Structural and thermal characterization of sugarcane bagasse phthalates prepared with ultrasound irradiation

Chemical modification of sugarcane bagasse was achieved by esterification with phthalic anhydride in pyridine after ultrasound irradiation. The parameters including ultrasonic irradiation time 0-40 min, phthalic anhydride dosage 2.5-7.5 g, reaction time 30-150 min, and reaction temperature 80-115 °C were optimised and the extent of phthalation was measured by weight percent gain. It was found that degradation of the cell wall polymers occurred at higher temperature (>90 °C) under the experimental conditions used.FT-IR and CP/MAS ¹³C NMR spectroscopy studies also clearly produced evidence for phthalation reaction. The phthalated bagasse preparations showed decreased thermal stability after chemical modification.     

An NMR study of the species produced by the reactions of dialkyl magnesium and HCl with calcined silica and the polymerisation performance of Ziegler-Natta catalysts produced from this support material

The effect of calcinations on the silica surface groups and thereby on the activity of Ziegler-Natta catalysts in ethylene homopolymerisation has been studied. Silica was calcined at different temperatures and treated with MgR₂ and HCl. Silica surface groups were identified by using ¹H MAS NMR and ¹³C and ²⁹Si CP MAS NMR techniques. Magnesium, titanium and chlorine were measured by elemental analysis. Ziegler-Natta catalysts were prepared from these supports and subsequently used in ethylene homopolymerisation. Maximum activity was obtained with the catalyst based on 590 °C calcined silica. The results indicate that MgR₂ reacts with siloxane-groups (Si-O-Si) in the 300 °C calcined silica, leaving the hydrogen-bonded hydroxyl-groups unreacted. Low activity Si-O-Ti(Cl)₂-O-Si species are formed after reacting with TiCl₄. The higher activity in the catalyst based on 590 °C calcined silica can be explained by the formation of -Si(R)-O-Si-O-TiCl₃ groups, originating from the siloxane bridges which cannot form in 300 °C calcined silica. Other explanations for the higher activity are a higher Mg/Ti ratio or small amounts of crystal water formed in the 590 °C calcined silica.     

Reaction of 2-hydroxyethylhydrazine with a trifluoromethyl-β-diketone: Study and structural characterization of a new 5-hydroxy-5-trifluoromethyl-4,5-dihydropyrazole intermediate

The reaction of the β-diketone 4,4,4-trifluoro-1-pyridin-2-yl-butane-1,3-dione and the monosubstituted hydrazine 2-hydroxyethylhydrazine has been investigated. Two products have been identified, 2-(2-hydroxyethyl)-3-pyridin-2-yl-5-trifluoromethyl-4,5-dihydropyrazole (P) and 2-(3-pyridin-2-yl-5-trifluoromethylpyrazol-1-yl)ethanol (L) in proportion 2:8, when the reaction was done at room temperature in ethanol for 15 h. The preparation of P as a pure product was performed in ethanol at 0 °C for 7 h. P has been characterized by ¹H, ¹³C{¹H} and ¹⁹F{¹H} NMR spectroscopy and by other techniques as appropriate.     

Highly fluorinated graphite prepared from graphite fluoride formed using BF3 catalyst

Fluorinated graphites (CF_0.47) were obtained by reaction at room temperature of fluorine gas with graphite in the presence of boron trifluoride and hydrogen fluoride as catalysts. Their thermal treatments under fluorine at temperatures up to 600 °C lead to a progressive increase of the fluorine level resulting in an highly fluorinated graphite (CF_1.02). Whatever the fluorination level, a stage one fluorine-graphite intercalation compound is obtained. The sp² carbon hybridization is maintained for treatment temperature below 300 °C and two types of structure coexist for T_T in the range 350-550 °C. Finally, above 550 °C, carbon hybridization is sp³.The resulting materials were studied by ¹¹B, ¹H, and ¹⁹F NMR and EPR at different experimental temperatures giving informations about the intercalated fluoride species, the temperature of their removal from the host fluorocarbon matrix, as well as their mobility.     

