DE667744C - Process for the preparation of condensation products which are soluble or easily dispersible in water - Google Patents

Description

Process for the preparation of water-soluble or easily dispersible Condensation products It has been found that they are soluble or easily in water distributable condensation products are obtained if one uses organic compounds, which contain one or more amino groups in the molecule, such amounts of ethylene oxide or polyglycol ether residues of such molecular size or compounds providing them brings about that in the molecule of the starting material at least one polyglycol ether residue with q. or more -C2 H4 groups occur. One brings, for example, the ethylene oxide on the as Aus. Compounds containing amino groups and used as precursors in such a way to act that one in the latter, expediently in dissolved or molten form and possibly with the application of pressure, the calculated amount of ethylene oxide introduces gaseous or liquid. By measuring the weight gain from the excess Ethylene oxide-free reaction product can easily be determined whether the required Number of moles of ethylene oxide has entered the molecule.

The amount of ethylene oxide used depends on the number of reactive hydrogen atoms present in the starting material, so that, for example, when using primary amines, the action of at least 7 moles of ethylene oxide per mole of the starting material is required. According to the present process, the introduction of polyglycol ether residues with at least q. -CpH4 groups give the products particularly valuable properties. They are characterized by an excellent dispersing effect, e.g. B. for fatty acids, waxes, soot and the like., And are therefore particularly effective emulsifiers and excellent detergents for materials containing oil or dirt, eg. B. wool or cotton. They have an excellent protective colloid effect, which enables them to a high degree to prevent the precipitation of water-insoluble compounds, e.g. B. from lime soaps to prevent. ' The novel polyethers obtained can be used in the dyeing industry for all types of dye in a very `` versatile '' manner. wendbär, in particular, they offer Vo rteile in. the wool dye stand out etiQ "z`- üncE älisiermi t impossible the rejection is not shown to the right to be a driving force. Far - exercises. - For the present process are suitable, for. B. aliphatic, cycloaliphatic or aliphatic-aromatic or aromatic amines or carboxamides which have at least one hydrogen atom bonded to nitrogen, e.g. B. methyl-, ethyl-, diethyl-, butyl-, hexylamine, ethylenediamine, oc -pronylenediamine sauce (ethyl-, oleyl-, octodecyl- hylolctodecyl "-, didodecylamine, further A`niTin, Ätliylanilin, Phenylenediamine, Benzidine, Aminoazobenzol Naphthylamines, aminoanthraquinones, piperidine, and the like. Acid amides also come into consideration, e.g. urea and its derivatives, lauric acid amide, stearic acid; # endiaiiain-ode, r - Tri # tvyietite '! # amine, Palmitinsäureätliy lamid, Ülsäureanilid and the like. Ether, nitro or sulfo groups contained in the molecule are suitable for the present process.For example, methylbutanolamine, chloroctodecylamine, p-aminobenzaldehyde, p-aminophenol, glycocollate, o-nitranilin, urethanes, taurines and their homologues, etc. are also suitable Imino compounds that still have a free hydrogen atom bound to nitrogen can also be z. B. piperidine have, use for the condensation with Äthylcnoxyd.

The polyglycol ether residues can be added to the starting materials mentioned by treatment with ethylene oxide or substances that form such, if necessary using catalysts and / or pressure, possibly at elevated temperature and with the use of solvents or diluents, attach. Depending on the applied amount of ethylene oxide succeeds in polyglycol ether residues in the molecule of the Introduce the starting material, in many cases even a much larger one Having number of carbon atoms as the starting materials. Depending on the type of raw material one can obtain products that contain one or more polyglycol ether residues in the molecule of the type described. You can already use the starting materials mentioned Introduce formed higher molecular weight polyglycol ether residues, e.g. B. in such a way that amines, for example ethylamine or ethylenediamine, or alcohols or carboxylic acids Ethylene oxide can act in appropriate amounts and the compounds thus formed introduces into the amino group of amines or carboxamides.

The. Products obtainable in the manner described are soluble or dispersible in water and have a high dispersibility for liquid and solid substances, e.g. U as oils, resins, waxes, dyes, carbon black, hydrocarbons like: @; @ are the @ zesondere as auxiliaries in the dyeing and D -uc @erei, v or a dyeing em eirn .in @ a.uren.. Baths. In, the latter case, they permit the production of particularly egale r and he reibech dyeings; You can also join us. Advantage in carbonizing, mercerizing, finishing, sizing, cupping, washing, fulling, etc. can be used. They also have a very good protective colloid effect, which makes their usability particularly valuable in all cases in which the precipitation of insoluble compounds is to be avoided. Since the polyglycol compounds described have no salt-forming groups, they are resistant * to metal salts of any kind. The condensation products described can also contain Advantage use. As far as viscous substances with polyglycolate residues of the specified type are involved, they are also suitable for the production of reel oils for rayon as well as lubricating and drilling oils.

