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United States Patent Office Patented Feb 3,367,956 United States Patent Office Patented Feb. 6, 1968 1 2 3,367,956 or cycloaliphatic hydrocarbons. When following the pro PREPARATION OF BIURET POLYISOCYANATES cedure of the present invention, it is critical to elevate Hans Joachim Hennig, Cologne-Starnmheim, and Otto the temperature at least in the later stage of the reaction Bayer, Erwin Windemuth, and Wilhelm Bunge, Lever ' to about ISO-250° C. to bring about formation of mono kusen, Germany, assignors to Farhenfabriken Bayer isocyanate which must be continuously removed substan Aktiengesellschaft, Leverkusen, Germany, a German corporation tially as soon as it is formed, preferably by operating at N0 Drawing. Filed Apr. 1, 1964, Ser. No. 356,650 the elevated temperature at a reduced pressure or by Claims priority, application Germany, Apr. 13, 1963, using a carrier gas to remove the organic monoisocyanate F 39,482 from the reaction mixture substantially as soon as it is 6 Claims. (Cl. 260—453) formed. Then the well-de?ned biuret polyisocyanates of the invention are formed instead of high molecular weight This invention relates to organic polyisocyanates and condensation products. Thus, it is an essential feature of more particularly to a process for the preparation of this invention to carry out the process under such tem biuret polyisocyanates. Moreover, this invention provides perature conditions that a monoisocyanate is split off and a new and unexpected way of preparing biuret polyiso the reactants may recombine to form a biuret polyiso cyanates which may also contain carbamyl groups with cyanate. Instead of high molecular weight condensation out the formation of undesirable by-products. products referred to in the German patent, when the It is known to prepare biuret polyisocyanates, for ex present procedure is followed, one obtains polyvalent ample, according to the method of German Patent isocyanates with biuret groupings which are well-de?ned 1,101,394, by reacting an organic diisocyanate with water. and preferably correspond substantially to the general The heretofore known method produces a biuret polyiso formula: cyanate including carbon dioxide as a by-product which must be removed from the reaction mixture. It is desirable to obtain this type of product without the formation of undesirable by-products. 25 or those with a carbamyl biuret structure which corre It has been proposed in German Patent 883,504 to re spond to the general formula: act ureas with isocyanates to prepare a reaction mixture having a high isocyanate content. The heretofore known process results only in condensation products which could be hardened by heating and thus could only be used for In the foregoing formulas, n represents a positive integer the production of coatings or baked enamels for wire greater than 2, X represents hydrogen or the grouping coating. ——CO—NX-—R—NCO and X represents the latter group Ureas are also known to react with diisocyanates ac ings at least once in the molecule. The group represented cording to “Angewandte Chemie” 72 (1960), page 1002. by R may be the same or different divalent group which The products there disclosed are substituted ureas and low is obtained by removing the —NCO groups from the di boiling monoisocyanates. isocyanates which are used as starting materials. It is therefore an object of this invention to provide an The starting materials may be represented by the fol improved process for the production of biuret polyiso lowing general formula: cyanates. Another object of this invention is to provide a process for the preparation of biuret polyisocyanates while 40 avoiding the formation of useless by-products. A further object of this invention is to provide a method of simul taneously preparing a biuret polyisocyanate and a low molecular weight volatile organic monoisocyanate. Still another object of this invention is to provide a process for 45 the preparation of a carbamyl biuret polyisocyanate with the formation of undesirable by-products. A further ob The order of the list is simultaneously the order of prac ject of this invention is to provide a process for the prep tical importance of the urea starting material. It is es aration of biuret polyisocyanates including those which sential that the substituted ureas contain at least one contain carbamyl groups and contain at least three 50 grouping NHR'—CO. Bis-ureas of the type —NCO groups per molecule which are substantially free of gaseous contaminates. The foregoing objects and others which will become do not work. apparent from the following description are accomplished Speci?c examples in support of these formulas may be in accordance with the invention, generally speaking, by 55 found below in working Examples 1 through 18. R prefer providing a process for the prepartion of biuret polyiso ably has l-l8 carbon atoms and R’ preferably has l-6 cyanates wherein at least three mols of an organic diiso carbon atoms. A monoisocyanate, R'—NCO, is continu_— cyanate are reacted with a substituted urea, in such