DE1045098B - Process for the production of nitrogen- and phosphorus-containing polycondensation products - Google Patents

Description

Process for the production of nitrogen- and phosphorus-containing polycondensation products The polymeric substances are obtained according to the invention by a condensation or polymerization reaction of a tetraoxymethylphosphonium salt or trioxymethylphosphine oxide with one or more nitrogen compounds capable of reacting with formaldehyde and containing several reactive hydrogen atoms, with the exception of urea, melamine, Guanidine and its water-soluble partial formaldehyde condensation products. They differ advantageously from phosphorus-containing plastics of a known type, which the grouping contain or in which the phosphorus atom is bound directly to the nitrogen (PN bond), because the PCN bond formed according to the invention is particularly resistant to hydrolysis, which is a remarkable superiority z. B. brings about the stability of the products over the previously known, similarly structured with it.

Preferred among the nitrogen-containing compounds are those which their polyfunctional nature of the presence of more than one to the nitrogen bonded hydrogen atom or the presence of bonded to an aromatic radical Owe hydrogen atom.

Examples of suitable nitrogen-containing compounds are those. which one of the following formulas PntsmrP @ hPm Compounds according to formula (1) are: cyanamide, hydrazine, sulfamide, sulfamic acid and carbohydrazide.

Compounds according to formula (2) are: dicyandiamide, aminoguanidine, guanylurea, Biguanide, amidodicyandiamidine, cyanurea, semicarbazide, biuret, triuret, tetrauret and arninobiuret. The salts of the compounds listed can also be used in the present Procedures are used.

Other examples of nitrogen-containing compounds are primary aliphatic and alicyclic amines, e.g. B. mono-tert-octylamine, aliphatic and alicyclic primary and secondary polyamines such as ethylenediamine and Cyclohexylamine, as well as aromatic primary, secondary and tertiary amines and polyamines, z. B. aniline, diphenylamine and benzylethylaniline. In the case of the tertiary aromatic In amines, the benzene nucleus is the reactive part.

Further suitable substances are ammonia and hexamethylenetetramine as well as the acid amides, e.g. B. adipic acid, acrylic acid amide, butyric acid amide and Phthalic acid diamide.

As tetraoxymethylphosphonium salts come z. B. in question the chloride, the acetate, the phosphate, the formate and the sulfate.

Aldehydes or substances that under the reaction conditions are aldehydes - can also be involved in the reaction. Examples of this are formaldehyde, glyoxal, acrolein and furfural. The aldehyde can be used together with the nitrogen-containing compound or as a precondensation product with this Compound can be added. The precondensate can optionally with a catalyst getting produced.

Also other substances that are capable of forming polymers, may be present so that copolymerization or co-condensation takes place. For this purpose, methylated methylolmelamine and methylated, among others, are suitable Methylolurea and other alkylated amine-formaldehyde condensation products.

Any suitable solvent, in particular Water, can be used. Heating the reaction mixture, e.g. B. to 100 to 200 ° C is not always necessary for the polymerization to proceed to the desired extent allow.

When using tetraphosphonium compounds can cause trapping the acid a neutralizing substance, e.g. B. sodium carbonate, calcium carbonate or Triethanolamine, are added.

The polymeric substances according to the invention can be used for the most varied Purposes in the plastics industry, e.g. B. for molding, for the production of webs or plates and as coatings, find use; Fillers and plasticizers can, be attached if necessary. Many of the polymeric substances that are in use obtained from primary amines as the nitrogenous component are liquids. They can be used to modify the properties of solid polymers that are compatible with them to be used. An important application for the polymeric substances that According to the invention arise, consists in it with organic fibers in the most intimate To connect what is particular for the changes in properties of textiles is important. As an advantage of many of the fabrics according to the invention their resistance to fire and their non-flammability is suitable they are particularly suitable for making fireproof materials such as textiles, Paper, etc. ö = It has also been shown that in the implementation; initiation of the procedure, particularly when one of the reaction components is an aldehyde, advantageous is, before, during or towards the end of the reaction, an excess of the polyfunctional nitrogen-containing compound beyond the amount that would normally allow for condensation with the phosphonium compound is necessary to add. You can also have two or several polyfunctional nitrogen-containing compounds such as ammonia or thiourea or one of its salts. So can, for example the phosphonium compound primarily condenses with thiourea or with a Condensation product of this compound are reacted with an aldehyde, one of the aforementioned polyfunctional nitrogen-containing compounds being present or can be added later. In such a case, the presence or later addition of an excess of nitrogenous compounds such as ammonia about the normally necessary for condensation with the phosphonium compound Amount is not necessary, but for example to produce a possible great flammability and afterglow resistance or for condensation under Advantageous circumstances.

