C, suggesting that the improvement of the thermal properties stems from the branched structure and the phenyl‐s‐triazine units. © 2017 Society of Chemical Industry     

Novel N‐ethyl‐2‐styrylquinolinum iodides as sensitizers in photoinitiated free radical polymerization of trimethylolopropane triacrylate (TMPTA), part 3

Three‐component systems, which contain a light‐absorbing species (dye), an electron donor (n‐butyltriphenylborate salt), and a third component (N‐alkoxypyridinum salt or 1,3,5‐triazine derivative), have emerged as efficient, visible‐light sensitive photoinitiators of free radical polymerization. It was found that three‐component systems are more efficient than their two‐component counterparts. Kinetic studies based on microcalorimetry revealed a significant increase in polymerization rate with increasing concentration of N‐alkoxypyridinum salt. Such results were not obtained for photoinitiating systems possessing 1,3,5‐triazine derivative as a second coinitiator. Based on the experimental results we concluded that the primary photochemical reaction involves electron transfer from the borate anion to the excited dye followed by the reaction of resulting dye‐based radical with second coinitiator that regenerates the original dye and simultaneously produces the alkoxy radical or triazynyl radical which could start the polymerization chain reaction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of liquid‐type silane additives and organoclay on the morphology and thermal conductivity of rigid polyisocyanurate‐polyurethane foams

This article investigates the effects of liquid‐type silane additives and organoclay as a solid‐type additive on the morphological, mechanical and thermal insulating properties of polyisocyanurate‐polyurethane (PIR‐PUR) foams. The organoclay likely acted as nucleating agents during the formation of PIR‐PUR foams. When the liquid silane additives and organoclay were added, the cell size and thermal conductivity of the PIR‐PUR foams appeared to be decreased. However, organoclay did not contribute to reduce the cell size distribution of the foam. PIR‐PUR foams synthesized with tetramethylsilane as a liquid‐type additive showed a smaller average cell size and lower thermal conductivity than that of PIR‐PUR foams synthesized with the other silane additives or with organoclay as a solid‐type additive. For the PIR‐PUR foam with organoclay/TEMS (1.5/1.5 php) mixture, cell size and thermal conductivity of the foam showed similar to the foam with TEMS. These results suggest that smaller cell size appears to be one of the major factors in the improvement of thermal insulation properties of the PIR‐PUR foams. Silane additives did not seem to have a strong effect on the flammability of the PIR‐PUR foams. However, heat resistance was more dominant for the foam with the organoclay at the higher temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and Characterization of the Nitrogen‐Rich Hyperbranched Polymers – Poly([1,2,3]‐Triazole‐[1,3,5]‐Triazine)s

Novel hyperbranched poly([1,2,3]‐triazole‐[1,3,5]‐triazine)s (HBP TT) were synthesized by a 1,3‐dipolar cycloaddition reaction from AB₂ monomer – 2‐azido‐4,6‐bis‐prop‐2‐yn‐1‐yloxy‐ [1,3,5]‐triazine (ABPOT). The monomer contains one azide group A and two terminal alkyne units B. Thermal polymerization of ABPOT in bulk or in DMF solution leads to hyperbranched polymers containing both 1,4‐ and 1,5‐disubstituted [1,2,3]‐triazoles. The monomer was also polymerized catalytically in the presence of Cu(I) salts under mild reaction conditions in DMSO solution and in bulk affording hyperbranched poly‐[1,2,3]‐triazoles 1,4‐disubstituted only. The reactions lead to the products soluble in aprotic polar solvents like DMSO or DMF. Side reactions can proceed in a few cases, particularly: (i) homocoupling of alkyne groups, leading to the formation of insoluble products as a result of cross‐linking, (ii) isomerization of propynyloxytriazine fragments to propynyl‐ or propadienyltriazinone ones, and (iii) hydrolysis of triple bonds without the loss of solubility. Heats of formation of monomer and synthesized polymers were calculated from their combustion heats. All products were characterized by NMR‐, IR‐spectroscopy, and size exclusion chromatography (SEC) data. The obtained results open the prospect for the use of HBP TT as the high‐enthalpy modifiers for energetic and non‐energetic binders.     

An Ab Initio Theoretical Study of 2,4,6‐Trinitro‐1,3,5‐Triazine, 3,6‐Dinitro‐1,2,4,5‐Tetrazine,and 2,5,8‐Trinitro‐Tri‐s‐Triazine

In order to evaluate 2,4,6‐trinitro‐1,3,5‐triazine (TNTAz), 3,6‐dinitro‐1,2,4,5‐tetrazine (DNTAz), and 2,5,8‐trinitro‐tri‐s‐triazine (TNTsTAz), the geometries of these compounds have been fully optimized employing the B3LYP density functional method and the AUG‐cc‐pVDZ basis set. The accurate gas phase enthalpies of formation have been obtained by using the atomization procedure and designing isodesmic reactions in which the parent rings are not destroyed. Based on B3LYP/AUG‐cc‐pVDZ calculated geometries and natural charges, the crystal structures have been predicted using the Karfunkel–Gdanitz method. Computed results show that there exists extended conjugation over the parent rings of these compounds. More energy content is reserved in DNTAz than in both TNTAz and TNTsTAz. The title compounds are much more sensitive than 1,3,5‐trinitrobenzene. The calculated detonation velocity of DNTAz reaches 9.73–9.88 km s⁻¹, being larger than those of CL‐20 and TNTAz. TNTsTAz has no advantage over the widely used energetic compounds such as RDX and HMX.     

The Low‐Temperature High‐Pressure Phase Diagram of Energetic Materials: I. Hexahydro‐1,3,5‐Trinitro‐s‐Triazine

The reaction phase diagram of hexahydro‐1,3,5‐trinitro‐s‐triazine (RDX) has been studied as a function of temperature and pressure by Raman spectroscopy to 29 GPa and temperatures ranging from 4 to 298 K. Three stable phases (α, γ, and δ) have been found and their phase stabilities have been investigated. Phase boundaries were studied as a function of pressure and temperature, permitting a delineation of the various polymorph stability fields. A pressure–temperature reaction/phase diagram is constructed from the results of this study and compared to previous high temperature work.