Discoloured

If an impure and discoloured sample of m-dinitrobenzene is used in the above preparation, add some animal charcoal to the solution immediately prior to the 20 minutes boiling the use of charcoal is to be avoided when possible, however, as it is liable to absorb an appreciable quantity of the /-nitroanilinc. 

No corks or rubber stoppers are, in general, required. Contamination or discolouration due to these is therefore avoided. Occasionally, a small rubber stopper may be employed, e.g., for the insertion of a thermometer, but, should the very small surface of rubber thus exposed to the action of the organic vapours be undesirable, a thermometer with a ground glass cone can be used. 

Pimelic acid. Heat a mixture of 18 g. of pentamethylene dicyanide and 250 g. of 50 per cent, sulphuric acid by weight in a 750 ml. round-bottomed flask under reflux for 9 hours. INIost of the pimehc acid separates from the cold reaction mixture. Filter oflF the crystaUine acid upon a sintered glass funnel. Saturate the filtrate with ammonium sulphate and extract it with three 50 ml. portions of ether. Dissolve the residue on the filter (which is shghtly discoloured, but is fairly pure pimehc acid) in the combined ethereal extracts, dry with anhydrous sodium or magnesium sulphate, and remove the ether by distiUation. Recrystallise the residual sohd acid from benzene containing 5 per cent, of ether. The yield of pure pimehc acid, m.p, 105-106°, is 22 g. 

Pure aniline has a b.p. of 184°. When freshly distilled it is a colourless liquid, but becomes discoloured on standing, particularly when exposed to light owing to atmospheric oxidation. The colour may usually be removed by distillation from a little zinc dust. 

Acetylene is obtained from a cylinder (at ground level outside the fum chamber) and is freed from acetone by passing through two 500 ml. wash bottles, half filled with concentrated sulphuric acid, at the rate of 2-3 litres per minute when the acid in the second wash bottle becomes discoloured, the wash bottles should be recharged with fresh acid. The... 

The following alternative procedure is recommended and it possesses the advantage that the same tube may be used for many sodium fusions. Support a Pyrex test tube (150 X 12 mm.) vertically in a clamp lined with asbestos cloth or with sheet cork. Place a cube (ca. 4 mm. side = 0 04 g.) of freshly cut sodium in the tube and heat the latter imtil the sodium vapour rises 4 5 cm. in the test-tube. Drop a small amount (about 0-05 g.) of the substance, preferably portionwise, directly into the sodium vapour CAUTION there may be a slight explosion) then heat the tube to redness for about 1 minute. Allow the test tube to cool, add 3-4 ml. of methyl alcohol to decompose any unreacted sodium, then halffill the tube with distilled water and boil gently for a few minutes. Filter and use the clear, colourless filtrate for the various tests detailed below. Keep the test-tube for sodium fusions it will usually become discoloured and should be cleaned from time to time with a little scouring powder. 

Impurities in mineral fillers can have serious effects. Coarse particles (grit) will lead to points of weakness in soft polymers which will therefore fail under stresses below that which might be expected. Traces of copper, manganese and iron can affect the oxidative stability whilst lead may react with sulphur-containing additives or sulphurous fumes in the atmosphere to give a discoloured product. 

Other polymers can be more troublesome. Poly(vinyl chloride) requires the incorporation of stabilisers and even so may discolour and give off hydrochloric acid, the latter having a corrosive effect on many metals. At the same time some metals have a catalytic effect on this polymer so that care has to be taken in the construction of barrels, screws and other metal parts liable to come into contact with the polymer. 

The disadvantages of the suspension process are that about 70% of the volume of the kettle is taken up by water, the need for a drying stage which could cause discolouration by degradation and the need to convert the small spheres formed into a larger shape suitable for handling. Furthermore, the suspension method cannot easily be converted into a continuous process. 

Notable among the alternative materials are the MBS polymers, in which methyl methacrylate and styrene are grafted on to the polybutadiene backbone. This has resulted in two clear-cut advantages over ABS. The polymers could be made with high clarity and they had better resistance to discolouration in the presence of ultraviolet light. Disadvantages of MBS systems are that they have lower tensile strength and heat deflection temperature under load. 

The resins tend to be dark in colour and it has been suggested that this is due to a fulvenation process involving the unsaturated end group of a polymer molecule. Hydrogenation of the polymer molecule, thus eliminating unsaturation, helps to reduce discolouration. 