There is a reason for the resistance of polymers to fire in several different but often interlocking effects. That's what polymers are like such as those according to formulas (1) and (2), which have a relatively small proportion of Have C and H atoms in relation to N and 0 atoms, incombustible and therefore particularly effective as a fire protection resin for textiles. On the other hand, polymers burn the z. B. in the reaction of phosphonium compounds with amines (e.g. ß-naphthylamine, see example 14) and have a relatively high proportion of C and H atoms, pretty easy. The flammability of these polymers also depends on the ratio the number of phosphorus atoms to the total number of C and H atoms; that's how it burns Polymers (Example 10) from p, p = diaminodiphenylmethane not at all, while the Polymers (Example 11) from p-phenylenediamine, which has a much smaller proportion of Has phosphorus atoms, partly burns. Polymers of cyclohexylamine (2 moles) and Tetraoxymethylphosphonium chloride (1 mole) melt and burn, if a sort of as a "wick" is present, however, leaves a base anti-inflammatory crust.

The incombustible polymers in particular are particularly useful for refractory of z. B. wood or fiberboard, such as components of Paint and varnish preparations. In the event of a fire, it forms an incombustible polymer then a porous or foamy charcoal crust that covers the inflammatory substrate in front of the Flame protects. The presence of any acidic phosphorus compound resulting from originates from the initial decomposition of the polymer, however, is essential for the fire protection effect, as this results in the coal crust in the event of further exposure does not burn from heat.

The following examples explain the extension in more detail. The parts given are parts by weight. Example 1 To a solution of 25 parts of tetraoxymethyl phosphonium chloride in 10 parts of water Parts of triethanolamine given and the mixture one = solution of 15 parts of methylolmelamine and 10 parts added water. You leave the whole thing for 24 hours Stand at 20 ° C and then heat the clear Gel for 1 hour at 130 ° C, creating a non-flammable resin.

Example 2 -A solution of tetraoxymethylphosphonium chloride is neutralized as in Example 1 with triethanolamine. To 50 parts of this solution are under @S ": @ F @ 'hear slowly 25 parts of hydrazine hydrate in 25 parts - given, taking the temperature to 25 ° C After a violent reaction, a viscous x @ a, ye that syrup. Upon drying, a clear, translucent, non-flammable resin is obtained.