Synthesis and characterization of layered double hydroxides (LDH) intercalated with non-steroidal anti-inflammatory drugs (NSAID)

Layered double hydroxides (LDHs) with the hydrotalcite type structure and a Mg:Al ratio of two have been prepared, with salicylate or naproxen in the interlayer. Two synthetic routes have been used: reconstruction from a mildly calcined hydrotalcite-CO₃ precursor, and a coprecipitation method with chlorides of the metals. The solids have been characterized using several physicochemical techniques, i.e., powder X-ray diffraction, FTIR and ¹³C CP/MAS NMR spectroscopies and thermal analysis (thermogravimetric and differential thermal analyses). The gallery height determined is in all cases larger than the size of the drug, 11.5 Å for salicylate and 15.8 and 16.6 Å for naproxen, depending on the specific synthesis route followed. Experimental data suggest the anion molecules form a tilted bilayer, with the carboxylate groups pointing towards the brucite-like layers. The solids are stable up to 230 °C and their evolution from 350 °C upwards is very similar to that observed for a carbonate-containing hydrotalcite, forming mostly amorphous solids with a large specific surface area.     

Investigation of homopolymerization rate of perfluoro-4,5-substituted-2-methylene-1,3-dioxolane derivatives and properties of the polymers

Five perfluoro-4,5-substituted-2-methylene-1,3-dioxolane monomers were synthesized. These monomers were found to readily polymerized by a free radical initiator in bulk and/or in solutions. Homopolymerization rates were determined using in situ ¹⁹F NMR measurements and found to be 0.25 to 1.66 × 10⁻⁴ mol L⁻¹ s⁻¹ in 1,1,2-trichlorotrifluoroethane at 41 °C using the perfluorodibenzoyl peroxide as an initiator. The rates depend on the substituents on the 4 and 5 positions of the dioxolane. The purified polymers were thermally stable (up to 350 °C). They show low refractive indexes (1.33-1.36 at 532 nm). They are transparent from UV to near IR region and have high glass transition temperatures (100-170 °C).     

Synthesis and thermal properties of the thermosetting resin based on cyano functionalized benzoxazine

A novel thermosetting resin based on cyano functionalized benzoxazine (BZCN) has been synthesized from 2,6-bis(4-diaminobenzoxy)benzonitrile phenol and formaldehyde by solution reaction. The structure of the monomer is supported by FTIR, ¹H NMR and ¹³C NMR spectra, which have exhibited that the reactive benzoxazine rings and cyano group exist in the molecular structure of BZCN. The curing reactions of BZCN are monitored by the disappearance of the nitrile peak and the tri-substituted benzene ring that is attached with oxazine ring peak at 2231 and 930 cm⁻¹, respectively. The complete cured materials could achieve char yields up to 70% at 800 °C in nitrogen atmosphere, above 64% at 600 °C in air (20% oxygen) environments and the glass transition temperature up to 250 °C. The thermally activated curing polymerization reaction of BZCN follows multiple polymerization mechanisms via the ring-opening polymerization of oxazine rings and the triazine ring-formation of cyano groups, which contribute to the stability of the polymer.     

Synthesis of fluorinated hyperbranched polymers capable as highly hydrophobic and oleophobic coating materials

A series of coating materials were prepared from two classes of hyperbranched polymers containing short fluorocarbon chains (HPEFs/HPUFs). The obtained hyperbranched polymers were characterized by FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, GPC and TG analyses. HPEFs/HPUFs exhibited very low surface free energies (13.67-24.49 mJ/m²) which almost are independent of their internal backbone but dependent on the terminal fluorocarbon chains. Highly hydrophobic and/or oleophobic surfaces of cotton woven fabric can be achieved from these polymers by solution-immersion coating method. The static and dynamic wettabilities of the HPEFs/HPUFs treated fabrics have been investigated. The static contact angles reached to 146°, 122° and 102° for water, hexadecane and decane, respectively. The lowest contact angle hysteresis reached to 5.9°.     

Quality control of solid-phase synthesis: C PST/MAS NMR analysis on non-destructed SynPhase lantern

Pulse saturation transfer (PST)/MAS was highly effective for enhancing a magic angle spinning (MAS) ¹³C NMR of the inter-mobile region of polymer supported organic compounds. Direct monitoring of solid-phase synthesis on non-destructed SynPhase lantern was demonstrated using a 7 mm probe on the ¹³C PST/MAS NMR study.     

