Patented May 29, 1945 2,377,038

w UNITED STATES PATENT OFFICE MANUFACTURE OF PERACDS Joseph S. Reichert, Samuel A. McNeight, and Arthur A. Elston, Niagara Falls, N. Y., assign ors to E. I. du Pont de Nemours & Company, Wilmington, Del, a corporation of Delaware No Drawing. Application September 15, 1941, Serial No. 410,878 6 Claims. (C. 260-502) This invention relates to a new and improved ods require the use of peroxide solutions having process for the preparation of peracids and their active concentrations equivalent to at salts, and to the novel peracids and persalts re least 7 volumes if satisfactory yields of peracids . Sulting therefrom. More particularly, it relates are to be obtained. The temperature under which to a new and improved method for the prepara the reaction proceeds is also of considerable in tion of the organic peracids, particularly the portance in these methods, and it has generally monoperacids, and the salts of these acids in been necessary to maintain an unusually low aqueous solutions of relatively dilute concentra temperature. These disadvantages have restrict tion. This application is, in part, a continuation ed the use of such methods, both because the of our copending application Serial No. 317,318, handling of peroxide solutions of high concentra filed February 5, 1940. tion may be inconvenient, as well as because of The organic peracids constitute a class of acids the necessity for cooling or otherwise controlling which are chemically characterized by the pres the temperature of the reaction mixture. Our ence of the perhydroxyl grouping OOH as part improved procedure makes it possible to prepare of the molecule. They may be regarded as de peracid solutions from peroxide solutions of rela rived from other acids by replacing the hydroxyl tively low active oxygen concentrations, concen group containing the ionizable hydrogen atom of trations of from 0.006 to 7.0 volumes, although it Said acids by the perhydroxyl group OOH. Thus, may also be employed effectively for manufac monoperSuccinic acid has the chemical constitu turing organic peracid and persalt Solutions of tion 20 as high as 12.5 volumes. Rigorous control of the CH2COOOH temperature under which the reaction proceeds &H cooh is avoided, and by suitable control of the pH we have found it possible to prepare peracids and and may be regarded as derived from succinic persalts in high yields at temperatures ranging acid, 25 anywhere from 15° C. to 90° C. CHCOOH In referring to the concentration of a Solution CHCOOH of a peroxygen compound, such as alkali metal by replacing a hydroxyl group containing an ion peroxide, hydrogen peroxide, sodium perborate, izable hydrogen atom with the perhydroxyl group. etc., or in referring to the concentration of an The invention with which this application is 30 aqueous solution of a peracid or persalt, it is especially concerned involves a process for pre usual in the art to refer to "volume concentra paring Solutions of Organic peracids or their salts, tion.' The volume concentration of such an more particularly aqueous Solutions of mono aqueous solution is the number of Volumes of peracids and the alkali-forming salts of the oxygen gas, measured at 0° C. and 760 mm, of monoperacids, by reacting an acid anhydride with 35 mercury pressure, that would be released upon an inorganic peroxide or peroxygen compound Complete decomposition from One Volume of the under conditions wherein the pH of the resulting solution measured at 20° C. There is, of course, peracid or persalt solution is carefully controlled, a definite correlation between the actual concen so as to fall within certain limits. As the in 40 tration of the solution and the volume concentra or percompound, ordinarily we tion, depending on the particular oxidizing agent prefer to utilize hydrogen peroxide or sodium involved. Thus a solution of hydrogen peroxide peroxide, and We have found that the peracids of 100 volumes concentration, a Solution Solid gen and their salts are produced in very satisfactory erally for commercial use under the trade-mark yields in the dilute solutions that we are espe 45 name “Albone,' for example, contains at least cially interested in preparing when the reaction 27.6% H2O2 by weight. is carried out under controlled conditions. In adueous solution the organic peracids and 'Methods previously employed for preparing the salts of these peracids, particularly their peracids have involved either reacting acid an alkali-forming salts, are full equivalents of each hydrides