The accumulation of polyglycol ether residues of the type described products available on organic compounds with amino groups usually have nor one or more terminal free hydroxyl groups that are reactive with Connections can be implemented. The acids are primarily suitable for this, which react to form esters, e.g. B. sulfuric acid, phosphoric acid, phthalic acid, Fatty acids and their derivatives, as well as haloparaffins, chlorocarbonic acid esters, phenyl isocyanate and the like. The described compounds containing polyglycol ether residues can also be used halogenate and then, especially after replacing the terminal hydroxyl groups by halogen, with basic compounds such as amines, acid amides or containing hydroxyl groups Bring compounds, etc., or alcoholates to the reaction. All of these combinations also provide valuable aids - for textile, leather, paper, paint, Rubber industry etc.

The condensation products described can be used either on their own or together with other agents. For example, preparations show the products and soaps mentioned, saponin, sulfuric acid esters. Or real sulfonic acids of organic compounds, e.g. B. Turkish red oils, sulfuric acid esters of alcohols, glue, rubber-like substances, dextrin, sulfite cellulose waste liquor, cellulose ethers or other colloids, such as ethylene oxide inside the polymer, very valuable properties: in many cases it is also advantageous to use them - together with salts of inorganic or organic acids and bases, e.g. B. hydroxides of mono- or polyvalent metals, or amines, e.g. B. methyl, diethyl or monoethanolamine, as well as piperidine, pyridine, etc., z. B. water glass, salts of phosphoric acids, glycerine, polyglycerine, or organic solvents, bleaching agents such as perborates and the like, or other substances to be used. In particular, highly concentrated aqueous solutions of Turkish red oils, true organic sulfonic acids and the like can be prepared using the condensation products mentioned. Example i About 12 moles of ethylene oxide are allowed to act on 1 mole of butylamine in a pressure vessel with the addition of a small amount of caustic alkali, then 1 part of the condensation product obtained in this way is heated to about 1.40 ° under reduced pressure for 3 hours with 1 part oleic acid. A product is obtained which is suitable for emulsifying substances insoluble in water, e.g. B. of organic solvents, is very suitable. EXAMPLE 2 1 mole of octodecylamine is heated with 8 moles of ethylene oxide in the Aütöklgven under pressure to about 1500 and in this way a waxy, water-soluble product is obtained which, among other things, has very good leveling properties when dyeing wool in acidic baths. For example, a very smooth dye is obtained if Wollcheviot is put in a '° dye bath with 0.250 % anthraquinone blue SR extra (Schultz, Dye tables 1931, no . 737) and 0.05 % of a red dye obtainable according to the method of patent 288838 and 10% sodium bisulfate for one hour at boiling temperature with the addition of 0.25 g of the above-mentioned condensation product of octodecylamine and ethylene oxide.

.A product of similar properties can be obtained if you use the Oxyäthyloktodecylamin instead of octodecylamine, the z. B. by reacting the sulfuric acid ester of octodecyl alcohol with monoethanolamine - is available. For example, the action of almost 10 moles of ethylene oxide on 1 mole of oxyethyloctodecylamine produces a product which, among other things, is - Very suitable for washing loose wool or piece of wool. Similar products are also obtained if condensation products from z. B. ethylene chlorohydrin or polyglycerol chloride and dodecylamine or octodecylamine are used. EXAMPLE 3 About 30 moles of ethylene oxide are allowed to act under pressure on one mole of an amine obtainable by reacting hard trichloro paraffin with ammonia and having an average molecular weight of 400. The result is a brown water-soluble product, which z. B. is well suited as an emulsifier for fatty oils or mineral oils. Said condensation product is clearly soluble in mineral oil and the like. Such solutions have a higher viscosity than machine oil, etc .; they can therefore be used with advantage as lubricants, for example. Example q. About 7 moles of ethylene oxide are allowed to act on 1 mole of coconut fatty acid amide under pressure at 160 ° in the presence of 1% of sodium ethylate. An ointment-like, water-soluble product with high wetting power is obtained which can be used with advantage in hard water. For example, the precipitation of lime soaps in the presence of the condensation product in treatment liquors for textiles can be avoided. Lime soaps that have already failed can be restored by adding the product and heating it to about 6o0. be brought into solution. An aqueous solution of the product is suitable on its own or together with organic solvents as a spotting agent. It can also be used as a finishing agent for rayon, e.g. B. copper silk, serve, at the same time, especially in the presence of organic acids such as lactic acid and the like., A silk-like handle is achieved. Due to its acid resistance, the product can be used with advantage in felling baths for rayon.

