DE671724C - Process for the preparation of aldehyde condensation products of aminotriazines - Google Patents

Description

Process for the preparation of aldehyde condensation products of aminotriazines The present invention provides a process for the production of new valuable condensation products from aminotriazines or their derivatives and Aldehydes that contain at least 2 atoms of carbon, or substances that contain such Eliminate aldehydes. It also includes the manufacture of condensation products, in their production, in addition to such aldehydes, also formaldehyde or its polymers can also be used.

As a representative of the aminotriazines, the 2 # 4 # 6-triamino-i comes in particular # 3 # 5-triazine, usually called melamine, in question, (found to be particularly cheap has proven. In addition, derivatives of melamine are suitable, such as, for example by Des. amidation from melamine arise, such as melain, melem, melon, or how they are formed by replacing one or two amino groups with OH groups, like Ammelin and Ammelid. It can also be implemented aminotriazines in which some of the amino groups (for other groups of various kinds, e.g. halogen, Aryl, alkyl or Aralkvi groups. As a representative of such aminotriazines are mentioned: 2-Clilor-4 # 6-diamino-r # 3 # 5-triazine, 2- (p-oxyplienyl) -4 # 6-diamino-i # 3 # 5-triazine, 2-phenyl-4-amino-6-oxy-i # 3 # 5-triazine, etc. One can also use from such, #, bl: ömmlingeii of the aminotriazines, in which the hydrogen atoms the amino groups have been completely or partially replaced by the above-mentioned groups. such as symmetrical triary melamines, mono-, di-, trialkylmelamines or the like Aralkyl melamines, etc.

The aldehydes are aliphatic, aromatic, hydroaromatic, aliphatic-aromatic or heterocyclic, both saturated and unsaturated, mono-like Polyaldehydes in question, e.g. B. acetaldehyde, benzaldehyde, hexahydrobenzaldehyde, cinnamaldehyde, Terephthalaldehyde, furfural and the like. Mixtures of these aldehydes can also be included use yourself or with formaldehyde.

The condensation is preferably carried out at an elevated temperature. You can either in the absence of a solvent or diluent be performed. The molar ratio between aminotriazine and aldehyde can be within further limits fluctuate, e.g. B. between i: i and i: -2o, where appropriate the excess aldehyde acts as a solvent.

The rate of condensation can be adjusted by adding catalysts acidic or basic character. It's for making technical condensation products often not necessary, so much aldehyde for conversion; to bring than can be bound malimally, since those with less aldehyde are also obtained Kondelisa-. tion products have good technical properties.

The condensation can also be carried out in several stages by one first uses either aniinotriazine or aldehyde in excess and then on the resulting solution in one or more mares in it component located in deficit can act. For example, you can click Let the mol of 1felamin 'J2 lIol aldehyde act and the resulting product with treat further amounts of aldehyde. But you can also first use condensation products Produce with a lot of aldehyde and react the same with further amounts of aminotriazines. -If the reaction is carried out in a suitable organic medium, so can directly solutions of the condensation products in question in organic solvents are obtained, which are used for the production of paints or as additives to such become '. Such organic solvents are, for example, ethyl and butyl alcohol mentioned.

When using solvents, it can be advantageous to use the ini closed vessel (autoclave), which also makes it possible to use the Reaction temperature above the boiling point of the solvent, e.g. B. Ethyl alcohol, to choose.

The new condensation products are usually resins that can be hardenable in the heat. They are therefore of many uses; able to, z. B. in the industry of plastic masses as casting masses. as a binder for the production of molding compounds and laminated products, also for lining purposes, especially in the wood processing industry, for finishing, cutting right, Matting etc. in the textile industry, as lacquer hinders or lacquer additives etc.

Instead of using the aminotriazines alone, condensation also occurs with the addition of other compounds that form resins with aldehydes, such as phenols, Urea, Thioharlistotf, aniline u. Tlgl. or mixtures thereof where co-condensation products are obtained. Also there is the customer satisfaction be carried out in several stages, with z. B. a component to a lilit Sufficient amount or a few hours of aldehyde-emptied priniiirkondensationsprodukt can be added afterwards. The aminotriazine condensation products can also be used daily with other natural or synthetic resins, e.g. B. phenol-formaldehyde or Urea or thiolarea formaltlehvtl condensation products, mix or condense further. Furthermore, further substances can be used in each stage of the condensation such as dyes, fillers, plasticizers, water-repellent gowns, etc., added will.

It is already known that melamine and glucose are a condensation product to be produced (Chemisches Zentralblatt zgi3I 2iio), it is also a condensation product from methyl-2 # 4-diamino-z # 3 # 5-triazili and benzaldehyde (1I e y e r -J a c o b s o n, Textbook of Organic Cheillie,: 2. Volume, Part 3 [z92ol, Page r523). In both cases, however, the products are crystallized, while the present invention relates exclusively to the production of non-crystalline, usually resin-like condensation products.