with solutions of hydrogen peroxide 5 other. As far as the utility of the Solution of the which were acidic in reaction at ordinary room Oxidizing agent is concerned, it makes little dif temperatures or temperatures below room tem ference whether the peracid radical is part of the peratures, or reacting them with strongly alkaline acid or of the salt of the acid. In any given peroxide Solutions at temperatures below 10° C. Solution the relative amounts of organic peracid and preferably below 0°C. These known meth 55 and salt of this peracid depend generally upon 2 2,877,088 the pH of the solution. In view of the full equiv Such as and naphthalene alency between the organic peracids and persalts, sulfonic acid. Among heterocyclic acids, nicotinic it is usual to use the term “peracid' generically acid, quinolinic acid, and furoic acid are also to include not only the acids themselves, but their compounds from which peracids may be derived. salts, particularly the alkali-forming salts. Else In fact, any organic peracid such as, for ex where throughout this specification and the ap ample, in addition to the acids previously men pended claims this procedure will be adopted, the tioned, perpropionic acid, monopercrotonic acid, term "peracid' or “peracids' including the salts monoperadipic acid, persulfobenzoic acid, non Of these acids. - Opernaphthalic acid, and the peracids derived AS previously stated, the peracids may be gen 0 from acid anhydrides by the Diels-Alder diene erally regarded as derived from acids by replace Synthesis Such as those prepared from maleic an ment of one or more of the hydroxyl groups con hydride with cyclopentadiene, butadiene, benzene, taining an ionizable hydrogen atom by the per terpenes and rosin hydrocarbons, and derivatives hydroxyl group OOH. A typical example is mon of naphthoquinoline, and heterocyclic Opersuccinic acid, which may be generally re hydrocarbons may be prepared by our improved garded as derived from succinic acid. Other ex method. Among organic acids containing no car amples of organic monoperacids which can be boxyl groups which may be regarded as base acids manufactured in high yields in relatively dilute . from which peracids are derivable by the previ solution. Without the necessity for controlling the ously noted substitution, we may include phos temperature, in accordance with our improved 20 phonic acids, the corresponding peracids being process, include peracetic acid, monoperphthalic capable of manufacture by our improved method. acid, monopermaleic acid, monoperglutaric acid, In accordance With our improved process, solu and monoperterephthalic acid. In addition to tions of peracids or their salts are prepared by such monoperacids derived from organic acids reacting an organic acid anhydride and a solution containing One or more carboxyl groups, there are of a peroxygen compound of the desired concen of course monoperacids derived by the introduc tration, the alkali content of the solution being so tion of a perhydsoxyl group into other classes of adjusted that the peracids formed during the re organic acids. Thus, monoperacids which may be action are partly or completely neutralized. prepared in accordance With our process include When a peroxide solution, such as a solution of those derived by introducing a perhydroxyl group 30 Sodium peroxide or hydrogen peroxide, is utilized in place of the hydroxyl group containing the as the peroxygen compound, the reaction is car ionizable hydrogen atom of a hydroxy organic ried out by preparing a peroxide solution of the acid. Peracids may in this way be derived from desired concentration. The alkali content of this all classes of Saturated and unsaturated acids, Solution is then so adjusted that the peracids and Whether the acids be aliphatic or aromatic. Other acids subsequently formed, upon the addition of organic acids not characterized by the presence the organic acid anhydride, are partly or com of a carboxyl group, such as the Sulfonic acids, pletely neutralized. Generally an equimolar either aliphatic or aromatic, may be regarded as amount of the Selected organic acid anhydride base acids from which peracids capable of manu is dissolved in the alkaline peroxide solution, facture by means of our improved method may be 40 Whereupon the reaction proceeds to form the de derived by the substitution previously noted. sired peracid or persalt. Peracids may also be derived from heterocyclic We have found that by suitable adjustment of compounds such as furoic acid. While our inven