DE922711C - Process for the conversion of compounds with reactive hydrogen atoms into their reaction products with isocyanate esters - Google Patents

Description

Process for the conversion of compounds with reactive hydrogen atoms in their reaction products with isocyanic acid esters. The invention relates to a new one Process for the transfer of compounds with reactive hydrogen atoms in their reaction products with isocyanic acid esters. The term isocyanic acid ester is intended to include both the monofunctional and the polyfunctional compounds include. The substances mentioned are characterized by their high reactivity from which they become interesting starting materials or intermediates for organic syntheses and for finishing operations, e.g. B. in the textile industry, makes. From the structure Aside from simple organic compounds, one can, for example, from polyfunctional Isocyanic acid esters and polyfunctional compounds with reactive hydrogen atoms, z. B. polyoxy compounds, polyamino compounds or polycarboxylic acids, high molecular weight Manufacture plastics. Such reactions can take the form of stoving enamels be carried out on a pad. One can also use them for the production of Take advantage of prepregs, adhesives and the like. Furthermore, mono- and polyfunctional Isocyanic acid esters alone or in combination with mono- or polyfunctional compounds with reactive hydrogen atoms, e.g. B. oxy compounds, amino compounds or carboxylic acids for the finishing of absorbent materials such as textiles, paper, Cardboard, Wood, leather and the like can be used. Depending on the compounds used and depending on the absorbent material in question, the effect of this treatment can for example in a hydrophobization, in a change in the coloring capacity, in an improvement the wet tensile strength or other mechanical properties. So far the isocyanic acid esters in these cases alone without additional compounds reactive hydrogen atoms are used, let it remain an open question, whether the effect achieved on a reaction with reactive groups of the to be refined Material or is due to a reaction with water contained therein. The reactions mentioned are, if a diluent is used at all was usually carried out in inert organic solvents.

According to the invention are now used for the transfer of compounds with reactive hydrogen atoms in their reaction products with isocyanic acid esters instead of the free isocyanic acid esters, their water-soluble addition products used with acid sulfuric acid salts such as those available under patent $ 59I56 are. According to the invention, these reactions are preferably carried out in an aqueous medium. Addition compounds from isocyanates and acidic sulphurous acid salts are in usually soluble in water and also sufficiently stable in an aqueous medium, to allow the preparation of reasonably long-lasting solutions. The durability of the solutions depends largely on the underlying isocyanate, with the Adducts of the aliphatic isocyanates give more stable solutions than those of the aromatic. On the other hand, the addition compounds can be used in an aqueous medium under suitable conditions Conditions are split into the isocyanic acid ester on which they are based. In particular, you have it in hand, their disintegration in the aqueous medium in the desired manner Way to regulate. The rule that applies here is that the attachment compounds are stable. the more acidic character of the aqueous medium increases, and vice versa in alkaline Medium falls off. As a result, the addition of acids has a stabilizing effect while the addition of amines favors the decomposition. One uses for the latter Purpose of course preferably tertiary amines, since these with the isocyanic acid esters not react. Furthermore, the disintegration can be caused by the addition of salts of the nitrous Acid or accelerated by using higher temperatures. It recommends sometimes especially in textile finishing after evaporation of the solvent the water used to heat it to I2o to I5o °. Eventually the decay will presumably also influenced by the nature of the reactive compound to be used.

As addition compounds of isocyanic acid esters, for example those of monoisocyanates, diisocyanates and polyisocyanates of the aliphatic, aromatic and aliphatic aromatic series in question. Examples are Methyl isocyanate, ethyl isocyanate, I-chlorhexyl-6-isocyanate, hexyl isocyanate, dodecyl isocyanate, Stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, toluyl isocyanate, chlorophenyl isocyanate, Ethylene diisocyanate, butane and hexane diisocyanate, thiodipropyl-3, '3'-diisocyanate, Cyclohexyl-4,4'-diisocyanate, phenylene-1,4-diisocyanate and phenyl-r, 3,5-triisocyanate. In contrast to the free isocyanic acid esters, the ones used here are adducts odorless and have no physiological irritation whatsoever.

As a connection with reactive hydrogen atoms, let us begin Called water, which reacts with isocyanic acid esters to form ureas. In addition, mono- and polyamino compounds should be mentioned in the first place, as they are in uniform amines or in higher molecular weight protein products of gelatine or Casein or its cleavage products are present.

The new invention is capable of the most versatile applications depending on the starting materials and working conditions. For example, absorbent materials, such as paper, can be treated with addition compounds composed of isocyanic acid esters alone, that is to say without the use of other reactive compounds, an increase in the wet tensile strength being obtained. Using the same procedure, staple viscose can be rendered hydrophobic with the aid of addition compounds from higher fatty monoisocyanates. The same procedure makes it possible to improve the dyeability of wool with the aid of the addition compounds from aromatic mono- or diisocyanates. In all of these areas of application, it may be left open whether, in chemical terms, there is only a conversion with water, with the incorporation of the ureas formed in the fibers, or whether there is also a reaction with the fiber material. The new reaction can be used to produce simple organic syntheses, by reacting the addition compounds of isocyanates with mono- or polyamino compounds. Another possible application consists in incorporating the aqueous solutions of the above-described isocyanic acid ester addition compounds, including in particular the polyfunctional compounds, gelatin solutions, such as those used, for example, for the production of photographic halide silver emulsions or other gelatin layers used in the construction of photographic layers, e.g. B. protective layers, filter layers, antihalation layers, cast back layers, barite layers and the like., Can be used. In this case, the addition of the stressed body serves to. Increasing the melting point, the mechanical strength and reducing the swellability of the layer in question.

