Fluorinated 3-diethylaminopropenoates and their reactions

1981 ◽  
Vol 46 (6) ◽  
pp. 1389-1396 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
František Liška ◽  
Václav Dědek
Keyword(s):  
Thermal Decomposition ◽  
Point Of View ◽  
Hydroxyl Group ◽  
Chlorine Atoms ◽  
Vinylic Substitution ◽  
Diethylamino Group ◽  
Fluoro Derivatives

The reaction of diethylamine with methyl trifluoropropenoate (I), methyl 2-chloro-3,3-difluoropropenoate (II), methyl 3,3-difluoropropenoate III) and methyl 3-chloro-2,3-difluoropropenoate (IV) affords halogenated 3-diethylaminopropenoates V-VII via the vinylic substitution of fluorine or chlorine atoms. When hydrolyzed the latter give methyl N,N-diethylcarbamoylacetates X-XII. On addition of 1-butanol and 2,2,3,3-tetrafluoropropanol to aminopropenoates V-VII fluorinated 3-alkoxy-3-diethylaminopropenoates XIII-XVI were prepared which when hydrolyzed eliminate the diethylamino group under formation of alkyl methylpropanedioates XX to XXIII. Heating of aminoethers XIII-XVI at 150 °C gives 1-fluorobutane or 1,1,2,2,3-pentafluoropropane, respectively. These fluoro derivatives are also formed on heating of the mentioned alcohols with 3-diethylaminopropenoates V-VII. During the thermal decomposition of methyl 2-chloro-3-diethylamino-3-fluoro-3-(2,2,3,3-tetrafluoropropoxy)propanoate (XV) 3-chloro-1,1,2,2-tetrafluoropropane was formed as a by-product. The substitution of the hydroxyl group with fluorine is discussed from the point of view of preparative application.

AN INVESTIGATION OF THE CHLORINATION OF SPRUCE WOOD AND OF THE RESULTING CHLOROLIGNIN

1937 ◽  
Vol 15b (7) ◽  
pp. 279-294 ◽  
Author(s):  
G. V. Jansen ◽  
J. W. Bain
Keyword(s):  
Methyl Alcohol ◽  
Ring Structure ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Hydrogen Atoms ◽  
Chlorine Atoms ◽  
Spruce Wood ◽  
Simple Substitution ◽  
Homogeneous Fraction ◽  
Acid Reduction

Spruce sawdust was chlorinated under various conditions in an attempt to procure a homogeneous lignin chloride. Success finally attended the use of methyl alcohol as a medium for chlorination. The lignin chloride, which was dissolved by the alcohol during the chlorination and subsequently precipitated by the addition of water, was cream white in color, and analysis showed it to be an alcohol lignin.A homogeneous fraction (No. 2) was obtained from the re-chlorinated product, and it proved to be a chlorinated analogue of Hibbert's monomethylated methyl alcohol lignin, the formulas of the two products being C42H22O6Cl13(OH)2(OCH3)7, and C42H32O6(OH)3(OCH3)7. The molecular weight and the presence of the two hydroxyl groups were confirmed by acetylation, when 2.0 acetyl groups entered the molecule. Eleven of the chlorine atoms in Fraction 2 have evidently replaced ten hydrogen atoms and one hydroxyl group by simple substitution in methyl alcohol lignin, leaving two chlorine atoms which have apparently entered to saturate a double bond. Seven of these chlorine atoms have been shown to be readily removable either by an alkali or by acid reduction. The other six, because of their stable union with the molecule, are surmised to be joined to an aromatic nucleus or at least to some type of ring structure. The product has been shown to react stoichiometrically within limits as narrow as could be expected for such a large molecule.

The thermal decomposition of methylene chloride

1959 ◽  
Vol 250 (1261) ◽  
pp. 180-196 ◽  
Keyword(s):  
Thermal Decomposition ◽  
Hydrogen Chloride ◽  
Methylene Chloride ◽  
Flow System ◽  
Vessel Diameter ◽  
Chlorine Atoms ◽  
System A ◽  
Pressure Time ◽  
A Chain ◽  
Kinetic Features