In and F MAS NMR study of (NH4)3InF6 phases

This study presents for the first time an NMR spectroscopic characterization of the room and high temperature phases of (NH₄)₃InF₆ using ¹⁹F and ¹¹⁵In as probe nuclei. The reversible phase transition to the cubic phase at 353 K was followed by MAS NMR in situ. Static NMR experiments of the room temperature phase and MAS NMR experiments of the high temperature phase allowed the determination of the NMR parameters of both nuclei. Finally, the scalar In-F coupling, rarely observed in solid state NMR, is evidenced in both room and high temperature phases of (NH₄)₃InF₆, and measured in the high temperature phase.     

A novel zinc chelate complex containing both phosphorus and nitrogen for improving the flame retardancy of low density polyethylene

A novel metal chelate complex containing phosphorus, nitrogen and zinc (II) ion was synthesized and used as the flame retardant of low density polyethylene (LDPE). The zinc chelate complex was synthesized by reacting zinc acetate with the ligand of tetraethyl (1,2-phenylenebis(azanediyl)) bis (2-hydroxylphenylmethylene) diphosphonate (TEPAPM). The chemical structure of the target Zn-TEPAPM was confirmed by FTIR, ¹H NMR, ¹³C NMR and ³¹P NMR spectra. The flame retardancy and thermal behavior of LDPE containing various amount of Zn-TEPAPM were investigated by limiting oxygen index test, thermogravimetric (TG) analysis and cone calorimetry. The results show that Zn-TEPAPM can greatly increase the thermal stability, the char formation and smoke suppression ability of LDPE. The TG curves show that even when the filler content of Zn-TEPAPM is as low as 1 wt% in LDPE, the onset degradation temperature of LDPE is increased from 429 °C to 442 °C, and the maximum degradation temperature is increased from 469 °C to 488 °C. Also, a reduction of 32% for the peak heat release rate (PHRR) is obtained in the cone test. Moreover, Zn-TEPAPM is demonstrated to be a very effective synergist of ammonium polyphosphate (APP). When 1 wt% of Zn-TEPAPM was introduced into the LDPE/APP (mass ratio 80/19) blend, the PHRR value is reduced by 32%, compared with that of LDPE/APP blend without Zn-TEPAPM, and the char layer becomes more compact and intact.     

The stability of poly(m-carborane-siloxane) elastomers exposed to heat and gamma radiation

Poly(m-carboranyl-siloxane) elastomers containing a mixture of di-methyl- and methylphenyl-silyl units were synthesised using the ferric chloride catalysed condensation reaction between di-chloro-diorganosilane and bis(di-methylmethoxysilyl)-m-carborane. These elastomeric materials were originally developed to have greater stability to extreme thermal environments and retain tailorable physical and chemical properties relative to comparable non-carborane containing elastomers. Prepared samples were aged either by heating in air at elevated temperatures or by gamma irradiation from a ⁶⁰Co source. Multinuclear (¹H, ¹³C and ¹¹B) solid and solution state nuclear magnetic resonance (NMR) was used to assess degradation. This included measurements of segmental chain dynamics using a solid-echo pulse sequence reflecting changes in crosslink density and assessing changes to the carborane fragment by ¹¹B and ¹H Magic Angle Spinning (MAS) methods. Thermogravimetric measurements were also performed to assess thermal stability. Gamma radiation (to a dose of 1 MGy) was found to induce only a small degree of elastomer hardening as evidenced by a reduction in segmental chain dynamics. The carborane cage however, remained intact at these dose levels. Thermal degradation was observed to lead to oxidative crosslinking, the degree of which is dependent on temperature. At temperatures below 350 °C, only small changes in segmental dynamics were observed commensurate with only minor weight loss at this temperature. At temperatures above 350 °C, the degradation of the elastomer increased dramatically with decreased segmental dynamics and presumed partial oxidation of the carborane cage. The integrity of the m-carborane cage and the segmental dynamics were found to be significantly reduced at temperatures above 580 °C, in line with the known cage rearrangement temperature for icosahedral carboranes.     