Example 3 10 parts of sulfamide and 12 parts of a solution of 50 parts of glyoxal in 50 parts of water are added to a solution of 20 parts of tetraoxymethylposphonium chloride in 10 parts of water. When the mixture is heated, a vigorous reaction forms a viscous solution which, on evaporation to dryness at 110 ° C., gives a hard, brittle, water-insoluble resin. EXAMPLE 4 To a solution of 20 parts of tetraoxymethylphosphonium chloride in 10 parts of water, 10 parts of sulfamic acids (amidosulfonic acid) are added with stirring, the mixture is boiled for 5 minutes and the viscous solution formed is evaporated to dryness at 110 ° C., giving a clear, hard, brittle one Resin is produced. Example 5 A mixture of 13 parts of tetraoxymethylphosphonium phosphate, 6 parts of triethanolamine, 5 parts of biuret and 10 parts of water is heated to 100 ° C. for 60 minutes. The solution is poured onto a glass or tin plate and allowed to dry for 15 minutes at 100.degree. C. and 10 minutes at 140.degree. The resulting film adheres well to the base and is completely fire-proof. Example 6 20 parts of cyclohexylamine are added to a solution of 21 parts of tetraoxymethylphosphonium chloride in 50 parts of hot water. A sticky white polymer forms immediately, which hardens somewhat on standing at room temperature. It is insoluble in formaldehyde solution and in boiling water, but it dissolves in dilute strong mineral acids and in glacial acetic acid and up to 5% in boiling alcohol. Example 7 60 parts of cyclohexylamine are dissolved in 80 parts of alcohol at 30 ° C. and a solution of 19 parts of tetraoxymethylphosphonium chloride in 80 parts of alcohol is added over the course of 30 minutes with stirring. After standing overnight, the polymer is precipitated as a pale yellow syrup by adding water. It contains 8.43% P and 10.44% N. This polymer reacts further with the phosphonium salt in alcoholic solution. Example 8 A low-melting polymer is obtained by mixing a solution of 1 part of tetraoxymethylphosphonium chloride in 4 parts of water with a solution of 1 part of cyclohexylamine in 4 parts of water. When heated to 145 ° C for 15 to 20 minutes, the polymer forms a light brown liquid that solidifies at 70 to 80 ° C and melts again at this temperature. The polymer is insoluble in water, but easily soluble in dioxane. Example 9 3.5 parts of cetylamine dissolved in 30 parts of 600% alcohol are added to 2 parts of tetraoxymethylphosphonium chloride dissolved in 12 parts of 80% alcohol, with an addition of 0.3 part of sodium carbonate. A polymer which melts below 100 ° C and is soluble in hydrocarbon solvents, but insoluble in water and alcohol, precipitates almost instantly. The polymer contains 5.6% P and 4.4% N. Example 10 20 parts of p, p'-diaminodiphenylmethane are dissolved in 40 parts of boiling alcohol and 20 parts of tetraoxymethylphosphonium chloride, dissolved in 24 parts of alcohol, are added at the same temperature. A pale yellow polymer forms instantly, which is filtered off and dried. When heated, the polymer neither melts nor burns; if necessary, it carbonizes to an encrusted mass. It is insoluble in formaldehyde solution and in dilute strong mineral acids. Example 11 8 parts of tetraoxymethylphosphonium chloride are dissolved in 25 parts of alcohol and 6 parts of triethanolamine are added; the precipitate from triethanolamine hydrochloride is filtered off. 11 parts of p-phenylenediamine, dissolved in 15 parts of alcohol, are added, whereupon a pale yellow solid polymer immediately separates out which, when heated vigorously, crusts with partial burning and forms a voluminous carbon residue. The polymer is insoluble in formaldehyde solution and dilute mineral acids. Example 12 8 parts of tetraoxymethylphosphonium chloride are dissolved in 25 parts of cold alcohol, whereupon 6 parts of triethanolamine are added. The precipitated triethanolamine hydrochloride is filtered off. A solution of 11 parts of benzidine in 15 parts of alcohol is added and a solid polymer is immediately formed which has the same properties as the product obtained from p-phenylenediamine according to Example 11. Example 13 18 parts of tetraoxymethylphophonium chloride and 15 parts of dodecylamine are dissolved together in 80 parts of boiling alcohol and 14 parts of triethanolamine are added. An oil is instantly deposited, which remains liquid at room temperature. Example 14 8 parts of tetraoxymethylphosphonium chloride are dissolved in 25 parts of ethanol and 6 parts of triethanolamine are added, whereupon the triethanolamine hydrochloride is filtered off. 10 parts of B-naphthylamine in 30 parts of alcohol are added to the solution. A soft polymer is instantly deposited, which hardens on standing. This polymer is highly flammable, insoluble in formaldehyde and in dilute mineral acids. Example 15 a) Tetraoxymethylphosphonium acetate is prepared from the chloride as follows: 95 parts of the phosphonium chloride are dissolved in 400 parts of alcohol; 68 parts of sodium acetate trihydrate, dissolved in 210 parts of acetic acid and 80 parts of alcohol, are added. The precipitated Na Cl is filtered off and the filtrate is evaporated to a syrup. This is dissolved in 160 parts of alcohol; when standing overnight, some NaCl still precipitates. After filtering, the solution is evaporated in vacuo to a thick syrup containing 89% of the acetate. The pure compound is crystalline and melts at 90 to 92 ° C. b) 12.1 parts of 89% tetraoxymethylphosphonium acetate are mixed with 6.2 parts of biuret and 15 parts of water and heated on a steam bath. After 90 minutes a white gelatinous polymer forms, which is taken up with alcohol, filtered off and dried to a white, granular solid. Yield 10.1 parts.

