DE1009805B - Process for the preparation of new amino-1, 3, 5-triazine-formaldehyde condensation products - Google Patents

Description

Process for the production of new amino-1, 3, 5-triazine-formaldehyde condensation products It has been found that new, curable, higher molecular weight residues can be obtained Derivatives of a formaldehyde condensation product of at least two NI-I. groups containing amino-1, 3, 5-triazines is obtained when a) a formaldehyde condensation product an amino-1, 3, 5-triazine having at least two NH, groups, in which per NH2 group of the aminotriazine at least one oxymethyl group with a lower, alcohol containing at most 4 carbon atoms is etherified and in which further on at least one NI-I, group at least one oxymethyl group with a higher molecular weight Prevention is condensed which has at least one reactive hydrogen atom on an oxygen, sulfur or non-basic nitrogen atom, in particular a high molecular weight non-aromatic carboxylic acid or a higher molecular weight Alcohol. with b) partial esters from polyhydric aliphatic alcohols and exclusively non-aromatic saturated carboxylic acids containing at least 12 carbon atoms or with partial ethers made from polyhydric aliphatic alcohols and at least 12 carbon atoms containing monohydric aliphatic alcohols or with amides or N-methylolarnides of non-aromatic carboxylic acids containing at least 12 carbon atoms in the heat under practically anhydrous conditions, optionally in the presence a catalyst of acidic nature, with elimination of the lower, at most 4 carbon atoms containing alcohols, the molar ratio between the reaction components is chosen so that at least one with a lower alcohol in the end product etherified methylol group or at least one free methylol group is present, and the reaction mixture is freed from the catalyst, if one is used became.

The presence of at least one free or with a lower alcohol etherified methylal group in the end product is necessary in order for the latter to be curable remain.

The preparation of the reaction component a) for the present Process used as starting materials formaldehyde condensation products, the at least one with a lower alcohol containing at most 4 carbon atoms have etherified oxymethyl group, can in principle differ from all aminotriazines derive as long as they have at least two NH2 groups and deal with formaldehyde Convert into the corresponding methylol compounds and then ätliern permit. For economic reasons, however, the most easily accessible ones are recommended Products, such as especially melamine, also N-phenyl melamine, benzoguanamine, acetoguanamine, Formoguanamine, ammeline and 2, 4-diamino-6-chloro-1, 3, 5-triazine.

These methylol ethers can be treated by known methods of appropriate amounts of formaldehyde to aminotriazines, which at least two \? H2 groups possess, and by simultaneous or subsequent etherification of the resulting M ethylolaminotriazines or methylolaminotriazine mixtures with the alcohols such as ethyl, propyl, butyl or preferably methyl alcohol obtained. This very often results in mixtures which are used for the preparation of the reaction components a) can be used, provided that they are aminotriazine per amino group of the amount of aminotriazine used contain at least one etherified oxymethyl group. May be mentioned e.g. B. the methyl ethers of methylolmelamines with four to six mediylene groups in which two to six Methylol groups are etherified. Such ethers can for example by heating the methylolmelamines with methanol in the presence of small amounts of mineral acids in can be obtained in a known manner.

The reaction components a) can act in a known manner of the higher molecular weight compounds mentioned that have a reactive hydrogen atom contain, are obtained on the methylol ethers. For the representation of such starting materials Both such methylolaminotriazine ethers can be used in which all Methylol groups are etherified by low molecular weight alcohols, as well as those that are still free Contain methylol groups. Among the higher molecular weight compounds that are reactive Contain hydrogen atom and are used to produce the starting materials mainly aliphatic compounds that have a carbon chain of at least Have 7 carbon atoms and at least one reactive hydrogen atom contain bound to an oxygen, sulfur or non-basic nitrogen atom, into consideration. The compounds having a non-basic nitrogen atom are amide-like or urethane-like bodies; Examples include amides from ammonia or from primary amines, such as methyl, ethyl, dodecyl, octadecyl or cyclohexylamine, on the one hand and from carboxylic acids, such as vinegar, chloroacetic, butter, capric, lauric, Stearic, earthquake or oleic acid, on the other hand; also substituted ureas, such as Monododecylurea; Urethanes, as they are e.g. B. from the chloroformic acid esters of higher molecular weight Alcohols with ammonia or primary amines are available, such as octadecyl urethane; furthermore secondary amides, such as dilaurinamide or N, N'-diacylated alkylene or Arylene diamines, e.g. B. L \ Iethy lendistearinamide.