the alkali content of the solution of the peroxygen tion is directed to the manufacture primarily of compound reacted with the anhydride, solutions the organic monoperacids, under certain circum of peracids may be formed at temperatures rang. stances our process may be used to form diper ing from 15° C. to 90° C. and with active oxygen acids and, even under certain circumstances, tri concentrations ranging from 0.006 volume to 12.5 peracids. volumes. In all cases satisfactory yields of per Among aliphatic organic acids from Which acid or persalt are secured. This process con Inonoperacids may be regarded as derived, which 50 stitutes a distinct improvement as far as prepar monoperacids may be prepared in accordance with ing peracid Solutions of these low concentrations our improved process, We may mention both mon is concerned, since previous methods for prepar obasic acids, of which is an example, ing such Solutions, particularly solutions of con as well as dibasic acids, of which succinic acid is centration ranging from 0.006 volume to 7.0 vol an example. Among hydroxy acids yielding per 55 umes, have necessitated the maintenance of un acids are acids such as lactic acid, glycolic acid, usually low temperature conditions during the tartaric acid, and malic acid. Unsaturated ali reaction. phatic dibasic acids such as maleic acid, and mon The adjustment of the alkali content of the obasic acids such as Crotonic acid, also yield cor Solution of peroxygen compound reacted is sim responding organic peracids which may be manu 60 ple and convenient. Within certain limits exact factured by our improved method, adjustment is not essential. The amount of al The aromatic acids also yield peracids, a typi kali required to insure satisfactory conversion of cal example of which is monoperbenzoic acid, pre the peroxygen compound such as hydrogen per pared by replacing the hydroxyl group contain oxide or sodium peroxide to the peracid when pre ing the ionizable hydrogen atom of benzoic acid 65 paring the aqueous solution of peracid or persalt by a perhydroxyl group. Other aromatic acids may be stated either in terms of chemical equiv. yielding peracids include the previously mentioned alence of a particular alkalizing agent, or in phthalic acid, yielding monoperphthalic acid, as terms of hydrogen ion concentration of the per Well as Various alicyclic Organic acids such as acid solution after the anhydride has more or cyclohexane and cyclohexane di 70 less completely reacted with the peroxide. carboxylic acid. Among Specific sulfonic acids The various alkalies or alkalizing agents which from which both monoperacids and, where two may be employed in preparing peracids and per ionizable hydrogen atoms are present, diperacids salts in Solution vary individually from one an may be derived, which acids are capable of being other in amount required to neutralize the acids manufactured by Our improved method, are acids 5 and peracids formed. For this reason we prefer

2,877,038 3 to express the amount of alkali or alkalizing agent quantity of alkali that the final pH, at the con necessary in terms of the hydrogen ion concen clusion of the reaction, falls within the range 8.0 tration (pH) of the solution after substantially to 11.0. When the amount of alkali present is all of the anhydride has reacted with the per reduced so that the final pH drops below 8.0 in oxygen compound. Throughout this specification s the preparation of the peracid, the conversion of and claims we designate this pH for convenience peroxygen compound to peracid decreases, but not as the "final pH' of the solution. In expressing Seriously, until a pH of below 5.0 is reached. With the amount of alkali or alkalizing agents required volume concentrations of 1 volume or less, how in terms of final pH, we found that while the ever, satisfactory yields of peracid are obtained amounts Will vary with the different alkalizing O even With final pH values which fall within the agents which may be employed, the preparation range 3.0 to 5.0. At higher concentrations, those of the solutions of peracids and perSalts Will pro ranging from 1 volume to 12.5 volumes, satisfac ceed essentially in the same manner and with tory yields are not in general obtained when the substantially the same conversion of peroxygen final p is below 5.0, and for most purposes we compound to peracid, regardless of the alkalizing prefer to operate so that the final pH is 8.0 to agent utilized, when a sufficient quantity of the 11.0. When the peracid or persalt is