This polymer decomposes without melting or burning, when heated to over 300 ° C in air. The residue is black and voluminous and significantly delays heat transfer when a flame passes over the surface deletes. The surface of the carbonaceous residue glows in the flame and radiates a large part of the heat, but burns very slowly and glows not after when the flame is removed. Example 16 1145 parts of aqueous ammonia solution (specific weight: 0.880) are for 5 minutes while stirring vigorously a Solution of 1000 parts of tetrahydroxymethylphosphonium chloride in 3000 parts of water added. The mixture is stirred for a further 20 minutes, the colorless solid product filtered off, washed by stirring for 10 minutes with 2000 parts of cold water and filtered again. The product is air dried to give 1200 Parts air dry material, which contains 546 parts anhydrous polymer with 23.93% Contains phosphorus.

400 parts are required to produce a stable aqueous suspension of the above air-dry material (= 182 parts of anhydrous product) 21/2 hours in a ball mill with 950 parts of water and 50 parts of a 20% strength aqueous solution milled by cetyltrimethylammonium bromide.

Claims (7)

PATENT ANSPA (JCIII ;: 1. Process for the preparation of nitrogen- and phosphorus-containing polycondensation products, characterized in that a tetraox, ymethylphosphonium salt or trioxymethylphosphine oxide is used with at least one nitrogen-containing, formaldehyde-convertible and containing several reactive hydrogen atoms with the exception of urea, melamine, guanidine and their water-soluble partial formaldehyde condensation products, optionally in the presence of an aldehyde, an aldehyde-releasing substance or their initial or condensation products with a nitrogen-containing compound. 2. The method according to claim 1, characterized in that the nitrogen-containing compound is a compound of the general formula R, -NHz wherein R1 is the group -CN, -NH2, -SOz # \ TH2, -5020H or -NH.CO.NH # NH2 or a salt of such a compound is used. 3. The method according to claim 1, characterized in that there is a compound of the general formula as the nitrogen-containing compound wherein I22 is the group and X the group -CO .NH-CO # NH2, -CO-NH # CO # NH.CO.NHz, -NH # CO.NHz or -CO # NH.NH2 means, or a salt of such a compound is used. 4. The method according to claim 1, characterized in that there is a nitrogen-containing compound, a primary aliphatic amine or polyamine or an aromatic primary, secondary or tertiary amine or polyamine used. 5. The method according to claim 1, characterized in that that ammonia or hexamethylenetetramine is used as the nitrogen-containing compound. 6. The method according to claim 1, characterized in that the nitrogen-containing Compound an aliphatic or aromatic carboxamide used. 7. The method according to claim 1 to 6, characterized in that the nitrogen-containing compound is used in excess over the amount normally required for condensation. B. The method according to claim 1 to 7, characterized in that the reaction is carried out in the presence of one or more additional compounds capable of forming condensation products, in particular alkylated amine-formaldehyde condensation products, methylated methylolamine and / or methylated methylolurea. 9. The method according to any one of claims 1 to 8, characterized in that the condensation is carried out at 100 to 200 ° C. Documents considered: German Patent No. 854651; USA. Patents Nos 2 366129, 2 642 413. Contemplated older patents: German patent no. 1009 394th.