As compounds that have a reactive hydrogen atom attached to one Contain a bonded sulfur atom, are mercaptans, such as dodecyl or octadecyl mercaptan, to mention, also esters of higher molecular weight alcohols with mercaptocarboxylic acids, such as Thioglycolic acid esters.

As compounds that have a reactive hydrogen atom attached to one Containing an oxygen atom bonded come carboxylic acids, alcohols and N-methylol compounds into consideration. Among the carboxylic acids that have a carbon chain of at least 7 Have carbon atoms, be capric, lauric, stearic, quake, (il, ricinol or Montanic acid mentioned. Primary, secondary or tertiary alcohols can be used as alcohols that can be either straight-chain or branched, such as. B. Lauric alcohol, cetyl alcohol, octadecyl alcohol, 2-butyloctanol. Furthermore are Condensation products of polyglycols or alkylene oxides, preferably of ethylene oxide, with alcohols, 'amines, amides or carboxylic acids to consider like that Addition product of 1 mole of ethylene oxide with 1 mole of Octadecylalkoho.l or 1 1 \ Zol Octadecylamine.

The N-methylol compounds are preferably N-methylol compounds of amides or amide-like compounds as mentioned above, e.g. B. methylol urethanes.

Of the compounds mentioned, which are used as reaction components for the production of the raw materials that can be used, those are preferably used; which have at least one carbon chain of 18 carbon atoms, in particular derivatives stearic acid, octadecyl alcohol or octadecylamine. A suitable one The starting material is, for example, the condensation product, which is obtained from 1 mol of a highly methylated methylolmelamine and 1 to 2 moles of stearic acid is available.

For the method according to the invention, as mentioned at the outset, as Reaction component b) amides or N-1-lethylolamides of non-aromatic carboxylic acids with at least 12 carbon atoms or partial esters of polyvalent aliphatic Alcohols and saturated, non-aromatic ones containing at least 12 carbon atoms Carboxylic acids or partial ethers from polyhydric aliphatic alcohols and at least Monohydric aliphatic alcohols containing 12 carbon atoms are required. Such Compounds are also known or can be readily made by known methods will. The amides and N-methylolamides are preferably derived from aliphatic Carboxylic acids, for example from lauric, palmitic, stearic, oil, quake, linoleic, Myricylic acid, or of fatty acids obtained by the oxidation of paraffin. Very effective end products are obtained when one of urethanes or their methylol compounds goes out, e.g. B. of methylol octadecyl urethane.

The partial esters or partial ethers preferably used are on the one hand Derivatives of glycols, polyglycols, glycerine, or glycerine-like compounds and on the other hand non-aromatic ones having at least 12 carbon atoms saturated carboxylic acids or monohydric aliphatic alcohols. Among the to Production of such compounds serving polyhydric alcohols are z. B. called ethylene glycol, 1,3-propylene glycol, 1,3 or 1,4-butylene glycol or higher Glycols, furthermore polyglycols, such as diethylene glycol, triethylene glycol, or higher Polyglycols, which are obtainable by condensation of ethylene oxide., Also compounds, that contain more than two hydroxyl groups, such as glycerine. Erythrite, Pentite, Hexite. Finally, derivatives of such polyhydric alcohols can also be used, those in the reaction with a saturated carboxylic acid or a derivative thereof or with an aliphatic monohydric alcohol having at least 12 carbon atoms capable of forming a partial ester or partial ether of a polyhydric alcohol. Such compounds may be mentioned, for. B. Glycid, but especially halohydrins, such as ethylene chlorohydrin, ethylene bromohydrin, glycerol chlorohydrin or epichlorohydrin. Such halogen-containing compounds can, for. B. by reaction with an alkali salt a carboxylic acid or an alkali metal alcoholate of a monohydric aliphatic alcohol with at least 12 carbon atoms to form a partial ester which can be used according to the invention or partial ethers are implemented.

