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United States Patent Office Patented July 29, 1969

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United States Patent Office Patented July 29, 1969 3,458,281 United States Patent Office Patented July 29, 1969 2 into phosphoric acid alone, and they generally have a 3,458,281 short life in concentrated phosphorous acid solutions. MANUEFACTURE OF PHOSPHOROUS ACID The conventional method for the manufacture of phos Michel Charles Demarcq, Lyon, France, assignor, by phorous acid comprises hydrolyzing phosphorus trichlo mesne assignments, to Ugine Kuhlmann (Societe Ano nyme), Paris, France, a French corporation ride according to the diagrammatically simplified reaction: No Drawing. Filed Mar. 7, 1966, Ser. No. 532,115 (1) PCls--3HO->HPO-3HCI (Claims priority, application France, Mar. 8, 1965, 8,329 and evaporating the excess water and the hydrogen chlo int. C. CO 25/16 ride which are formed. U.S. C. 23-65 8 Claims Actually traces of phosphorus compounds other than O phosphorous acid, including phosphoric acid are also formed in the course of said hydrolysis. The two main ABSTRACT OF THE DISCLOSUIRE Sources of said compounds are: A method for the production of phosphorous acid sub (a) The lack of purity of the phosphorus trichloride stantially free of phosphorus acids having a degree of 15 used in which traces of phosphorus oxychloride and phos oxidation higher than that of phosphorous acid which phorus pentachloride evidently lead to the formation of comprises the steps of (a) reacting phosphorus trichloride phosphoric acid in the course of the hydrolysis; with from 3 to 6 moles per mole of phosphorus trichloride (b) The spontaneous dismutation of nascent phos of a hydroxylated compound having the formula phorous acid, which leads on one hand to superoxidized 20 phosphorus acids (orthophosphoric, hypophosphoric, iso ROH hypophosphoric, pyrophosphoric acids) and on the other wherein R represents a member selected from the group to underoxidized derivatives (hypophosphorous acids, consisting of alkyl, chloroalkyl, hydroxyalkyl, alkoxyalkyl phosphine etc. .). phenyl, alkylphenyl, alkoxyphenyl and chlorophenyl at a It is possible to remedy the lack of purity of the initial temperature between -30° C. and the boiling tempera 25 phosphorus trichloride by using only a freshly prepared ture of said hydroxylated compound, whereby a mixture and perfectly rectified phosphorus trichloride. On the other containing phosphorous esters and phosphoric esters is hand, the spontaneous dismutation of nascent phosphorous obtained, (b) hydrolyzing said mixture with water at a acid is practically impossible to avoid even when hydroly temperature of between 20° C. and 100° C. until said sis is carried out in iced water and in the complete absence phosphorous esters are completely hydrolyzed without sub 30 of oxygen. stantially hydrolyzing said phosphoric esters, whereby a In practice the phosphoric acid contents may, in com mixture of phosphorous acid, phosphoric esters and vola mercial phosphorous acids, be 1 to 3% of the dry weight tile constituents is obtained, (c) separating said phosphoric of the substance. acid from said mixture and (d) recovering phosphorous In a number of uses the presence of a small quantity of acid substantially free of phosphorus acids having a de 35 phosphoric acid is not detrimental. To the contrary, in gree of oxidation higher than that of phosphorous acid. other uses where high degree of purity is required, the conventional commercial phosphorous acid cannot be -as-as used. The present invention relates to the manufacture of An object of the present invention is to provide a method phosphorous acid and more particularly of phosphorous 40 for the manufacture of phosphorous acid capable of being acid which is substantially free from phosphorus acids used in reactions in which a high degree of purity is having a higher degree of oxidation. required. The term phosphorus acids having a higher degree of A further object of the invention is to provide for the oxidation as used herein essentially means orthophos obtention of phosphorous acid free from phosphorus acids phoric acid (I) but also condensed acids such as hypo 45 of a higher degree having oxidation, which contain for phosphoric acid (II) and isohypophosphoric acid (III) instance not more than .01 to 0.5% of phosphoric acid. and pyrophosphoric acid (IV); A further object of the invention is to provide mixtures of phosphorous acid and small quantities of esters of O O O phosphorus acids having a degree of oxidation higher 50 than that of phosphorous acid, which are substantially HO-P-OH, HO-P-P-OH free from free phosphorus acids of the said type, which &H ÖH ÖH. mixtures are obtained in the course of the manufacture of (I) (II) the pure phosphorous acid. The method according to the invention essentially con O O O O 55 sists in reacting phosphorus trichloride and an alcohol or HO-P-O-B-H, HO-P-O-P-OH phenol of the formula ROH, in which R is an alkyl or ÖH bit ÖH &H aryl radical which may be