Fast Ion Conducting Nanocrystalline Alkaline Earth Fluorides Simply Prepared by Mixing or Manual Shaking

Simple mixing or shaking of alkaline earth hydroxides with ammonium fluoride results in nanocrystalline phase pure metal fluorides MF₂ (M: Ca, Sr, Ba). The formation of the alkaline earth fluorides was investigated by varying the reaction conditions. Evidence was found that just the contact between the starting materials is sufficient for the reaction to take place. X‐ray diffraction, elemental analysis, ¹⁹F MAS NMR spectroscopy, and measurements of DC conductivities were used to characterize the fluorides regarding properties like crystal structure, crystallite sizes, local fluorine coordination, and fluorine ion conductivity. The ¹⁹F MAS NMR spectra of the phase pure fluorides prepared showed several signals, which were assigned to defects, impurities, or geometric distortions. The fluorides prepared by mixing or shaking revealed fluorine ion conductivities several orders of magnitude higher than observed for the respective microcrystalline alkaline earth fluorides. Therefore, the synthesis routine presented in this study may open a path to a very quick and simple synthesis of nanocrystalline fast fluorine ion conductors.     

An experimental study of 19F-19F and 13C-19F spin-spin coupling in molecules of difluoro(fluorosulfonyl)- and difluoro(fluorosulfonyloxy)acetyl fluorides

High-resolution ¹⁹F and ¹³C NMR spectra of difluoro(fluorosulfonyl)- and difluoro(fluorosulfonyloxy) acetyl fluorides were studied, and specific features of complex spin-spin coupling of fluorine and carbon nuclei were characterized. The mechanisms of ¹⁹F and ¹³C coupling were interpreted.     

Highly carbonized polyaniline micro- and nanotubes

We have obtained unique highly carbonized polyaniline micro- and nanotubes as a new, thermally stable nanomaterial for nanosensors and nanodevices with a wide range of possible applications, comparable to carbon nanotubes. Polyaniline nanostructures are easy to prepare and handle in wet conditions, including controlled growth. Temperature-induced transformations of polyaniline micro- and nanotubes into highly carbonized analogues have been observed at and above 800 °C, while the temperature was elevated slowly from 20 °C up to 1100 °C. Carbonized products have the same morphology (micro- and nanotubes), but a lower spin density than the starting material (e.g. 10¹⁴ g⁻¹ for the sample heated at and above 800 °C, and 10¹⁹ g⁻¹ before heating). Simultaneously, the electrical conductivity changes from 7.4 × 10⁻⁵ S/cm for the starting material to 4.8 × 10⁻⁹ S/cm, 1.3 × 10⁻¹¹ S/cm and finally 2.4 × 10⁻⁶ S/cm for samples obtained at room temperature, 250 °C, 500 °C and 800 °C, respectively. Chemical transformations and unique molecular structures formed are discussed. Applications in nanotechnology, including sensors and electronic nanodevices, are expected in the light of experiments already performed.     

Novel fluoroacrylated copolymers: synthesis, characterization and properties

The development of polymer waveguides leads to synthesis of fluorinated amorphous polymers with high transmission capacity, potential to tune their optical properties by tailoring the molecular structure, together with good processability, easy handling, good flexibility and low cost.In this work we have investigated new thermoplastic fluoroacrylated copolymers, synthesized by radical copolymerization of fluoroalkene(s) with five-membered cyclic carbonate and a third monomer or transfer agent, both containing OH group susceptible to be used for grafting of photocrosslinkable groups. The reaction of hydroxy functionalized copolymers with different acrylating agents results in fluoroacrylated resins with molecular weight in the range of 2000-3000 g mol⁻¹, yield >75% and good solubility in reactive diluents. In the presence of photoinitiator(s), they were crosslinked under UV-radiation in order to obtain optical waveguides.The copolymers synthesized were characterized by ¹H, ¹⁹F and ¹³C NMR as well as FT-IR spectroscopies and have good thermal stability (T_d > 200 °C). The refractive indeces of hydroxy functionalized fluorooligomers and acrylated resins were found to range from 1.44 to 1.45 at 23 °C and the T_gs (by DSC) varied from 40 to 110 °C depending on the content of the cyclic monomer. The optical characteristics of these thermoplastic fluoroacrylated copolymers are under progress.     

