DE1192646B - Process for the production of resinous, phosphorus-containing condensation products - Google Patents

Description

Process for the production of resinous, phosphorus-containing condensation products The invention relates to the production of resinous phosphorus-containing condensation products by reacting phosphorus trichloride or phosphorus oxychloride with amines at higher levels Temperature.

It is known to react phosphorus chlorides with ammonia. So will z. B. in J. R. van Wazer, Phosphorus and its Compounds, 1958, pp. 324 to 327, the reaction of phosphorus oxychloride with ammonia at 150 to 200 "C described. However, this creates insoluble, probably three-dimensional reaction products.

Primary and secondary organic amines or their hydrochlorides can be known to be in good yields with phosphorus halides or phosphorus chalcogen halides, such as. B. phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorothiotrichloride or phosphorus oxychloride, to defined halogen-containing phosphorus nitrogen compounds, such as. B. N-substituted phosphoramidodichlorides (I) or phosphorothioamidodichlorides, but only difficult to convert to phosphorodiamidochlorides (II) or phosphorus thiamides (III) (A. Michaelis, A. 326, pp. 129 to 258, 1903).

Depending on the reaction conditions, different types of but well-defined end products.

According to M i c h a e 1 i 5 one works z. B. for the synthesis of N-methylanilidophosphoramidodichloride instead of equimolar parts with an excess of phosphorus oxychloride the methylaniline used and heats the reaction mixture to the boil for so long until no more hydrochloric acid escapes and the reaction temperature towards the end of the reaction has risen to 1500C.

According to M i c h a e 1 i 5 it is also possible by heating the primary resulting phosphoramides, amidochlorophosphates or thionophosphoramides at temperatures to produce from 170 to about 200 "C imido derivatives of phosphorus of the formula R2N-P (O, S) = NR. However, the products are insoluble or sparingly soluble, and only the corresponding ones Sulfur analogs have a slightly better solubility (K o s o 1 a p o f f, Organophosphorus Compounds, 1950, pp. 282 to 284).

It is also known from U.S. Patent 2,151,380, halides a phosphoric acid with primary or secondary aliphatic and aliphatic aromatic Amines containing at least 10 carbon atoms in the chain at temperatures to convert from 0 to 200 "C to crystalline phosphoramides or phosphoramic acids. According to the examples, the reaction is preferably carried out at about 40 to 120 ° C the reaction of e.g. B. Phosphorus oxychloride with N-dodecylaniline at 180 to 200 "C carried out, so predominantly brown discolored oily products are obtained.

It has now surprisingly been found that phosphorus trichloride can be used or phosphorus oxychloride and amines at higher temperature light resinous and in organic solvents can produce soluble condensation products, if according to the invention, primary or secondary aromatic amines, optionally one to three alkyl radicals each with 1 to 4 carbon atoms, a methoxy group or carry 1 to 5 halogen atoms as substituents, or their mixtures or their Salts with volatile organic or inorganic acids with the phosphorus compounds mentioned at 180 to 400 "C in a molar ratio of phosphorus to amine compound of 1: 1.25 to 4 implements.

It is thus obtained in a simple manner from technically easily accessible cheap raw materials resinous condensation products, which are suitable Choice of components based on their phosphorus, oxygen and halogen content due to flame retardancy or incombustibility and great thermal stability distinguish.

While phosphorus chloride mixtures with primary or secondary Amines generally become very dark when heated or even at room temperature color, the phosphorus chloride-amine mixtures produced by the process according to the invention lighten during the condensation process proceeding with elimination of hydrogen chloride so that almost colorless to pale yellowish condensation products are obtained.

Depending on the duration and temperature of the condensation, you have it in your hand, to obtain sticky, brittle or fragile thermoplastic resins. The condensed Hard resins generally contain relatively little chlorine, since the condensation takes longer and a higher condensation temperature, the hydrogen chloride is for the most part split off will. But you can also choose very halogen-rich, flame-retardant resins suitable, halogen-rich amine components obtained.

A preferred embodiment of the method is that the amine component is a mixture of different organic amines, including mixtures primary amines with secondary amines.

Aromatic primary and secondary amine components are suitable as amine components Amines, which optionally contain one to three alkyl radicals each with 1 to 4 carbon atoms, carry a methoxy group or 1 to 5 halogen atoms as substituents. Exemplary may be mentioned: anilines, toluidines, xylidines, methyl, ethyl, propyl, butyl, isobutyl anilines and toluidines, di- and trialkylanilines, haloanilines, such as mono-, di-, tri-, tetra- and pentahalogenanilines, anisidines, diphenylamines, also diamines, such as benzidine, 4,4'-diaminodiphenylmethane, and their salts with volatile organic or inorganic acids, such as. B. hydrobromic acid, formic acid, carbonic acid or oxalic acid. Excellent the hydrochlorides of the amines mentioned above are suitable.

The reactions are expediently carried out by directly heating the reaction components achieved.

If one works in solution, then only very high-boiling indifferent ones can Solvents such as B. l-chloronaphthalene or nitrobenzene can be used. the The boiling point of the solvent used must be at least as high like the condensation temperature.

During the reaction, the molar ratio of phosphorus chloride or Phosphorus oxychloride to amine are in the range between 1: 1.25 and 1: 4.

Acid-binding substances in particular are not required for condensation to be added.