produced agent is present to give in each case the same under conditions Such that the final pH is sub final pH. It may be remarked that one experi stantially higher than 1.1.0, the peroxide or other enced in acidimetry and alkalimetry can readily perOXygen Compound appears to be unstable in establish and calculate the relationship between 20 the reaction mixture and cooling is generally nec the amount of alkalizing agent and the final pH essary in order to Secure satisfactory yields. which that amount Will give to the solution, but Since our process is one capable of being car the determination of such relationship is not nec lied out at Ordinary room temperature, for yields essary for the practice of our invention, as the high enough to satisfy commercial requirements amounts of alkalizing agents added may be We prefer that the final pH fall within the range varied within wide limits Without appreciable ef 8.0 to 11.0. Under such conditions the prepara fect on the preparation of the peracid. tion of the peracids may be carried out at higher Among peroxygen compounds capable of utili temperatures, for example temperatures up to zation in our process, by reaction. With the or 180° F., without too seriously reducing the yields. ganic acid anhydride to form peracids and per 30 The ability to carry out the reaction at tempera salts in solution without the necessity for careful tures up to 180° F. is particularly advantageous regulation of the temperature conditions under When it is desired that the resulting peracid or which the reaction is carried out, we may spe pei'Salt Solution be utilized for treating materials cifically mention hydrogen peroxide, the alkali at those temperature conditions. While the re metal peroxides such as Sodium peroxide, and per action between the organic acid anhydride and salts such as sodium perborate. For adjusting the peroxide or other . peroxygen compound is the alkaline condition of the Solution and for Se.. more rapid at high temperatures, the tendency of curing the final pH, we prefer to use alkalizing the peracid or perSalt to decompose is also greater agents such as caustic soda, sodium carbonate. under such conditions. When the solution of the Sodium bicarbonate, tetrasodium pyrophosphate. 40 peracid is therefore prepared at high tempera trisodium phosphate, and ammonium hydroxide. tures, Such for example as temperatures in excess When it is necessary to reduce the alkalinity of of 120° F., it is essential that it be employed for the solution in order to secure the final pH, We its intended use without substantial delay. This prefer to utilize acids such as sulfuric and boric, is practical Where the peracid solution which is to although almost any mineral acid, and organic be utilized at high temperature is prepared in the acids such as acetic, citric, and tartaric may be presence of the material which is to be treated utilized with equal succeSS, with the peracid or persalt. In carrying out our process the acid anhydride As a generalized preferred procedure for carry and the peroxygen compound are reacted under ing out our invention, the following may be taken such conditions, the alkali content of the reaction 50 as illustrative. mixture being so adjusted, that the final pH, i.e., A perOXygen compound, Such for example as the pH when the reaction is complete, Will fall hydrogen peroxide, sodium peroxide, or sodium within the range 5.0 to 11.0. In carrying out the perborate, is dissolved in Water in amount suf process so that a final pH. Within this range is ob ficient to yield a solution of the desired active tained we have Secured maximum conversion of 55 oxygen concentration. This concentration will the peroxygen compound to peracid. This maxi fall within the range 0.006 volume to 12.5 volumes. mum conversion will vary to a slight extent with The alkali content of this Solution is adjusted the active oxygen concentration of the peacid so that the final ph. Secured at the end of the re solution, and to some extent upon the particular action will fall within the range 5.6 to 11.0 and peracid being formed, but in most cases We secure 60 preferably, especially when commercially in a yield in excess of 70%. Yields in excess of 90% portant yields are to be secured, within the range are not uncommon, and When preparing peracids 8.0 to 11.0. such as peracetic acid, monoperSuccinic acid, or Since Sodium peroxide or Sodiun perborate in monoperphthalic acid, high yields are Ordinarily solution contribute considerable alkali thereto, obtained. 