Acetates, molten

Leonesi D, Cingolani A, Franzosini P (1973) ElecUic conductivity of sodium-potassium acetates molten system. J Chem Eng Data 18 391-393... 

For this preparation, it is particularly necessary that the sodium acetate should be free from traces of water. The anhydrous material can be prepared by gently heating the hydrated salt (CHsCOONa,3HjO) in an esaporating-basin over a small Bunsen flame. The salt dissolves in its water of ciystallisation and resolidifies as this water is driven off further heating then causes the anhydrous material to melt. Stir the molten anhydrous material to avoid charring, and then allow it to cool in a desiccator. Powder the cold material rapidly in a mortar, and bottle without delay. 

Extrusion Processes. Polymer solutions are converted into fibers by extmsion. The dry-extmsion process, also called dry spinning, is primarily used for acetate and triacetate. In this operation, a solution of polymer in a volatile solvent is forced through a number of parallel orifices (spinneret) into a cabinet of warm air the fibers are formed by evaporation of the solvent. In wet extmsion, a polymer solution is forced through a spinneret into a Hquid that coagulates the filaments and removes the solvent. In melt extmsion, molten polymer is forced through a multihole die (pack) into air, which cools the strands into filaments. 

First,/)-hydroxybenzoic acid (HBA) and 6-hydroxy-2-naphthoic acid (HNA) are acetylated to produce the low melting acetate esters which are molten at 200°C. In an inert gas, the two monomers are melted together at 200°C. The temperature is raised to 250—280°C and acetic acid is coUected for 0.5 to 3 h. The temperature is raised to 280—340°C and additional acetic acid is removed in vacuum for a period of 10 to 60 min. The opalescent polymer melt produced is extmded through a spinning jet, foUowed by melt drawdown. The use of the paraUel offset monomer, acetylated HNA, results in the formation of a series of random copolyesters of different compositions, many of which faU within the commercially acceptable melting range of... 

The anhydride can be made by the Hquid-phase oxidation of acenaphthene [83-32-9] with chromic acid in aqueous sulfuric acid or acetic acid (93). A postoxidation of the cmde oxidation product with hydrogen peroxide or an alkaU hypochlorite is advantageous (94). An alternative Hquid-phase oxidation process involves the reaction of acenaphthene, molten or in alkanoic acid solvent, with oxygen or acid at ca 70—200°C in the presence of Mn resinate or stearate or Co or Mn salts and a bromide. Addition of an aHphatic anhydride accelerates the oxidation (95). 

Rosin, modified rosins, and derivatives are used in hot-melt adhesives. They are based primarily on ethylene—vinyl acetate copolymers. The rosin derivative is used in approximately a 1 1 1 concentration with the polymer and a wax. The resin provides specific adhesion to the substrates and reduces the viscosity at elevated temperatures, allowing the adhesive to be appHed as a molten material. 

Anhydrous stannous chloride, a water-soluble white soHd, is the most economical source of stannous tin and is especially important in redox and plating reactions. Preparation of the anhydrous salt may be by direct reaction of chlorine and molten tin, heating tin in hydrogen chloride gas, or reducing stannic chloride solution with tin metal, followed by dehydration. It is soluble in a number of organic solvents (g/100 g solvent at 23°C) acetone 42.7, ethyl alcohol 54.4, methyl isobutyl carbinol 10.45, isopropyl alcohol 9.61, methyl ethyl ketone 9.43 isoamyl acetate 3.76, diethyl ether 0.49, and mineral spirits 0.03 it is insoluble in petroleum naphtha and xylene (2). 

Titanium Silicides. The titanium—silicon system includes Ti Si, Ti Si, TiSi, and TiSi (154). Physical properties are summarized in Table 18. Direct synthesis by heating the elements in vacuo or in a protective atmosphere is possible. In the latter case, it is convenient to use titanium hydride instead of titanium metal. Other preparative methods include high temperature electrolysis of molten salt baths containing titanium dioxide and alkalifluorosiUcate (155) reaction of TiCl, SiCl, and H2 at ca 1150°C, using appropriate reactant quantities for both TiSi and TiSi2 (156) and, for Ti Si, reaction between titanium dioxide and calcium siUcide at ca 1200°C, followed by dissolution of excess lime and calcium siUcate in acetic acid. 

Substituents in the 6-position (cf. 267) show appreciable reactivity. 6-Bromo-as-triazine-3,5(2j, 4j )-dione (316) undergoes 6-substitution with secondary amines or hydrazine, with mercaptide anions or thiourea (78°, 16 hr), with molten ammonium acetate (170°, 24 hr, 53% yield), and with chloride ion during phosphorous oxychloride treatment to form 3,5,6-trichloro-as-triazine. The latter was characterized as the chloro analog of 316 by treatment with methanol (20°, heat evolution) and hydrolysis (neutral or acid) to the dioxo compound. The mercapto substituent in 6-mercapto-as-triazine-3,5(2iI,4if)-dione is displaced by secondary... 