An advantage of using aromatic amines in manufacturing of the phosphoramide condensation products consists in that per chlorine atom of the phosphorus compound not 2 amine molecules are required, since the aromatic amines are the released Binding hydrogen halide with salt formation, but these salts under the reaction conditions disintegrate again and the released aromatic amines continue to react can. So you save considerable amounts of amines and can do the implementation in one simple Perform one-pot process. If, on the other hand, phosphorus halides are used according to the state of the art with ammonia or lower aliphatic amines, an end product is obtained, which contains ammonium chloride or salts of lower aliphatic amines and thereby when used for paint purposes, easy flocculation in the paint solutions or causes the formation of brittle paints.

The amount of volatile acids split off during the condensation depends on the reaction temperature and duration and at the same time is a measure for the degree of condensation. When using amine mixtures, condensation begins usually below 100 ° C. For condensation one works in the range of 180 to 400 "C, optionally in a vacuum and under an inert gas such as nitrogen.

The reactions to the condensation products which can be prepared according to the invention can be carried out either continuously or batchwise. at continuous production, the condensation occurs when passing through a heated one Pipe or pipe system.

The type of amine or phosphorus components used and the Condensation conditions determine the properties of the extraordinarily variable End products such as B. Color, mechanical hardness, softening point, K value, flammability, Adhesion and absorption as paint and miscibility with other resins and paint raw materials.

The products which can be prepared according to the invention dissolve in organic compounds Solvents, * such. B. methanol, ethanol, glycol, ethyl glycol, butyl acetate, tetrahydrofuran, Dimethylformamide, and, when applied in a thin layer, result in well-drying, smooth, tough films. They can be used alone or in combination with other resins and / or solvents be used to manufacture flame retardant paints, films and plastics.

The parts mentioned in the examples are parts by weight.

Example 1 154 parts of phosphorus oxychloride are, initially with ice cooling, added dropwise to 214 parts of monomethylaniline (molar ratio POS13 to amine = 1: 2).

Then the mixture is slowly heated up to 220 ° C. until the strong evolution of hydrochloric acid slowly subsides, pours into an enamel bowl and gets a solid, pale yellow-greenish resin in a thick layer.

Comparatively carried out conversions according to the USA patent specification In contrast, 2,151,380, as the following comparative tests show, do not produce light colors Resin-like, rather brown-colored liquid products.

Comparative Experiment 1 40 parts are added to 52 parts of N-dodecylaniline Phosphorus oxychloride was added dropwise at 60 to 1000 C (molar ratio POS13 to amine = 1.3 :1). The mixture is heated to 180 to 200 ° C. for 4 hours, hardly any hydrogen chloride escaping. After cooling, a dark brown liquid product is obtained.

Comparative Experiment 2 11.8 parts are left in 26 parts of N-dodecylaniline Add dropwise phosphorus oxychloride (molar ratio of POCl3 to amine = 1: 1.3), increasing the temperature a little. The mixture is heated to 200 ° C. for a further 5 hours.

This results in only a weak evolution of hydrogen chloride, and after cooling, a green-brown liquid product with a low crystalline part.

Comparative experiment 3 26 parts of N-dodecylaniline are added dropwise at slowly increasing temperature (from 50 to 1000 C) 6.2 parts of phosphorus oxychloride (molar ratio POCI3 to amine = 1: 2.5) and then heated for 4 hours to 190 to 200 "C. At weak evolution of hydrogen chloride gives a dark brown color after cooling liquid product.

Example 2 170 parts of phosphorus trichloride are slowly added to 186 parts of aniline added dropwise with weak cooling (molar ratio of POC13 to amine = 1: 1.25).

The mixture is heated for 3 to 4 hours at a slowly increasing temperature (up to 210 ° C), so that the hydrochloric acid is constantly split off. After pouring out and cooling a very hard, slightly yellowish resin is obtained.

Example 3 To a homogeneous mixture of 60 parts of monoethylaniline and 64 parts of p-chloroaniline, 77 parts of phosphorus oxychloride are added dropwise (molar ratio POCC to amine = 1: 2). The mixture is slowly heated to 290 ° C. and after the strengthen Hydrochloric acid developed an almost colorless solid resin.

Example 4 To a homogeneous mixture of 81 parts of 3,4-dichloroaniline, 63 parts of m-chloroaniline and 53 parts of monomethylaniline are 154 parts of phosphorus oxychloride added dropwise (molar ratio POS13 to amine - 1: 1: 1.5). It is first condensed at 180 to 250 "C and finally heated to 360" C. One receives after cooling an almost colorless, very hard resin.

Claims (1)

Claim: Process for the production of resinous phosphorus-containing Condensation products from the reaction of phosphorus trichloride or phosphorus oxychloride with amines at a higher temperature, characterized in that one primary or secondary aromatic amines, optionally with one to three alkyl radicals each 1 to 4 carbon atoms, a methoxy group or 1 to 5 halogen atoms as substituents carry, or their mixtures or their salts with volatile organic or inorganic Acids with the phosphorus compounds mentioned at 180 to 400 "C in a molar ratio from phosphorus to amine compound from 1: 1.25 to 4 converts. ~~~~~~~~~ Considered Extracted publications: German Auslegeschrift No. 1 042 228; U.S. Patent No. 2,151,380; J. R. v a n W a zer, Phosphorus and its Compounds, 1958, p. 327.