As a carboxylic acid, which itself or its reactive derivatives for Production of the partial ester (reaction component b) can be used those mentioned above in the case of the amides can be considered, but only those which have one have saturated hydrocarbon chain. Among the monovalent aliphatic Alcohols, of which the partial ethers which can be used according to the invention (likewise a reaction component b) derive, may be mentioned, for example: Mvricyl-, Ceryl-, Stearyl-, Cetyl-, Laurin-, Oleic, linoleic, linoleic alcohol. Alcohols or their mixtures are also very suitable, which by reduction of fatty acids, which in turn by oxidation of paraffin are obtained, as well as those obtained by total synthesis from carbon monoxide and hydrogen representable higher alcohols or mixtures thereof. Also suitable Mixtures of saturated alcohols, such as those from drying, semi-drying and non-drying oils by reduction with sodium and alcohol or by other methods and subsequent hydrogenation of the multiple bonds are made from linseed oil, soybean oil, hemp oil, poppy seed oil, wood oil, dehydrated castor oil, Cotton oil, coconut oil, cod liver oil, whale oil, menhaden oil and sperm oil. Even those from tall oil Preparable alcohols can be used,% - "earth. Instead of Free alcohols are expediently their alkali metal alcoholates for the preparation of the partial ethers or the halogen compounds corresponding to the alcohols, d. H. the alkyl halides, used.

If the partial esters or partial ethers that can be used according to the invention are derive from such polyhydric alcohols that have more than two hydroxyl groups in the Own molecule, one or more hydroxyl groups can be esterified or etherified be. It is necessary, however, that at least one hydroxyl group remains free. Particularly suitable compounds which are used as reaction component b) are the partial ester of 2 moles of stearic acid and 1 mole of glycerol and the partial ether from 2 moles of stearic alcohol and 1 mole of glycerine.

As catalysts of acidic nature, which may be used in the implementation are used, inorganic and organic acids can serve or substances, which give acids during the reaction or act analogously to acids, e.g. B. Acid anhydride or Friedel-Crafts catalysts. Your selection will be beneficial after practical Considerations such as removability, price, influence on the end product are made. So that the reaction can be carried out under practically anhydrous conditions can, it has proven to be useful to use catalysts that are as water-free as possible use. Advantageous catalysts are, for. B. concentrated hydrochloric acid, sulfuric acid, Phosphoric acid, hypophosphorous acid, phthalic acid or phthalic anhydride, maleic anhydride. Acetic acid, chloroacetic acid and formic acid. The catalysts are generally Hardeners for the lower alkoxymethyl-aminotriazines used as the reaction component a) as well as for the end products. So it has been found beneficial not to ; to use large quantities of these catalysts. Usually a few are sufficient Per mille to percent, calculated on the entire reaction mixture. To be stable, To obtain neutral to weakly basic end products, it is advantageous to use such Use the catalogs for c, which after implementation, d. H. before further processing of the reaction mixture by simple measures such as distilling off, neutralizing and optionally subsequent filtering off of the precipitated salts, washing out with water or solvents, can be removed from the reaction mass. this applies particularly when using strong acids as catalysts, which are particularly careful need to be neutralized. These measures to remove the catalysts are allowed exert no adverse influence on the end products.

The reaction components a) and b) are reacted at increased Temperature, preferably at temperatures above 100 °, e.g. B. at 120 to 200 °. the Reactants can simply be merged, or they become reacted in the presence of an inert organic solvent. It can be expedient be to carry out the reaction under reduced pressure, the resulting volatile products, d. H. the low molecular weight alcohols, from the reaction mixture can be removed.

The molar ratio between the components used depends primarily on the number of methylol ether groups present in component a). It is advantageous to use 1 to 2 mols of a compound per mole of a compound under a) implemented under b). The new products generally represent waxy bodies and are insoluble or sparingly soluble in water and often also in lower alcohols, in contrast, readily soluble in solvents with a more pronounced organic character, such as esters, ketones, higher alcohols and especially aromatic hydrocarbons and aliphatic in nature. They are compatible with fatty oils, which are in solvents with a pronounced organic character are soluble, as well as with a large number of Natural and synthetic resins, such as rosin and its derivatives, rosin-phenol resins, soluble phenolic resins, 11aline acid esters, copal in the melted state, Alkyd resins, with styrene-modified oils, soluble in organic solvents Condensation resins, e.g. B. urea and aminotriazine resins, also with soluble ones Ketone and vinyl resins and resins containing epoxy groups. The solubility or compatibility is strongly influenced by the type and number of imported higher molecular groups in the new products.

The Prxlukte obtainable according to the present invention can, if they were made from suitable starting materials, as auxiliaries, for example in the textile, leather and paper industries. In particular are they are suitable as a water repellent agent for making textiles made of cotton, regenerated Cellulose, cellulose ester, wool, silk, polyamide or polyacrylonitrile fibers or as components of such agents.