chloro-substituted, while main (III) (IV) taining the temperature of the reaction mixture at a value which is at most equal to that of the boiling point of However, said condensed acids have a low stability in 60 said alcohol or phenol, thereby obtaining a mixture of acidic media, in which they are converted through hydrol phosphorous esters, hydrogen chloride and possibly alkyl ysis either as concerns hypophosphoric acid (II) and iso chloride, submitting the mixture to the action of water hypophosphoric acid (III) into phosphorous acid and in order to completely hydrolyze said phosphorous esters phosphoric acid or as concerns pyrophosphoric acid (IV) without Substantially hydrolyzing the said phosphoric 3,458,281 3 4. esters, and separating the phosphorous acid resulting from The reaction temperature may be between -30 C. said hydrolysis from the accompanying volatile com and the boiling temperature of the alcohol or phenol used, ponents and phosphoric esters. the preferred range being from -10 to --50° C. for The separation of phosphorous acid may be conducted alcohols and -- 40 to +180° C. for phenols. by evaporation to dryness of the mixture resulting from The reaction may take place at atmospheric pressure the hydrolysis, whereby a residue, essentially formed of 5 or at pressures higher or lower than atmospheric pres phosphorous acid containing a Small quantity of neutral sure. Operating under lower pressure has the advantage or acid phosphoric esters is obtained, the proportion of of enhancing the evacuation of the hydrogen chloride and said esters in said residue generally being from 1 to 5% possibly the alkyl chloride, RCl, formed in the course of the dry mixture. After which, said residue is freed 0 of the reaction (2). It also makes it possible, while main from the phosphoric esters contained therein, by distilla taining a relatively low temperature, to cause the reaction tion under high vacuum or preferably by agitation with mixture to boil, thereby creating a further agitation. Fur an organic solvent which does not dissolve phosphorous thermore the reaction heat may, in case of an exothermic acid and/or aqueous solutions thereof, but does dissolve reaction, be eliminated not by cooling the reactor but by the phosphoric esters. condensing the vapors of volatile components. For certain uses in which the presence of small quan In the second step (B) the mixture of esters obtained tities of phosphoric esters can be accepted, a final elimi in step (A) from which the hydrogen chloride and the nation of said esters may be dispensed with. - alkyl chloride, RCl, may preferably or may not be pre In short, the method according to the invention com viously separated by moderate heating under vacuum or prises in the more general aspect thereof the four follow 20 by a flow of inert gas is, as hereinabove mentioned, sub ing steps: mitted to the action of water in such a manner that the (A) Reaction of phosphorus trichloride with an alco phosphorous esters are completely hydrolyzed, which hol or phenol. takes place according to the partial reversible reaction: (B) Hydrolysis of only the phosphorous esters result ing from the above reaction. (C) Evaporation of the mixture resulting from said hydrolysis. without substantially hydrolyzing the phosphoric esters, (D) Elimination of phosphoric esters from the residue which are much more resistant to hydrolysis. of said evaporation. Said hydrolysis is preferably carried out between 20 Step (A) is carried out by mixing the reactants with 30 and 100° C. with cooling since reaction (3) is exother strong stirring, and cooling. As hereinabove described mic, with or without stirring. The reaction may in cer said step leads to a mixture of phosphorous esters, hy tain cases be advantageously catalysed by a trace of hy drogen chloride, and, when ROH is an alcohol, to a cer drogen chloride. tain proportion of alkyl chloride RCl. The quantity of water used for said hydrolysis may The phosphorous esters which are formed by said re be between 1 and 20 times the theoretical quantity cor action, when ROH is an alcohol, include a major propor responding to Equation 3. tion of dialkyl phosphites (RO)2POH with a variable When the alcohol or phenol has a lower boiling tem proportion of monoalkyl phosphites, and, exceptionally, perature than that of water or forms with water a homo- or trialkyl phosphites; when ROH is a phenol triaryl phos heteroazeotrope having a lower boling point than water, phites are essentially formed, which may however con 40 it may be advantageous to distill off the freed alcohol tain traces of di- and monoaryl phosphites. or phenol as it forms with possibly part of the free wa ter, in order to shift the semiequilibrium (3) towards the In the general case, the reaction may be written as right. Total hydrolysis is thus reached more rapidly, with follows: a reduced water consumption. To this effect a reactor may be used, equipped with a plate or packed column and operating under atmospheric pressure or under WaCl.
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