Effect of surface fluorination on the electrochemical behavior of petroleum cokes for lithium ion battery

Surface structure change and electrochemical behavior of fluorinated petroleum coke samples (petroleum cokes: petroleum coke and those heat-treated at 1860 °C, 2300 °C and 2800 °C, abbreviated to PC, PC1860, PC2300 and PC2800, respectively) have been investigated. Surface oxygen of petroleum coke was decreased by the fluorination using elemental fluorine. Raman and EPR spectroscopies revealed that surface fluorination increased surface disorder and lattice defects. ¹⁹F NMR spectrum suggests that distribution of fluorine atoms in PC fluorinated 300 °C was similar to that in graphite fluoride with covalent CF bonds. Surface areas of fluorinated petroleum cokes were nearly the same as those of non-fluorinated ones or only slightly increased by fluorination, except PC fluorinated at 300 °C. It is noted that first coulombic efficiencies of PC2300 and PC2800 were highly increased to 80-84% by the fluorination at 300 °C. These values of 80-84% were 12-18% higher than those of non-fluorinated PC2300 and PC2800.     

New confined p-phenylenevinylene (PPV)-type polymer analogue of poly(phenylene sulfide)

A new confined p-phenylenevinylene (PPV)-type polymer (PPVS) has been synthesized using Wittig condensation. The chemical structure of the polymer was well defined by ¹H NMR, ¹³C NMR, and FTIR spectroscopic analysis. PPVS contains oligomeric PPV units separated by sulfide bridges in the main chain; it is fully soluble in common organic solvents and has a number-average molecular weight of 3500 g mol⁻¹. Thermogravimetric analysis and differential scanning calorimetry indicate that PPVS is amorphous, stable up to 360 °C in air and displays a glass transition temperature of 98 °C. The optical properties of the polymer were investigated by UV-visible absorption and photoluminescence spectroscopies. The polymer film absorbs at 375 nm and emits at 517 nm with a narrow emission spectrum. From the cyclic voltammetry analysis, the electrochemical bandgap was estimated to be 2.78 eV. A single-layer diode device of the configuration indium-tin oxide/PPVS/aluminium has been fabricated and has a relatively low turn-on voltage of 3.4 V. An electroluminescent emission similar to photoluminescence is demonstrated in a multilayer device.     

Structural and thermal characterization of sugarcane bagasse cellulose succinates prepared in ionic liquid

The chemical modification of SCB cellulose with succinic anhydride using 1-butyl-3-methylimidazolium chloride ionic liquid/DMSO system as reaction medium was studied. The parameters including the molar ratio of succinic anhydride/anhydroglucose units in cellulose from 1:1 to 12:1, reaction time 5-120 min, and reaction temperature 85-105 °C were investigated. The results showed that the degree substitution of succinylated cellulosic preparations ranged from 0.037 to 0.53. It was found that the treatment of the native cellulose in the ionic liquid/DMSO system under the conditions given significantly degraded the cellulose and completely destroyed the cellulose crystals. FT-IR and solid-state CP/MAS ¹³C NMR spectra produced evidence for succinoylation reaction and the results showed that succinoylation occurred at positions C-6, C-2 and C-3. The thermal stability of the succinylated cellulose decreased upon chemical modification.     

Preparation and characterization of fluorinated acrylate copolymer latexes by miniemulsion polymerization under microwave irradiation

Fluoroacrylate copolymer miniemulsion was prepared by miniemulsion polymerization under microwave irradiation. The composition of the copolymer was determined by FTIR, DSC, ¹H NMR and ¹⁹F NMR. The morphology, size, and size distribution of the latex particles as well as changes in the size during polymerization were characterized by TEM and photon correlation spectroscopy (PCS). The effects of kinetic parameters on the polymerization were evaluated. The particle size of latex underwent almost no change during microwave irradiation polymerization. The diameters of latex particles prepared by microwave irradiation were smaller and more monodispersed than those prepared by conventional heating and the latex had good centrifugal stability. Polymerization under microwave irradiation had a higher reaction rate and higher conversion than traditional heating. By using 10 wt% fluoromonomer, the surface energy of the latex film could be reduced from 27.24 mJ/m² (latex film of fluorine-free) to 17.59 mJ/m² and the decomposition temperature increased by 25 °C.