In Swiss patent specification 222 707 there are condensation products described that by etherification of esterified with stearic acid and phthalic acid Glycerin with a formaldehyde compound of melanin containing methylol groups can be obtained in butanol. However, these products are so prone to resinification, that from this without loss of solubility in organic solvents the at Excess butanol present during manufacture cannot be removed. In contrast to These condensation products are suitable for the end products of the present process therefore not for the production of emulsions used for water-repellent finishing.

In the following examples, the parts mean unless otherwise is noticed parts by weight. Example 1 In a closed round bottom flask 81 parts of technical stearic acid heated to 140 ° with stirring. Well be in small Portions a total of 8.11 parts of sodium carbonate (98 ° / aig) entered, with simultaneous Increase the melting temperature to 160 to 170 °. Once all the sodium carbonate is consumed can be recognized by the cessation of carbon dioxide formation, the stearic acid-sodium stearate melt is left Carefully cool down to about 130 °. Now: slowly add 14 parts of Fpichlorohydrin added dropwise, whereupon the melt is gradually heated again to 150 °. After this all epichlorohydrin has been entered, the mixture is stirred for a further 7 hours at 140 bis 150 °.

If you take a substance sample from the well-stirred melt and, after absorption in ether and shaking out with dilute acid and subsequent Washing with distilled water, which determines the acid number, is how an acid number is found from 1 to 3. The hydroxyl number is 96.5 instead of 94.5, calculated for a diglyceride made from technical stearic acid with a molecular weight of 270.

In the melt of the stearic acid diglyceride described above, cooled to 120 ° 67.6 parts of the ester, described in more detail below, are obtained from highly methylated methylolmelamine and stearic acid entered. If the water jet vacuum is good, the boiling point will be violently Flask contents initially at 120 ° for 2 hours, then at 160 ° in 1 hour and during Heated to 200 ° for 2 hours.

After pouring the reaction mass onto a metal sheet, a very hard and brittle product with a melting point of 41 to 42 °.

The ester from the highly methylated methylolmelamine and stearic acid was prepared analogously to the esters described in Swiss Patent 251,642.

To obtain the methylolmelamine methyl ether, 324 parts by weight are required (1 mol) finely powdered hexamethylolmelamine with stirring at room temperature in 2000 Parts by volume of methyl alcohol, which contains 100 parts by volume of concentrated hydrochloric acid, registered. After 10 minutes the methylol compound is dissolved. The solution will be Immediately mixed with about 160 parts by weight of calcined soda until it counteracts litmus reacts neutrally. The deposited salt is filtered off and the solution in vacuo evaporated to a syrup. The syrup, concentrated to about 991 / o, is then used for removal the remaining salt filtered hot.

1 part of this methylolmelamine methyl ether is mixed with 1.3 parts of stearic acid at a pressure of 10 to 20 mm heated to 180 to 200 ° until the acid number of the product has dropped to 5 to 8. Example 2 The instructions are followed in Example 1, 69 parts of a condensation product of methylated Methylol melamine and N-methylol stearic acid amide in 98 parts of the molten ester from 1 mole of glycerol and 2 moles of technical stearic acid enters. The thus obtained new condensation product forms a hard, waxy mass that z. B. in molten Paraffin is soluble.

The above-mentioned condensation product is produced by heating a mixture of 66 parts of N-methylol stearic acid amide and 39 parts of that in the example l mentioned methylolmelamine methyl ether at 115 to 120 ° for 1 to 2 hours at a pressure of 10 to 20 mm. A hard, brittle mass is obtained.

Example 3 The procedure is analogous to Example 1 by dividing into 98 parts molten ester of 1 mole of glycerol and 2 moles of technical stearic acid 77 parts of a condensation product of methylated methylolmelamine and N-methylol octadecylcarbamic acid ester enters, a product is obtained which has properties like that according to Example 2. The new condensation product thus obtained forms a hard, waxy one Mass, the z. B. is soluble in molten paraffin.

The above-mentioned condensation product is produced by heating a mixture of 68 parts of 11 \ T-methylol octadecyl urethane made from octadecyl urethane and formaldehyde according to known methods, and 39 parts of that mentioned in Example 1 Methylolmelamine methyl ether at 115 to 120 ° for 2 hours at one pressure from 10 to 20 mm. A brittle, waxy mass is obtained.