In the examples below, parts are parts by weight, unless otherwise stated. Example 37.0 parts of ground 1lelamin (0.31 01), 52.8 parts of acetaldehyde (1.2 mol) and zoo room parts of alcohol (95%) are heated to the boil with reflux cooling. -After i3 / ,, hours all melamine is dissolved. The solution is kept boiling for a further 3/4 hours and then cooled. The solution obtained is clear. When evaporated, it leaves a clear, brittle resin. Example-25.2 parts of ground melamine (0.2 mol) and 63.6 parts of benzaldehyde (0.6 lol) are heated to the boil in a small flask with an air-cooled attachment from which the water of reaction can escape. After 1 hour the melamine has dissolved. A sample taken from the solution solidifies in the cold to form a brittle resin, which is soluble in benzyl alcohol. The reaction is kept boiling for an hour and then cooled. The clear resin is still soluble in benzyl alcohol.

Instead of 63.6 parts of benzaldehyde, r27 parts are used, i.e. twice that amount Amount used, a very similar resin is obtained.

EXAMPLE 3 Sixth, -, parts of helamine ('= 0 mol) and 20 parts of zinitaldeliyd (3 /. The mass gradually turns dark; it soon turns into a sticky, brown resin, which quickly becomes gelatinous after about 15 minutes and, after foaming beforehand, forms a brown, solid mass. After boiling twice with water, a brown, odorless resin is obtained. Example 0.72 part of hexahydrobenzaldehyde (about 0.110 mol) and 0.27 part of elamine (about 1/100 mol) are heated together to boiling. Dissolution of the melamine soon occurs; with further heating, the condensation product becomes thicker and turns brownish-yellow in color. The viscous condensate solidifies on cooling. It is a clear, brittle resin that resembles rosin in appearance. After about 16 hours: when heated at 8o0, it sinters at about i2o0. It is not soluble in @. \ 'Water, but fairly soluble in alcohol. Example flame cooked. After about 3 hours of boiling, most of the white precipitate initially formed has dissolved and the solution begins to gelatinize slightly. It is cooled and the whitish, translucent jelly is rubbed with 32 parts of wood flour in a mortar, dried at 60 ° and then powdered and pressed. With a pressing time of 3 minutes at i; o 'and 300 kg / C1112 pressure, for example, very hard, brown, translucent compacts are obtained from this powder. Example 126 parts of melamine (once), 100 parts of glacial acetic acid, 10 parts of conc. Sulfuric acid and 264 parts of paraldehyde (2 mol) are refluxed for 4 hours. The somewhat brown-colored solution obtained is filtered, if necessary. When it evaporates in the oven, it leaves a thin, hard, brittle varnish behind. Evaporated in a vacuum, a dry, foamy resin is obtained which is very easily soluble in water. 0.25 parts of terephthalaldehyde (3/100 mol) are liquefied by melting, 0.25 parts of melamine (1/100 mol) are introduced and the mixture is further heated; included. soon foams the mass up a little and gives a solidifying, light brown mass that hardens when it has cooled down. It is insoluble in water. The condensation product is boiled with water to remove any starting materials that have not yet been released: it is a light brown powder. Example 5 parts of 3-amino-i # 2 # 4-plientriazoxine (reports from Deutsch. Chem. Ges. I6 [1913J 3522) are heated to boiling with i 5 parts of benzaldehyde while stirring. A solution has emerged after a few minutes. This solution is kept boiling for 2 hours and then cooled and diluted with ether. A brownish mass separates out, which is filtered off and washed with ether. This product melts around 15o0. It dissolves in hot toluene and separates out again when the solution cools down. The product dissolved in this way has not changed its melting point.

Example ? i o.6 parts of benzaldehyde (1/10 mol) are mixed with 12.6 parts Melarnin (1/10 mol) and 2 parts by volume of 50% sulfuric acid rubbed cold and with 21.1 parts by volume 4.2.6 percent by volume alcoholic formaldehyde (: '/, o i \ Iol) at reflux on an open Example 9 12o parts of urea (2 mol), 126 parts of melamine (1 mol), 600 parts 3o% formaldehyde solution (61Iol) and ii2 parts acrolein (2 Mo1) «-Erden combined and mixed with 20 parts of n-sodium hydroxide solution. That alkaline reacting mixture is heated to boiling with reflux cooling. In a short time a clear solution is produced, which is kept boiling for another 20 minutes and then cooled will. A clear, very viscous solution is obtained, which is applied in a thin layer, hardened in the oven and converted into a hard lacquer. On addition of .4o parts n-hydrochloric acid, the solution becomes even more viscous on standing, and so does the rate of hardening is thereby increased. Example 10 94 parts of phenol (1 mol), 63 parts of melamine (0.5 Mol) and 318 parts of benzaldehyde (3 11o1) are heated to the boil. In a few minutes a solution has emerged. which in the further treatment in a short time to a first goddess-like and then hardening clear hatred froze.

Claims (1)

PATENT CLAIM: i. Process for the production of aldehyde condensation products, characterized by (iali one aldehydes that contain at least 2 hollow stolatonia, or substances that split off such aldehydes, bmv. Mixtures of these Aldehydes or aldehyde-releasing compounds with formaldehyde or its polymers on aminotriazines or their derivatives up to the formation of non-crystalline masses can act. The method according to claim I, wherein the aminotriazine is the 2 # q. # 6-Triamino-I `3 '5-triazine (melainin) is used. 3. The method according to claims i and 2, wherein Condensation agents, especially acidic or basic in nature, can be used. q .. Process according to Claims I to 3. wherein, with the addition of further substances, which capable of forming condensation products with aldehydes. Mixed resins are produced.