The condensation reaction is promoted by certain polar solvents and of the many which have been tested dimethyl sulphoxide appears to be the most effective. As usual with linear condensation polymers molecular equivalence and near-absence of monofunctional material is necessary to ensure a high molecular weight. Moisture and alcohols can also have a devastating effect on the molecular weight. In the case of water it is believed that 4-chlorophenyl 4-hydroxyphenyl sulphone is formed which functions as an effective chain terminator. Gross contamination with air is also believed to reduce the maximum attainable molecular weight as well as causing intense discolouration. 

The chemical resistance of celluloid is not particularly good. It is affected by acids and alkalis, discolours on exposure to sunlight and tends to harden on aging. More seriously it is extremely inflammable, this being by far the greatest limitation of the material. 

Laminates prepared from highly chlorinated resins of this type tend to discolour on prolonged exposure to light and this retarded the early development of these resins. Stabilisers have, however, been developed and current resins are substantially superior to the early resins of this type. 

Compared with nylon 66 fibres, the polyurethane fibres (known as Perlon U) have a tensile strength at the higher end of the range quoted for nylon 66, they are less prone to discolouration in air, are more resistant to acid conditions and they have a lower moisture absorption. On the debit side they are less easy to dye, are hard, wiry and harsh to handle and have too low a softening point for many applications. They are currently of little importance but have found some use in bristles, filler cloths, sieves and a few other miscellaneous applications. 

In the 1990s this approach became more common in order to ensure sufficient compressive strength with the trend to lower bulk densities. Furthermore the proportion of SAN to polyol has been increased to about 40%. This may lead to serious stability problems and care must be taken to control the size and distribution of the particles and prevent agglomeration. Polymer polyols using polystyrene as the polymer component have recently become available (Postech-Shell) and are claimed to exhibit good stability, low viscosity and less discolouration as well as providing price advantages. 

During World War II, polychloroprene was chosen as a replacement for natural rubber because of its availability. Two copolymers of chloroprene and sulphur which contain thiuram disulphide were available (Neoprene GN and CG). One of the first successful applications of these polychloroprene adhesives was for temporary and permanent sole attachment in the shoe industry. However, these polychloroprene cements show a decrease in viscosity on ageing and a black discolouration appears during storage in steel drums. Discolouration was produced by trace amounts of hydrochloric acid produced by oxidation of polychloroprene... 

Mercaptan-inodified polychloroprenes provide lighter colour to solutions and are more resistant to discolouration than sulphur-modified polychloroprenes. Also mercaptan-modified polychloroprenes exhibit better ageing, and improved thermal and solution stability. 

Neoprene GN (1942). It is a general-purpose sulphur-modified polychloroprene used in the shoe industry. This polychloroprene has two limitations the viscosity decreases on ageing and a black discolouration appears during storage. 

Neoprene AC (1947). This polychloroprene was developed to provide better viscosity stability and resistance to discolouration, but it cures much more slowly at room temperature. It is a fast crystallizing grade and contains about 90% trans-, 4 structure. 

On the other hand, not only initial colour but colour change (discolouration) of the resin under UV light and heat is important. Colour retention of a resin is related to the chemical stability and increases as the degree of non-aromatic conjugated unsaturation of the resin molecule decreases. Thus, for rosins a high level of abietic-type resin acids lead to relatively unstable resins. Hydrogenation and disproportionation as well as esterification provide improved stability and colour retention to rosins. 

Aromatic amines are the most effective primary antioxidants (Fig. 34) but they are discolouring and can only be used where the darker colours are acceptable (for instance in rubber adhesive formulations containing carbon blacks as fillers). The... 

The other class of primary antioxidants are the phenols (hindered phenols, hindered bisphenols, hindered thiobisphenols, polyhydroxy phenols) (Fig. 34). Phenolic antioxidants are generally used when the discolouration of the amine antioxidants cannot be tolerated. Phenols may produce coloured reaction products (yellow, tan or pink) but the discolouration is significantly less than produced with amines. 

Acid acceptor. This is the main function of metal oxides in CR adhesive formulations. Upon age, small amounts of hydrochloric acid are released which may cause discolouration and substrate degradation. Magnesium oxide (4 phr) and zinc oxide (5 phr) act synergistically in the stabilization of solvent-borne polychloroprene adhesives against dehydrochlorination. 

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