Example 4 270 parts of technical octadecyl alcohol are added with stirring melted and with a solution made from 140 parts by volume of methanol and 11.5 Parts of sodium, added. By bubbling in nitrogen with gradual warming of the reaction mixture to 160 °, the methanol is driven off. In the 95 to 100 ° cooled melt, 46 parts of epichlorohydrin are entered, with sodium chloride immediately is deposited. The contents of the flask are then slowly heated to 150 ° and stirred a few hours after.

After cooling, you get a hard, greasy mass that is in alcohol is quite difficult to dissolve. It essentially consists of a glycerine diether.

65 parts of this Gly cerindiethers are with 45 parts of an ester from highly methylated methylolmelamine and stearic acid, its preparation in the example 1, fused and in 4 hours with stirring at one pressure heated from 10 to 20 mm to 200 °.

The reaction product solidifies to a hard, waxy mass, the z. B. is rather sparingly soluble in molten paraffin.

Instead of the ester of highly methylated methylolmelamine and stearic acid can also be a condensation product of 1 mol of methylolmelamine methyl ether and 2111o1 find technical stearyl alcohol use.

Example 5 In example 1, last section, the production of a Methylolmelamine methyl ether distearate is described. The corresponding monostearic acid ester can be prepared as follows: 100 parts of the highly etherified one mentioned in Example 1 Methylohnelamin methyl ethers are used with 65 parts of technical stearic acid Pressure of 10 to 15 mm heated to 180 to 200 ° until the acid number of the Product has dropped to 1 to 3.

62 parts of the methyl melamine methyl ether monostearate obtainable in this way are with 131 parts of glycerol distearic acid ester from 100 in 3 to 4 hours 200 ° heated in a water jet vacuum. The new condensation product thus obtained forms a hard, waxy mass that z. B. is soluble in molten paraffin.

Another waxy reaction product with similar properties becomes in the condensation of 1 mole of glycerol dioctadecyl ether with 1 mole of the above Get monostearate. Furthermore, analogous condensation products are with similar properties available if you 1 mole of highly methylated methylolmelamine with 1 mole of technical Stearic alcohol and then 2 moles of glycerol distearic acid ester or Act on the condensation product thus obtained leaves.

Example 6 The procedure described in Example 1 is followed, with 65 parts of a condensation product of methylated methylolmelamine and stearic acid amide in 98 parts of the molten ester from 1 mole of glycerol and 2 moles of technical stearic acid enters. The condensation product obtained in this way forms a hard, waxy mass, the z. B. is soluble in molten paraffin. The above mentioned Condensation product is made by heating a mixture of 108 parts Stearic acid amide and 39 parts of the methylolmelamine methyl ether mentioned in Example 1 to 120 to 125 ° for 2 hours at a pressure of 12 mm. It will be a very hard, brittle mass obtained.

Claims (2)

PATENT CLAIMS: 1. A process for the preparation of a curable, relatively high molecular weight derivative of a formaldehyde condensation product of an amino-1, 3, 5-triazine containing at least two NH2 groups, characterized in that a) a formaldehyde condensation product of at least two NI-I.- Amino-1, 3, 5-triazines containing groups, in which at least one oxymethyl group per NH = group of the aminotriazine is etherified with a lower alcohol containing at most 4 carbon atoms and in which furthermore at least one oxymethyl group with an at least one N H2 group higher molecular compound is condensed, which has at least one reactive hydrogen atom on an oxygen, sulfur or non-basic nitrogen atom, in particular a high molecular non-aromatic carboxylic acid or a higher molecular alcohol, with b) partial esters of polyhydric aliphatic alcohols and exclusively non-aromatic, minde Saturated carboxylic acids containing at least 12 carbon atoms or with partial ethers of polyhydric aliphatic alcohols and monohydric aliphatic alcohols containing at least 12 carbon atoms or non-aromatic carboxylic acids containing amides or N-methylolamides of at least 12 carbon atoms, in the heat, under practically anhydrous conditions, optionally in the presence of a catalyst acidic nature, with elimination of the lower alcohol containing at most 4 carbon atoms, the molar ratio between the reaction components being chosen such that at least one methylol group etherified with a lower alcohol or at least one free methylol group is present in the end product, and the reaction mixture is freed from the catalyst if such was applied. 2. Process according to Claim 1, characterized in that one mole of the reaction component a) 2 moles of the reaction component b) used and the reaction at 100 to 200 ° undertakes under reduced pressure. Publications considered: Österreichische U.S. Patent No. 167,124; Swiss patents nos. 222707, 251642.