By the action of about 10 moles of ethylene oxide on 1 mole of naphthenic acid amide obtained at about 150 ° under pressure and with the addition of 0.2% sodium hydroxide solution of 40 'B6 one z. B. a condensation product that can be used as a wetting agent when drying textiles suitable.

If, under the conditions given above, about 2o mol of ethylene oxide per c mol of ricinoleic acid oxyethyl amide, the z. B. is obtainable by condensation of rieiinoleic acid with monoethanolamine, so you get a very good leveling and dispersing agent, which is also very suitable as an additive to latex. EXAMPLE 5 If about 30 moles of ethylene oxide are exposed to 1 mole of oleic acid amide, a paste-like product which is easily soluble in water and has very good protective colloid properties is obtained. If this product is added when dyeing with chromizing dyes, acidic dyes or metal complex compounds of acidic dyes, dyeings that are very rubbing-fast are achieved.

'If one works, we obtain a preparation, which is very kalkbeständig and even with the use of water of 250 DH no precipitation of lime soap provides in a commercial Marseille soap or curd soap 3 to 15 0/0 of the above, condensation product made from oleic acid amide a. The product can also be incorporated into toilet and bath soaps with advantage; it is also suitable as an additive in the production of soap pastes and other cosmetic products, e.g. B. shaving soaps, toothpastes and the like. Soap mixtures of this type can be used with advantage in white laundry, among other things. EXAMPLE 6 One mole of dodecanesulfamide is allowed to act under pressure at from about 20 to 130 moles of ethylene oxide. A brown oil is obtained which has good wetting and washing properties. The product made in the same way from toluenesulfamide has a high leveling power when dyeing wool in an acid bath. By treating the amide of sulfopalrinitic acid with about 15 moles of ethylene oxide, a condensation product is obtained which has a good protective colloid effect. Example 7 By introducing 30 moles of gaseous ethylene oxide into 1 mole of molten oleylethylenediamine, a waxy product is obtained which has a high emulsifying power, in particular for olein, waxes and the like. Such emulsions can be used in particular in the textile industry and for the production of shoe polishes, floor polishes, polishing agents and the like. The product is also suitable as a protective colloid in the production of naphthol A S dyeings, and when added to the developing liquor it allows dyeings that are very rubbing to be achieved. If you use a condensation product of 15 moles of ethylene oxide and. 1 mole of dodecylethylenediamine when dyeing with vat or noun dyes, see above. you get a very level and well dyed product. .

. Example 8 If one mole of the condensation product, which by action of 14M01 ethylene oxide on 1 mole of m-phenylenediamine was produced without pressure, with 1 mole of oleic acid for several hours at about 1400, a product is obtained which has a good leveling capacity and advantageously z. B. when dyeing acetate silk with dyes insoluble in water is suitable. 'Treat the amide from stearic acid and m-phenylenediamine with about 25 moles of ethylene oxide, one obtains also enable a product with a high level of equality. Example 9 To 100 parts of a Condensation product, which by the action of 18 to 201U01 ethylene oxide on i Mol diethylene glycol or butylethanolamine is obtained, one gives i part of red phosphorus and then in small portions with ice-cooling 30 parts of bromine. After about an hour The reaction mixture is slowly heated on the water bath and then stirred the water formed and the hydrogen bromide removed in vacuo. Instead of the The starting material used diethylene glycol can also z. B. ethyl or butyl alcohol Find use.

ii parts of the bromide obtained in this way are treated with 2.7 parts of octodecylamine and 1.3 parts of potassium carbonate at 50 to 60 for about 3 hours; then about 20 parts of ethyl alcohol are added, whereupon the precipitated potassium bromide is sucked off and the ethyl alcohol is distilled off. The reaction product obtained is a semi-solid, water-soluble mass which has excellent leveling properties, e.g. B. in the dyeing of cotton and ZVoae possesses. When artificial silk is mixed with aqueous solutions of the product mentioned, it is given a soft, supple handle. Example 10 One brings to 1112o1 monobutanolamine .21 moles of ethylene oxide to act and reacts the condensation product with 1 mole of lauric acid. The product produced in this way is suitable because of its excellent dispersing, E alisier- and protective colloid we-. Particularly suitable for the acid dyeing of wool with poorly leveling and poorly soluble or slightly tending to precipitate wool dyes. When dyeing piece goods, woven from wool, silk, etc. or, loose wool or leather are perfect in this way. Staining achieved. - - '. Similar products of very good leveling for rapidly absorbing acidic dyes are obtained if about -25 mol of ethylene oxide are brought into action for 1 mol of the reaction product obtainable by heating equal parts of coconut oil and triethylenetetramine for several hours at 10 to 1400 .