The thermal decomposition of methylene chloride has been studied in the temperature range 500 to 650 °C by both the static technique of pressure-time measurement and the use of a flow system in conjunction with gas chromatographic analysis. The reaction, which leads principally to carbon and hydrogen chloride is characterized by a slow acceleration, the rate of which decreases with the vessel diameter. In vessels of diameter less than 5 mm the reaction is almost completely inhibited. The reaction rate is increased by the addition of inert gas, nitric oxide and, particularly, by dichlorethylene. Using the flow system a number of chlorinated hydrocarbons were detected as minor products of the reaction and their rate of formation relative to the major products was followed in detail. By identifying some of these as radical recombination products and one, dichlorethylene, as a degenerate branching agent, a delayed branching mechanism has been deduced which explains most of the kinetic features of the reaction as well as the formation of the observed minor products. This involves the production of the intermediate, dichlor­ethylene, in a chain carried by chlorine atoms and dichlormethyl radicals, and the conversion of this to carbon and hydrogen chloride by a coupled chain also involving chlorine atoms. The average primary chain length has been estimated as fifteen by measurement of the rate of formation of the supposed recombination products, but this figure is uncertain since the termination products appear to be destroyed in turn by chlorine atoms generated in the main chain.

A Mössbauer study of thermal decomposition of biotites

1975 ◽  
Vol 40 (309) ◽  
pp. 79-88 ◽  
Author(s):  
C. S. Hogg ◽  
R. E. Meads
Keyword(s):  
Heat Treatment ◽  
Thermal Decomposition ◽  
Hydroxyl Group ◽  
Mössbauer Study ◽  
Octahedral Sites ◽  
M6ssbauer Effect ◽  
Thermogravimetric Data ◽  
Infra Red ◽  
Structural Breakdown ◽  
Good Agreement

SummaryThe effect of heat treatment in air at temperatures from 200°C to 1000°C of two Cornish biotites has been studied using the M6ssbauer effect in 57Fe. One of the micas was also studied after heating in vacuo.Progressive changes in the Mössbauer spectra of the materials after heat treatment can be correlated with the following processes: Oxidation of Fe2+ ions in isolated octahedral sites to give Fe3+ in the co-ordination Fe3+(OsOH); oxidation of Fe2+ ions in adjacent a-octahedral (cis OH−) sites to give Fe3+(O6); and oxidation of Fe z+ in adjacent a and b (trans OH−) sites to give either Fe3+(O5OH) or Fe3+(O6) depending on whether a shared hydroxyl group remains intact or otherwise (these processes occur at temperatures below 500°C Also, at higher temperatures, dehydroxylation of Fe3+(O5OH) to give more Fe3+ in the Fe3+(O6) configuration. Finally, in the temperature range 900 to 1000°C structural breakdown yielding α-Fe2O3 as the iron-containing phase.The results and interpretation are in good agreement with thermogravimetric data and with a previous infra-red study. The mechanism of charge diffusion in the lattice during oxidation is discussed in the light of the results.

scholarly journals Interlamellar amino functionalization of kaolinite

1997 ◽  
Vol 75 (11) ◽  
pp. 1766-1772 ◽  
Author(s):  
James J. Tunney ◽  
Christian Detellier
Keyword(s):  
Thermal Analysis ◽  
Thermal Decomposition ◽  
Nmr Spectroscopy ◽  
Structural Model ◽  
Hydroxyl Group ◽  
Two Dimensional ◽  
Amino Groups ◽  
Surface Hydroxyl ◽  
Silicate Surface ◽  
Ir Analysis

The interlamellar surface of kaolinite has been modified with molecules possessing amino functionalities. Either the dimethyl sulfoxide intercalate of kaolinite (Kao/DMSO) or the N-methylformamide intercalate of kaolinite (Kao/NMF) were used as starting materials. One of the products, an ethanolamine functionalized kaolinite (Kao–EOA) was resistant to thermal decomposition in both air and N2 atmospheres up to temperatures greater than 150 °C. Based on results from thermal analysis, IR analysis, 13CCP/MAS NMR spectroscopy, and elemental analysis, a structural model is proposed in which every third interlayer surface hydroxyl group on the aluminol (Al-OH) surface of kaolinite is either replaced with an interlayer Al-OCH2CH2NH2 group or is strongly H-bonded to an aminoalcohol molecule. A mixture of both types of linkages could coexist. The amino groups that point away from this surface are each keyed into the -(SiO−)6 macro-rings of the adjacent silicate surface, resulting in an amino-functionalized ordered two-dimensional organo-mineral assembly. Keywords: kaolinite, halloysite, organo-mineral nanocomposites, clay functionalization, supramolecular assemblies.

Ag–Pd and CuO–Pd nanoparticles in a hydroxyl-group functionalized ionic liquid: synthesis, characterization and catalytic performance

2015 ◽  
Vol 5 (3) ◽  
pp. 1683-1692 ◽  
Author(s):  
Bin Zhang ◽  
Yuan Yuan ◽  
Karine Philippot ◽  
Ning Yan
Keyword(s):  
Thermal Decomposition ◽  
Ionic Liquid ◽  
Pd Nanoparticles ◽  
Catalytic Performance ◽  
Hydroxyl Group ◽  
Functionalized Ionic Liquid

Heteronuclear Ag–Pd and CuO–Pd nanoparticles with a controllable Ag : Pd or Cu : Pd ratio were easily synthesized through thermal decomposition of their acetate salts in a functionalized ionic liquid, [C2OHmim][NTf2].