pro ously formed and removed from the reaction mixture. portions that there are at least three mols of organic R’ represents a monovalent organic radical and may be diisocyanate present per mol of said substituted urea, aliphatic, cycloaliphatic, aromatic, linear or branched, sat at least in the later stage of the reaction at an elevated urated or unsaturated and can contain hetero atoms. R’ temperature with the continuous removal of the organic is obtained by removing one of the N-substituted or-. monoisocyanate formed in the reaction. It is an essential ganic radicals from the substituted ureas referred to above condition for this reaction to take place that the organic and speci?cally set forth below. monoisocyanate is removed substantially as soon as it is 65 Any suitable organic diisocyanate may be used either formed. German Patent 883,504 referred to above, shows, alone or in admixture with one another. The diisocyanates inter alia, the reaction of ureas with polyisocyanates. which are useful in the process of the present inven Moreover, that German patent discloses that the high mo tion are preferbly monomers and include those ’whose lecular weight condensation products containing isocya —-NCO groups have substantially the same reactivity nate groups, which are formed by the process disclosed, rates, such as tetramethylene diisocyanate, hexamethylene are freed of unreacted starting material after completion diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexyl of the reaction by extraction of the product with aliphatic methane - 4,4’ - diisocyanate, xylylene diisocyanate, p~ 3,367,956 3 4 phenylene diisocyanate, diphenylmethane-4,4'-diisocya products which correspond to the indicated formulas. nate, diphenyldimethylmethane-4,4’-diisocyanate, 3,3'-di While it is possible to carry out the invention using an methoxy-diphenylmethane-4,4'-diisocyanate and the like. excess of three mols of diisocyanate for each mol of Also very suitable are those diisocyanates whose —NCO urea, it is advantageous to use larger excesses, preferably groups have different reactivity rates, for example, l-meth 6 to 10 mols of diisocyanate per mol of urea. When the ylbenzene-2,4-diisocyanate, 1-methylbenzene-2,6-diisocya larger excess is used, the diisocyanate functions as a sol nate, 1-chlorobenzene-2,4-diisocyanate, B-methyldiphenyl- ~ vent for the biuret polyisocyanate or carbamyl biuret methane-4,4’-diisocyanate, l-methyl - cyclohexane-2,4-di polyisocyanate which results from the reaction. When the isocyanate and the like. Perchlorinated arylene diisocya reaction has reached the desired stage and after removal nates are also suitable such as, for example, perchloro 10 of all of the monoisocyanate formed, the excess mono m-phenylene diisocyanate or 1-methyl-3,5,6-chloroben meric diisocyanate can be separated from the biuret zene-2,4-diisocyanate. Also suitable are phosphoric acid polyisocyanate by distillation, by a thin ?lm evaporator or aryl ester isocyanates, such as described in German patent by extraction with an organic solvent such as hexane, ben speci?cation 1,126,379, e.g. tris-(4-isocyanatophenyl) zene, xylene, toluene or the like. phosphate. 15 In carrying out the process of the invention, the organic It is also possible to concurrently use triisocyanates, diisocyanate and the substituted urea are mixed in the for example, 1-methylbenzene-2,4,6-triisocyanate, di critical proportions set forth above. Usually the substi phenylmethane-2,4,4’ - triisocyanate, 3-methyl-diphenyl tuted urea dissolves readily in the organic diisocyanate methane-4,6,4'-triisocyanate and triphenylmethane-4,4', with moderate heating and some reaction. When the tem 4"-triisocyanate. The triisocyanates should be present perature is increased, that is to about 150° C.-250° C., only in relatively minor amounts, less than 30 percent by the organic monoisocyanate begins to split off as explained weight of the whole amount of isocyanate used and in ad above and there is further reaction and consequently fur dition to 3 mols of diisocyanate used per mol of urea. ther addition of the organic diisocyanate, The removal of All these polyisocyanates can be obtained by phosgena the organic monoisocyanate is accomplished as set forth tion of the corresponding amines. Reaction products of above. The progressive removal of the monoisocyanate is higher molecular weight obtained from the polyisocya preferably accelerated by carrying out the reaction under nates, for example, by reacting compounds containing hy reduced pressure or by continuously stripping the reac droxyl groups with excess of polyisocyanate, cannot be tion mixture with the aid of an inert carrier gas such as used to produce the polyisocyanates with a biuret struc nitrogen or the like. It is sometimes desirable to carry ture. Thus, the isocyanates are preferably free of urethane out the reaction in the presence of inert organic solvents groups. since this facilitates the preparation of more uniform re Any suitable substituted urea may be used including, action products.
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