Den Hertog and Overhoff - observed that when pyridine in sulfuric acid is added to molten potassium sodium nitrate the 3-nitro derivative is formed at 300°C, whereas at 450°C 2-nitropyridme is the main product. The latter is probably a free-radical process. Schorigin and Toptschiew obtained 7-nitroquinoline by the action of nitrogen peroxide on quinoline at 100°C, possibly through the homolytic addition of NOa. Laville and Waters reported that during the decomposition of pernitrous acid in aqueous acetic acid, quinoline is nitrated in the 6- and 7-positions. They considered that the reaction proceeds as shown in Scheme 3. 

TNT Coated RDX. 60g of molten TNT are added to a w slurry of 540g of finely divided RDX (w ppt from acet soln) under mechanical agitation. The temp of the TNT-RDX slurry is maintained at about 90° and stirring is contd for 0.5 hr. After cooling to about 50°, the TNT-coated RDX is recovered by filtrn. The RDX thus treated, and presumed to be 10% coated or a 90/10 RDX/TNT mixt, is further blended by hand after rolling to crush any aggregates formed during the process... 

Several laboratory explns have occurred when using the reaction between P trichloride and acetic acid to form acetyl chloride. Poor heat control probably caused formation of phosphine (Ref 2). Two later explns may have been due to ingress of air and combustion of traces of phosphine (Ref 8). Al powder burns in P trichloride vapor (Ref 4) K ignites and molten Na explds on contact (Ref 3). Each drop of chromyl chloride added to well-cooled P trichloride produces a hissing noise, incandescence, and sometimes an expln (Ref 5). It reacts with fluorine with incandescence (Ref 1), and with ignition... 

On an industrial scale, PA-6 is synthesized from e-caprolactam with water as the initiator. The process is very simple if the reaction is earned out at atmospheric pressure. The polymerization is earned out in a VK-reactor (Fig. 3.23), which is a continuous reactor without a stirrer, with a residence time of 12-24 h at temperatures of 260-280°C.5,28 Molten lactam, initiator (water), and chain terminator (acetic acid) are added at the top and the polymer is discharged at the bottom to an extruder. In this extruder, other ingredients such as stabilizers, whiteners, pigments, and reinforcing fillers are added. The extruded thread is cooled in a water bath and granulated. The resultant PA-6 still contains 9-12%... 

The explosion hazards associated with use of palm oil when coating steel sheets with molten alloys (8-12% tin) is eliminated by use of molten sodium acetate in place of the oil. 

A specific case of the carbonium ion mechanism [Eq. (5)] with reasonable plausibility is decarboxylation of metal arenoates by classic electrophilic aromatic substitution [Eq. (12)]. This mechanism would be favored by electron-donating substituents and has been invoked to explain the relative ease of decarboxylation of p-methoxybenzoic acid in molten mercuric trifluoroacetate (77) as well as the very facile decarboxylation on reaction of polymethoxybenzoic acids with mercuric acetate (18) (see below). 

In continuous process a mixture of molten Caprolactam, water and acetic acid is pumped continuously at 260°C through a reactor. Steam is removed at intervals. The residuence time in reactor is 18-20 hours. The product is directly spun into fibres ... 

The primary starting material for the synthesis of perylene tetracarboxylic acid pigments is the dianhydride 71. It is prepared by fusing 1,8-naphthalene dicar-boxylic acid imide (naphthalic acid imide 69) with caustic alkali, for instance in sodium hydroxide/potassium hydroxide/sodium acetate at 190 to 220°C, followed by air oxidation of the molten reaction mixture or of the aqueous hydrolysate. The reaction initially affords the bisimide (peryldiimide) 70, which is subsequently hydrolyzed with concentrated sulfuric acid at 220°C to form the dianhydride ... 

The 3-alkylthio groups in 1,2,4-thiadiazoles are difficult to replace. Thus, 3-alkylthio-l,2,4-thia-diazoles resist the action of aniline at 100°C, ammonia at 120°C, molten urea and ammonium acetate however, hydrazine attacks 3-methylthio-l,2,4-thiadiazole (142) forming 3-amino-1,2,4-triazole (143) (Equation (21)) <65AHC(5)119>. In contrast to 3-alkylthiogroups, 5-sulfonyl groups in... 

Reactions conducted in molten quaternary phosphonium salts require no other solvent (199). This material serves as both promoter and reaction medium. Care must be exercised in choosing the salt in such a reaction, since any decomposition could lead to products such as trialkylphosphines and alkyl halides which are expected to be deleterious to catalyst performance. Tetrabutylphosphonium bromide is reported to provide a stable catalyst medium which can be recycled (199, 200), but other related salts show evidence of thermal decomposition during catalytic reactions. Experiments in tetrabutylphosphonium acetate, for example, are found to produce large amounts of methyl and ethylene glycol acetate esters (199). 

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