Polyurethane Foams Reinforced with Biobased Materials: Properties and Applications

2019 ◽  
Vol 3 (1) ◽  
pp. 14-29
Author(s):  
Gholamali Sharifishourabi ◽  
Xiao Y. Chen ◽  
Tien-Binh Nguyen ◽  
Denis Rodrigue
Keyword(s):  
Construction Materials ◽  
Polyurethane Foams ◽  
Point Of View ◽  
Hydroxyl Group ◽  
Biobased Materials ◽  
Composite Foams ◽  
Wide Range ◽  
Multiphase Systems ◽  
Oil Absorbent ◽  
New Feature

Background:Today, polyurethane foams can be found in various commercial products such as bedding, home furniture, automotive interiors and even construction materials. From a chemical point of view, polyurethane foams are made from a chemical reaction between a polyol (molecules with more than one hydroxyl group) and a diisocyanate in the presence of a blowing agent.Objective:Because of their highly stable bonds, polyurethane foams are considered as nondegradable leading to some environmental impact. To address this concern different bio-based fillers have been used to create "greener" polyurethane materials. This review presents an overview of different bio-based fillers and containing natural polyols for polyurethane foams formulation with respect to their natural properties, sizes, geometries and contents.Method:A wide range of bio-based fillers derived from wood and non-wood sources are summarized based on their physico-mechanical properties. Then, possible applications are presented and future trends are discussed for the research and development of these complex (multiphase systems) materials (polymer composite foams).Conclusion:Beside traditional polyurethane foams applications including automotive, building, home furniture and package, bio-based filler addition could bring new feature and widen their applications such as shape memory and medication, as well as oil absorbent.

WATERPROOF ANTI-EXPLOSIVE POWDERS FOR COAL MINES

2014 ◽  
Vol 59 (1) ◽  
pp. 169-178
Author(s):  
Bronisław Buczek ◽  
Elżbieta Vogt
Keyword(s):  
Thermal Decomposition ◽  
Stearic Acid ◽  
Mining Industry ◽  
Vapour Phase ◽  
Point Of View ◽  
Raw Material ◽  
Limestone Powder ◽  
Powder Layer ◽  
Vapour Adsorption ◽  
Lime Powder

Abstract Limestone powder characterized by hydrophobic properties is used as an anti-explosive agent in coal mining industry. Unfortunately, the standard method of producing such powder by milling limestone with stearic acid is practically unprofitable in many modernized quarries and plants, and sometimes literally impossible due to the introduction of technological changes and implementation of modern mills. Then new methods of hydrophobization of limestone surfaces ought be searched. In the work two methods hydrophobization: from the stearic acid vapour phase and from silicone solutions are proposed. Lime dust from the Czatkowice Quarry of Lime was used as a raw material during investigations. It is a good agent for research because it is possible to compare the properties of samples modified in this work to the properties of anti-explosive lime powder (Polish Standard, 1994) used in mining industry in Poland. The first technique of limestone powder hydrophobization was carried out in an apparatus of own design (Vogt, 2008, 2011), and it consisted in free sedimentation of the powder layer dispersed by stearic acid vapour in powder counter current flow. The second way of modification consisted in mixing in the evaporating dish substrates: limestone powder and dope - silicone solution - Sarsil® H-15 (Vogt & Opaliński, 2009; Vogt & Hołownia, 2010). Evaluation of properties so-obtained waterproof powders was carried out according to the Polish Standard, as well as using original powder determination ways, with the Powder Characteristic Tester (Index tables, Tablets & Capsules, 2005). Moreover water vapour adsorption isotherms were obtained and the thermal decomposition of powder was made. All modified samples acquired the hydrophobic character. Therefore we can state that the both proposed methods of hydrophobization of the limestone powder are useful. The parameters obtained with the use of Powder Characteristics Tester enable us to make a characterization of limestone properties not only as a water resistant material but also from the cohesion point of view. On the base of TG, DTG or DTA and EGA curves for all investigated materials was stated that the character of the thermal decomposition of modified samples is the same as this one for raw powder, what is profitable for application of hydrophobized powders as an anti-explosive agent.

