Resins Aniline

Aniline—formaldehyde resins were once quite important because of their excellent electrical properties, but their markets have been taken over by newer thermoplastic materials. Nevertheless, some aniline resins are stiU. used as modifiers for other resins. Acrylamide (qv) occupies a unique position in the amino resins field since it not only contains a formaldehyde reactive site, but also a polymerizable double bond. Thus it forms a bridge between the formaldehyde condensation polymers and the versatile vinyl polymers and copolymers. 

Commercially available 2-fluoro-5-nitroaniline was diazotized and coupled to benzylaminomethylpolystyrene to give the immobilized triazene. After nucleophilic displacement with primary amines to furnish an aniline resin, the cleavage with trifluoroacetic acid in dichloromethane proceeded smoothly at room temperature within minutes, resulting in nitrobenzotriazoles [627],... 

M.W. thousand to tens of thousands) Cationic (P225) Amphoteric Nonionic Soluble aniline resin, polythiourea, polyvinyl ethylamine Poly-2-methacryloyloxy ethylene Trimethyl ammonium chlorate Animal gelatins Starches, gums... 

Aniline resins may be identified by pyrolytic decomposition. The addition of the gases produced to either sodium hypochlorite or calcium hypochlorite solution yields a red-violet or violet solution. 

Synonyms Butyraldehyde-aniline reaction prod. Butyraldehyde-aniline resin Uses Accelerator for NR, SBR, CR, MR, and latexes activator for acidic accelerators antioxidant for CR, NR, SBR, EPDM accelerator for food-contact rubber articles for repeated use... 

Butyraldehyde-aniline reaction prod. Butyraldehyde-aniline resin. See Butyraldehyde-aniline condensation product Butyraldehyde diethyl acetal CAS 3658-95-5... 

Thus, urea formaldehyde resins are particularly suitable as rapid-setting (curing, hardening) molding materials. Aniline formaldehyde resins are hardened with compounds such as paraformaldehyde, hexamethylene tetramine, or furfurol, since as no polycondensation reactions occur in the absence of acid catalysts, pre-cross-linked products have to be used for this purpose. Aniline resins therefore cannot be used as rapid-setting molding materials (cf. Section 12.2.2). 

Conversion of the salt of a weak base into the free base. Prepare a column of a strong base anion resin (such as Amberlite IRA-40o(OH) ) washed with distilled water as above. Drain off most of the water and then allow 100 ml. of A//2.Na.2C03 solution to pass through the column at 5 ml. per minute. Again wash the column with 200 ml. of distilled water. Dissolve 0-05 g. of aniline hydrochloride in 100 ml. of distilled water and pass the solution down the column. The effluent contains aniline in solution and free from all other ions. 

In 1993, worldwide phenol production was more than 5.2 million metric tons (1). The predominant uses of phenol are in phenoHc resins (qv), bisphenol A, caprolactam (qv), aniline, and alkylphenols (qv). 

Some other phenol derivatives are somewhat local in appHcation. Eor example, aniline is produced from phenol at only two plants, one in Japan and one in the United States. Likewise, phenol is used in the production of nylon, via caprolactam (qv) or adipic acid (qv) by only one United States producer and one European producer. These markets, like the phenoHc resin and polycarbonate markets, are quite cycHcal. Thus, the entire phenol market tends to be cycHcal and closely tied to the housing and automotive markets. 

Other Reactants. Other reactants are used in smaller amounts to provide phenoHc resins that have specific properties, especially coatings appHcations. Aniline had been incorporated into both resoles and novolaks but this practice has been generally discontinued because of the toxicity of aromatic amines. Other materials include rosin (abietic acid), dicyclopentadiene, unsaturated oils such as tung oil and linseed oil, and polyvalent cations for cross-linking. 

Other Materials. Benzoguanamine and acetoguanamine may be used in place of melamine to achieve greater solubiHty in organic solvents and greater chemical resistance. Aniline and toluenesulfonamide react with formaldehyde to form thermoplastic resins. They are not used alone, but rather as plasticizers (qv) for other resins including melamine and urea—formaldehyde. The plasticizer may be made separately or formed in situ during preparation of the primary resin. 

The term aminoplastics has been coined to cover a range of resinous polymers produced by interaction of amines or amides with aldehydes. Of the various polymers of this type that have been produced there are two of current commercial importance in the field of plastics, the urea-formaldehyde and the melamine-formaldehyde resins. There has in the past also been some commercial interest in aniline-formaldehyde resins and in systems containing thiourea but today these are of little or no importance. Melamine-phenol-formaldehyde resins have also been introduced for use in moulding powders, and benzoguanamine-based resins are used for surface coating applications. 

Although occasionally in demand because of their good electrical insulation properties, aniline-formaldehyde resins are today only rarely encountered. They may be employed in two ways, either as an unfilled moulding material or in the manufacture of laminates. 

To produce a moulding composition, aniline is first treated with hydrochloric acid to produce water-soluble aniline hydrochloride. The aniline hydrochloride solution is then run into a large wooden vat and formaldehyde solution is run in at a slow but uniform rate, the whole mix being subject to continuous agitation. Reaction occurs immediately to give a deep orange-red product. The resin is still a water-soluble material and so it is fed into a 10% caustic soda solution to react with the hydrochloride, thus releasing the resin as a creamy yellow slurry. The slurry is washed with a counter-current of fresh water, dried and ball-milled. 