Compared to the formalin hardening that was previously preferred for this purpose has the new way of working the following advantages: non-volatility and therefore precise dosing of the applied body, no unfavorable influence the photographic properties of the silver halide gelatin emulsion Sensitivity, gradation, blackening and image tone and no post-curing during storage.

Formalin hardening is known to behave in this latter point particularly unfavorable, as the gelatin layer hardened with formalin only takes weeks Storage reaches its highest melting point. In contrast, those with the stressed bodies hardened gelatin layers one day after drying the maximum of their hardening.

Finally, the aftertreatment of molded gelatin and casein materials, e.g. B. synthetic casein, mentioned, with an increase the use of which for lightening organic materials is described in patent 7.46 569 . Example 2 26.5 parts of the addition product of i-chlorohexyl-6-isocyanate with sodium bisulfite are dissolved in 150 parts of water. The solution of 8.6 parts of polyethyleneimine in 50 parts of water is added. The reaction mixture, which is initially clear, begins to become cloudy when heated gently and, when heated to the boiling point, separates out an initially slimy, then slowly hardening reaction product. This is isolated and dried. 22 parts of a pulverizable, chlorine-containing, water-insoluble resin are obtained which, for example, can be finely ground and added as an animalizing agent to viscose or copper silk spinning batches. Example 3 Cotton or cellulose fabric is soaked at 80 ° with an aqueous solution which contains 20 g of the adduct of stearyl isocyanate in sodium bisulfite dissolved per liter. As usual, the fabric is squeezed off and dried at 130 '. You then rinse with warm water and dry again. After this treatment, the fabric has become water-repellent to the extent that it is achieved by using stearyl isocyanate in an organic solvent. For example, the water absorption of a cotton fabric fell from 116 to 42% (measured according to a sprinkling method). tear resistance and an improvement in water resistance can be observed.

Example i 20.7 parts of diaminostilbene-2,2'-disulfonic acid sodium are dissolved with the addition of 5 parts of sodium carbonate in zoo parts of water. Man carries 2q in portions at 3o to 0 °. Parts of the adduct of phenyl isocyanate and Potassium bisulfite. Initially, this compound dissolves in the reaction mixture on; after some time, the new condensation product separates out. After 12 Hours is suctioned off, the filter residue is dissolved in hot water, of little insoluble constituents freed and salted out. A good yield is obtained the compound of the following formula: Instead of the above compound the adduct of stearylamine with ammonium bisulfite can also be used. Example q. Paper is made with a solution of 10 parts of the addition compound of -i-methyl-benzene-2, q.-diisocyanate impregnated with potassium bisulfite in parts of water and dried for 3/4 hours at 130 °. While the dry tensile strength of q.7o kg / qcm remains practically unchanged, the wet tensile strength increases as a result of this treatment from 17 to 128 kg / sqcm.

The addition product of i-isopropylbenzene-2, q.-diisocyanate on potassium bisulfite can be used. Example 5 wool yarn is used at q.0 ° with a 100% aqueous solution of the adduct of phenylene-1,3-diisocyanate Pickled on potassium bisulfite, squeezed off, pre-dried in the air and then short Time heated to io 'in the drying cabinet and rinsed. The yarn treated in this way becomes then together with untreated wool with an acidic wool dye, for example Dyed wool-blue FFG. The treated goods are colored faster and darker on than the untreated. Example 6 Synthetic casein wool which has been pre-hardened with formaldehyde was, is in the solution of 2o parts of the adduct of r-methylbenzene-2, 4-diisocyanate on potassium bisulfite placed in 25o parts of water at room temperature, pressed and dried at 80 ° in a drying cabinet. After rinsing, the fiber exhibits improved dry and especially improved wet tensile strengths. example 7 r kg of a photographic bromine-iodine-silver gelatin emulsion with a content of 8% gelatin and a pH; Value of 6.7 is just before going to any of the usual Layer support, such as glass, paper or film, is poured with 5o ccm of a 3% strength aqueous solution of the addition compound of 'benzene-2, 5-dimethyl-r, 4-diisocyanate added to potassium bisulfite. Just one day after it was made, it shows that way hardened photographic layer after processing in the usual photographic Baths a melting point of 6o ° in water while the uncured layer is underneath already melts in water of 30 ° under the same conditions. Example 8 z kg one Photographic chlorine-bromide-silver emulsion containing 8% gelatin and a pH value of 4.8 just before it is poured onto barite base paper, with 40 ccm of a 7.5% aqueous solution of the adduct of benzene-z-methyl-2, 4-diisocyanate added to potassium bisulfite. A common protective layer solution is applied to this layer applied with a content of 2% gelatin, which per liter 12 ccm of a 7.5% containing aqueous solution of the same curing agent mentioned above. the In this case, the hardening is so high that the Layer is resistant to boiling water and is quick-drying photographic papers used modern drying apparatus as well as in the Equipment used to produce a glossy finish is completely trouble-free at higher temperatures can be processed. A comparison with formalin in the emulsion and protective layer Hardened photographic paper reaches such a high degree of hardening in the first place after several weeks of storage. In addition, those with the stressed body lose hardened chlorine-bromide-papers reach the desired warm level after a very long period of storage brown-black picture tone, while the picture tone of the similar hardened with formalin photographic papers in a very undesirable way after just a few months turns to cold, pure black tones.

Claims (1)

PATENT CLAIM: Process for transferring compounds with reactive Hydrogen atoms in their reaction products with isocyanic acid esters, characterized in that that instead of the free isocyanic acid esters, their water-soluble adducts are used acidic sulfuric acid salts according to patent 859 156, preferably in an aqueous medium applies.