Sulfur Dioxide Production from Phosphogypsum: Thermodynamic Analysis and Experimental Results

2010 ◽  
Vol 660-661 ◽  
pp. 253-258
Author(s):  
Humberto Molinar Henrique ◽  
Priciane Martins Parreira
Keyword(s):  
Thermal Decomposition ◽  
Sulfuric Acid ◽  
Sulfur Dioxide ◽  
Phosphoric Acid ◽  
Rotary Kiln ◽  
Theoretical Approach ◽  
Point Of View ◽  
Experimental Results ◽  
Experimental Setup ◽  
Fertilizer Industry

Phosphogypsum or chemical gypsum is a by-product generated in the manufacture of phosphoric acid, generated in the proportion of 4 to 6 tons for every ton of acid produced by the fertilizer industry. Its reuse is important from the economic, social and environmental point of view. The purpose of this paper is to investigate the thermodynamic condition of sulfur dioxide recovering from thermal decomposition of phosphogypsum. The main advantage of this process is to return the sulfur dioxide to sulfuric acid manufacturing. In this case, sulfur demand by fertilizer industry and phosphogypsum generation could be greatly reduced. Experimental results were obtained from a lab scale rotary kiln. Theoretical approach and experimental setup were validated by using the actual data from thermal decomposition of limestone. Theoretical and experimental results showed the thermal decomposition of phosphogypsum is thermodynamically feasible only at high temperatures.

Water-Resistant Poly(Vinyl Alcohol) Hybrid Nanofibers Incorporating Polyhedral Oligosilsesquioxane (POSS)

2010 ◽  
Vol 89-91 ◽  
pp. 727-732 ◽  
Author(s):  
Byoung Suhk Kim ◽  
Hyo Kyoung Kang ◽  
Myung Seob Khil ◽  
Hak Yong Kim ◽  
Ick Soo Kim
Keyword(s):  
Thermal Decomposition ◽  
Pure Water ◽  
Hydroxyl Group ◽  
Poly Vinyl Alcohol ◽  
Polyhedral Oligosilsesquioxane ◽  
Before And After ◽  
Ft Ir ◽  
Decomposition Behavior ◽  
Nanofiber Mats ◽  
Straightforward Approach

We have explored a straightforward approach for achieving water-resistant properties of the electrospun PVA nanofibers. The electrospun PVA nanofibers are post-treated with a hydrophobic polyhedral oligosilsesquioxane (POSS) hybrid macromer via a direct urethane reaction between the hydroxyl group of PVA and the isocyanate group of POSS macromers. The POSS-modified PVA nanofibers are characterized by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and water resistant property. The morphologies of the electrospun PVA nanofibers before and after POSS post-treatments are regular and a narrow distribution of diameters was observed, indicating a uniform post-treatment of POSS macromers onto the PVA nanofibers. Thermal decomposition behavior of the POSS-modified PVA nanofibers was altered compared to the pure PVA nanofibers, suggesting the suppression of thermal decomposition due to the incorporation of POSS macromers. In addition, the pure PVA nanofiber mats immersed in pure water exhibited no characteristic morphology, whereas the POSS-modified PVA nanofiber mats showed the texture morphology, indicating an enhanced water-resistant property.

Thermal decomposition of magnesium sesquicarbide

1983 ◽  
Vol 48 (7) ◽  
pp. 1963-1968 ◽  
Author(s):  
Bohumil Hájek ◽  
Pavel Karen ◽  
Vlastimil Brožek
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Data ◽  
Arrhenius Equation ◽  
Kinetic Equations ◽  
Decomposition Reaction ◽  
Point Of View ◽  
X Ray Diffraction ◽  
X Ray ◽  
Diffraction Patterns ◽  
Thermal Stability Of

The structure of Mg2C3 and the course of its decomposition were studied. The powder X-ray diffraction patterns were analyzed to obtain the lattice parameters for hexagonal Mg2C3, a = 743.4 ± 0.5 pm, c = 1 056.4 ± 1.6 pm. Thermal decomposition data were obtained for temperatures 670-740 °C and pressure 130 Pa; they could be fitted satisfactorily by kinetic equations for various processes, including the 1 st order decomposition reaction, and so the controlling phenomenon of the reaction cannot be deduced based on the kinetic data. The 1 st order rate constants and reaction halflives were evaluated for various temperatures and approximated by the Arrhenius equation to calculate the parameters AA = 1.97 . 1014 s-1, EA = 333 kJ mol-1. The conditions of synthesis of Mg2C3 are discussed from the point of view of the choice of a suitable hydrocarbon for the reaction with magnesium. The thermal stability of the sesquicarbide increases with increasing pressure; it could be formed from dicarbide and sustained even at a temperature of 1 450 °C by applying a pressure as high as 6 GPa.

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