Because of the lack of solubility in the usual solvents, aniline-formaldehyde laminates are made by a pre-mix method. In this process the aniline hydrochloride-formaldehyde product is run into a bath of paper pulp rather than of caustic soda. Soda is then added to precipitate the resin on to the paper fibres. The pulp is then passed through a paper-making machine to give a paper with a 50% resin content. 

Aniline-formaldehyde resin has very poor flow properties and may be moulded only with difficulty, and mouldings are confined to simple shapes. The resin is essentially thermoplastic and does not cross-link with the evolution of volatiles during pressing. Long pressing times, about 90 minutes for a 5 in thick sheet, are required to achieve a suitable product. 

As with the other aminoplastics, the chemistry of resin formation is incompletely understood. It is, however, believed that under acid conditions at aniline-formaldehyde ratios of about 1 1.2, which are similar to those used in practice, the reaction proceeds via p-aminobenzyl alcohol with subsequent condensation between amino and hydroxyl groups (Figure 24.10). 

Development work by Russian workers had led to interesting products formed by reaction of furfuryl alcohol with acetone and with aniline hydrochloride. The resins formed in each case have been found to be useful in the manufacture of organic-mineral non-cement concretes with good petrol, water and gas resistance. They also have the advantage of requiring only a small amount of resin to act as a binder. 

Solubility of resins can be predicted in a similar way as for the solubility of polychloroprene rubbers in a solvent mixture (see Section 5.5) by means of solubility diagrams (plots of the hydrogen bonding index (y) against the solubility parameter (5). Another more simple way to determine the solubility of resins is the determination of the cloud point, the aniline and the mixed aniline points. 

Aniline and mixed aniline point (DIN 51 775 modified). It is similar to the cloud point test except that the solvent is aniline, a very polar liquid. The aniline point is defined as the temperature at which a mixture of equal parts of aniline and the resin show the beginning of phase separation (i.e. the onset of clouding). Phase separation for aromatic resins occurs between I5°C and below zero for resins with intermediate aromaticity, it lies between 30 and 50°C and for non-aromatic resins, it is 50 to 100°C. Sometimes the mixed aniline point is used. It is similar to the aniline point except that the solvent is a mixture of one part of aniline and one part of w-heptane. The problem of both procedures is that precipitation of resins can be produced before the cloud is generated. 

The largest user of phenol in the form of thermosetting resins is the plastics industry. Phenol is also used as a solvent and in the manufacture of intermediates for pesticides, pharmaceuticals, and dyestuffs. Styrene is used in the manufacture of synthetic rubber and polystyrene resins. Phthalic anhydride is used in the manufacture of DMT, alkyd resins, and plasticizers such as phthalates. Maleic anhydride is used in the manufacture of polyesters and, to some extent, for alkyd resins. Minor uses include the manufacture of malathion and soil conditioners. Nitrobenzene is used in the manufacture of aniline, benzidine, and dyestuffs and as a solvent in polishes. Aniline is used in the manufacture of dyes, including azo dyes, and rubber chemicals such as vulcanization accelerators and antioxidants. 

The GBR resin works well for nonionic and certain ionic polymers such as various native and derivatized starches, including sodium carboxymethylcel-lulose, methylcellulose, dextrans, carrageenans, hydroxypropyl methylcellu-lose, cellulose sulfate, and pullulans. GBR columns can be used in virtually any solvent or mixture of solvents from hexane to 1 M NaOH as long as they are miscible. Using sulfonated PDVB gels, mixtures of methanol and 0.1 M Na acetate will run many polar ionic-type polymers such as poly-2-acrylamido-2-methyl-l-propanesulfonic acid, polystyrene sulfonic acids, and poly aniline/ polystyrene sulfonic acid. Sulfonated columns can also be used with water glacial acetic acid mixtures, typically 90/10 (v/v). Polyacrylic acids run well on sulfonated gels in 0.2 M NaAc, pH 7.75. 

A biphenyl diglycidyl ether based epoxy resin was crosslinked with aminecuring agents (d -diaminodiphenylmethane and aniline novolac) and phenolcuring agents (phenol novolac and catechol novolac), and the thermomechanical... 

As for the solid support, several polymer-supported amines were tested (Fig. 2). For either the pyrazole and isoxazole synthesis, the best results were given by aniline-functionalized cellulose, which has also the advantage of a relatively low cost. For the 2-aminopyrimidine library, polystyrene-based piperazine and piperidine gave products with a much higher purity compared with other secondary non-cyclic or primary amines, hi both cases, the resins could be reused for up to four times before degradation in their behavior was observed. This reusability could be further enhanced (up to 10 cycles for cellulose-based aniline) when the microwave-assisted protocols were used. 

Pr)4, " borohydride-exchange resin,and formic acid. When the last is used, the process is called the Wallach reaction. Conjugated aldehydes are converted to alkenyl-amines with the amine/silica gel followed by reduction with zinc borohydride.In the particular case where primary or secondary amines are reductively methylated with formaldehyde and formic acid, the method is called the Esch-weiler-Clarke procedure. It is possible to use ammonium (or amine) salts of formic acid, " or formamides, as a substitute for the Wallach conditions. This method is called the Leuckart reaction,and in this case the products obtained are often the N-formyl derivatives of the amines instead of the free amines. Primary and secondary amines can be iV-ethylated (e.g., ArNHR ArNREt) by treatment with NaBH4 in acetic acid. Aldehydes react with aniline in the presence of Mont-morillonite KIO clay and microwaves to give the amine. Formaldehyde with formic acid converts secondary amines to the N-methyl derivative with microwave irradiation. 

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