Phenolic resins nitration

There was significant interest in developing commercial processes based on phenolic resins in the 1890-1910 era. By this time, cellulose nitrate, vulcanized rubber, and viscose rayon had all found places in commerce [24]. Smith patented processes for manufacture of commercially useful molded articles from phenolic in 1899-1900 [2,25-28]. His products were made with phenol, paraldehyde (2,4,6-trimethyl-1,3,5-trioxane) or parafonnaldehyde, and additives in the presence of HCl at elevated temperatures. 

Oya, A., Yoshida, S., Abe, Y., Iizuka, T. and Makiyama, N., Antibacterial activated carbon fiber derived from phenolic resin containing silver nitrate, Carbon, 1993, 31(1), 71 73. 

The ease with which the phenols are nitrated has already been discussed. The process is not satisfactory, however, even when dilute nitric acid is used, because resinous by-products are formed as a result of oxidation and condensation. Nitration with nitrogen peroxide in non-aqueous solvents such as benzene and petrol ether gives better results (Ber., 1921, 54, 1776). 

Pentachlorophenol Petroleum wax Phenolic resins, Novalak resin Pine rosin Polyethylene resins Polystyrene resins Polypropylene-maleic anhydride Potassium nitrate Resins... 

Uvinul 3040 is readily compatible with many plastics. It is a particularly effective UV absorber in PVC, acrylic resins, alkyd resins, cellulose nitrate, phenolic resins, and oil colors. 

The first plastic made was cellulose nitrate, which is a derivative of cellulose, obtained from wood pulp. The first truly synthetic polymer material was phenolic resin, which was synthesized from phenol and formaldehyde derived from coal. Today, the source of organic chemicals for the production of polymers has shifted from these traditional sources to petroleum and natural gas. Petroleum as a raw material for organic chemicals (petrochemicals) is relatively cheap, readily available in large tonnages, and more easily processed than the other main source of organic chemicals — coal. 

Binders are macromolecular products with a molecular mass between 500 and ca. 30000. The higher molecular mass products include cellulose nitrate and polyacrylate and vinyl chloride copolymers, which are suitable for physical film formation. The low molecular mass products include alkyd resins, phenolic resins, polyisocyanates, and epoxy resins. To produce acceptable films, these binders must be chemically hardened after application to the substrate to produce high molecular mass cross-linked macromolecules. 

Cyclohexyl acetate [622-45-7] is very slightly miscible with water, but completely miscible with common organic solvents. Its solvency properties are comparable to those of amyl acetate. Cyclohexyl acetate dissolves oils, fats, resins, waxes, cellulose nitrate, cellulose tripropionate and acetobutyrate, alkyd resins, unsaturated and saturated polyester resins, phenolic resins and aminoplasts, poIy(vinyI chloride), vinyl chloride copolymers, poly(vinyl acetate), poly(vinyl ethers), epoxy resins, and acrylic resins, basic dyes, blown oils, crude rubber, metallic soaps, shellac, and bitumen. 

This equation cannot stand for all hydrolysis process of esters [32, 33]. In the same conditions, the hydrolysis products of dUferent nitrate esters include phenolic resin, oxalic acid, and ammonium. In alkaline agents, glycCTol is not found in the... 

Rapidly curing resole phenolic resins have been reported to use barium acetate and zinc nitrate and organic peroxides [105],... 

Selected alkyd resins are compatible with cellulose nitrate, amino resins, phenolic resins, epoxy resins, silicones, acrylics, chlorinated rubber, and styrene. When added to cellulose nitrate, short-oil alkyds improve gloss, adhesion, and flexibility of these commercial coatings. The chemical resistance of short-oil alkyds is improved when they are reacted with amino resins. Alkyds also react with phenolics to produce chroman-type alkali-resistant coatings. 

Picric acid, the 2 4 6-trinitro derivative of phenol, cannot be prepared in good yield by the action of nitric acid upon phenol since much of the latter is destroyed by oxidation and resinous products are also formed. It is more convenient to heat the phenol with concentrated sulphuric acid whereby a mixture of o- and p-phenolsulphonic acids is obtained upon treatment of the mixture with concentrated nitric acid, nitration occurs at the two positicsis mela to the —SOjH group in each compound, and finally, since sulphonation is reversible, the acid groups are replaced by a third iiitro group yielding picric acid in both cases ... 

Cautiously add 250 g. (136 ml.) of concentrated sulphuric acid in a thin stream and with stirring to 400 ml. of water contained in a 1 litre bolt-head or three-necked flask, and then dissolve 150 g. of sodium nitrate in the diluted acid. Cool in a bath of ice or iced water. Melt 94 g. of phenol with 20 ml. of water, and add this from a separatory funnel to the stirred mixture in the flask at such a rate that the temperature does not rise above 20°. Continue the stirring for a further 2 hours after all the phenol has been added. Pour oflF the mother liquid from the resinous mixture of nitro compounds. Melt the residue with 500 ml. of water, shake and allow the contents of the flask to settle. Pour oflF the wash liquor and repeat the washing at least two or three times to ensure the complete removal of any residual acid. Steam distil the mixture (Fig. II, 40, 1 or Fig. II, 41, 1) until no more o-nitrophenol passes over if the latter tends to solidify in the condenser, turn oflF the cooling water temporarily. Collect the distillate in cold water, filter at the pump, and drain thoroughly. Dry upon filter paper in the air. The yield of o-nitrophenol, m.p. 46° (1), is 50 g. 

Several other resins can be blended with alkyd resins to introduce desired improvement in properties, e. g. cellulose nitrate, chlorinated rubber, phenolics, amino resins or silicons oils. Vinyl monomers like styrene can be added to alkyd resins along with initiator to get a tougher resin with shorter drying times and lighter colour. 

Subsequent tests in which small portions of these undiluted liquid amines and dried cellulose nitrate linters were contacted (with a little added butyl acetate for the solid phenol) under various conditions, gave ignition with the first 3 amines, and exotherms to 110°C with foaming decomposition for the remaining 4. Other amine resin components showed slight or no exotherms in either test [2], Contact of cellulose nitrate with a little butylamine caused explosive reaction [3]. 

What was the first synthetic plastic Although some nineteenth-century experiments should be mentioned, such as the 1869 molding process for cellulose nitrate discovered by John and Isaiah Hyatt, probably the first major breakthrough came in 1910 with Leo Baekeland s discovery of phenol formaldehyde resins (Bakelite ). These are still the leading thermoset plastics made today. The pioneering work of Wallace Carothers at Du Pont in 1929 produced the nylons now used primarily as fibers but known as the beginning of thermoplastic resin technology. 

---