Example ii One leaves in the autoclave for one mole of the monoabietic acid ester of ethylethanolamine at 6o to 700 in the course of about 30 minutes in the presence of 0.1% caustic potash, about 5 moles of ethylene oxide act. The highly viscous oily condensation product obtained in this way can easily be emulsified in water. A mixture of one part of the reaction product mentioned and one part of polymeric ethylene oxide is particularly suitable in the form of its aqueous solution as a sizing agent for viscose silk. EXAMPLE 12 If 6 moles of ethylene oxide are allowed to act on 1 mole of coconut fatty acid amide, a yellow-brown, waxy condensation product is obtained which is very suitable for the production of creams, ointments and functional skin oils.

For example, by mixing 1.5 parts by weight of the aforementioned condensation product, 4 parts by weight of cetyl alcohol, 3 parts by weight Wool fat, 10 parts by weight of Vaseline, 1 part by weight of glycerine and 3o parts by weight Water a skin cream that works well.

Instead of the abovementioned condensation product, you can also use the equal amount by weight of the product of action of 10 moles of ethylene oxide to 1 mole Use oleic anilide. Example 13 1 mol of oleylamine is brought in a stirred flask with the addition of o,: 20 /, sodium methylate 9. Mo1 ethylene oxide at 13o to 140 'for Action and thus receives a scl-yvach colored ointment-like product, which is a good dispersing power. for basic dyes and also as dyeing auxiliaries; z. B. when dyeing basic j and substituted or acidic at the same time Dyes, can be used advantageously, as well as in the production of colored or White etching.

A product with similar properties is obtained if one is in the specified manner on i mole octodecylamine 2'o mole ethylene oxide brings to action. This product is suitable e.g. B. as a substitute for bast soap and can with dyes and extenders are processed into dye preparations.

In some cases it is useful to use the condensation product mentioned. to mix with the dye from the outset; in this case the same is obtained Effect. A suitable mixture contains, for example, 13.50 /, Diamantgrün GX (Schultz, Dye Tables 1934 No. 754), 135 ° / o of the abovementioned condensation product from octodecylamine and ethylene oxide and 73% dextrin. When creating colored sentences with basic dyes or in the aftertreatment of the prints, the application offers the aforementioned condensation product of octodecylamine and ethylene oxide valuable Advantage, as this achieves good rubbing fastness of the prints as well as pure etching will. The products are also very well suited to the raffia soap when dyeing Replace silk with acidic or other dyes. Example 14 Transfer in the rotary bomb 1 mole of oleic anilide with 0.1% sodium hydroxide and brings it to 17o up to igo ° 16 to 20 moles of ethylene oxide for 7 hours to act (maximum pressure 25 atm). In this way, a semi-solid condensation product is obtained Use in the production of water-insoluble pigments due to its excellent properties protective colloid effect allows the achievement of very finely divided pigments.

In the production of pigments or colored lacquers, e.g. B. in the clutch of azo dye components, in the oxidation of leuco compounds of vat dyes or their sulfuric acid esters, can be achieved by using the at the same time above-mentioned condensation product a particularly fine distribution of the pigments; the same effect is achieved in the manufacture of salts or condensation products non-colored compounds, e.g. B. in the condensation of urea with formaldehyde in the presence of acid: Example 15 One mole of dodecylamine is admixed with 0.1% potassium ethylate and brings ethylene oxide to act at 130 ° 20M01 '. A colorless one is thus obtained Waxy product, colloidally soluble in water, its good detergency in acidic liquors e.g. B. the simultaneous dyeing and washing of sweat wool or oily woolen fabrics. You can dye or sweat wool. oily woolen fabric for 1 hour at the boiling point in an acidic dye liquor, the . except for the acid 3 11j0 of a red one, according to the method of patent 288 838 available coloring agent as well as io 11/0 Glauber's salt - contains and also per liter Liquor 2 g of the above-mentioned condensation product. It was next to the coloring at the same time a clear washing effect is achieved.

In an analogous way one can also use other animal, vegetable and artificial fibers using the ethy products described Wash and dye lenoxide for compounds containing amino groups at the same time.

Claims (1)

PATENT CLAIM: Process for the production of water-soluble or easily distributable condensation products, characterized in that one on organic compounds containing amino groups in the molecule, such amounts Ethylene oxide or polyglycol ether residues of such molecular size or those supplying them Brings compounds to action that at least in the molecule of the starting material a polyglycol ether residue with 4th or more -C @ H, - groups occurs and optionally free hydroxyl groups with reactive compounds still present in the reaction product implements.