65 it is obvious that these compounds are particu While the reaction should be carried out under larly useful in Our process. We have observed such conditions that the final pH of the solution that in general the final pH. Within the desired at the conclusion of the reaction will fall Within range Will be secured. When the solution contains the range 5.0 to 11.0, ordinarily for most purposes from 34 to 2 equivalents of an alkali or alkaline we prefer to operate so that this final pH falls 70 salt such as caustic soda, ammonium hydroxide, within the range 8.0 to 11.0. The preferred em borax, or the alkali metal Salts of. carbonic acid, bodiment of our process may therefore be regard pyrophosphoric acid, or phosphoric acid, for each ed as involving carrying out the reaction between mole of active oxygen present in the Solution. To the organic acid anhydride and the peroxygen this solution at the desired temperature, pref 5 compound in a reaction mixture containing such erably within the range 15° C. to 90° C., there is

pieti. Which 1737, give

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2,877,038 5 the reaction to form the peracid, within the pH The temperature of the solutions was main range 5.0 to 110. The number of moles of sodium tained at 90' F. and the stoichiometric amount of hydroxide per mole of peroxide present added to added. No attempt was made. each of the five solutions are given in the follow- to control the temperature in any way during ing tabular summary. 5 the reaction. At the end of a few minutes reac While the temperature was maintained at ap- tion was complete, the final pH values and the proximately 90° F., the stoichiometric quantity yields of peracetic acid being as follows: of acetic anhydride necessary to form peracetic acid was added to each of the Solutions. Re- Solution Final pH Yield action in each case was complete within a very 10 r few minutes, the yields of peracetic acid in each solution being as follows: Number of moles of Solution E. PESIt - Eacample 5 8 - prote Six solutions of hydrogen peroxide, each of 1

------volume concentration, were prepared. The tem - 1.00 92, 5 peratureproximately of the90°F. solutions Various in amountseach case of was the apal 8 E. . kalizing agents noted in the following table were added,anhydride and necessarythe stoichiometric to produce amount peracetic of acetic acid Eacample 3 then added to the alkaline solution. After suf. Four solutions of hydrogen peroxide of 3 vol- ficient time had been allowed for reaction to be ume concentration were prepared, and to each of complete, the final pH values were determined these solutions was added sufficient alkali to bring and the percentage yields of peracetic acid se the final pH, at the conclusion of the subsequent cured. The yields were in all cases very satis reaction with acetic anhydride, to one falling factory. Solution 1, solution #2, So., Solin, Solution #5, Solution #6, Alkalizing agent used . . bi:sodi Elite NSo carbonatesodium PEPs phosphatesodium ammoniumhydroxide NaHCOs 25Ut NaCO3 NaPO NaPO NEIOI Moles alkalizing agent per mole H2O2------5.0 1.00 a 1.00 1.50 .00 1.25 pH of E. solution before addition of anhydride. 7.6 8 10.5 9.7 0.7 10.2 Time required for complete reaction, minutes------15. 15 15. 5 1-2 5 Final pH of solution after reaction.------7:0 7.0 . 7.2 7.4 7.4 . 5, 7 Percent conversion of peroxide to peracid.------89.0 93,5 90.2 90.8 88.5 80.5 within the range 5.0 to 11.0. The amounts of Eacample 6 sodium hydroxide added permole of hydrogen Warious solutions of sodium perborate of vol peroxide are given in the following table. ume concentration ranging from 0.025 volume to To each of these solutions the stoichiometric 12.5 volumes were prepared by dissolving the salt quantity of acetic anhydride necessary was added, in water at a temperature of 80°F. An equimolar and the reaction permitted to proceed at room amount of succinic anhydride, the stoichiometric temperature until complete. The table gives the amount necessary to form persuccinic acid, was percentage yields of peracetic acid in each case, then added to each of the alkaline solutions, together with the final pH of the solution. which were then subjected to agitation. At the ------end of ten minutes the final pH of each solution N.E., of P r ntage was determined, as well as the percentage con solutiSolution perof "NABH. mole of Finalpi peraceticof versionbelow. to persuccinic acid. The results are given peroxide acid present 55

- Final pH of Percentage of 0.75 5. 73.9 Volume concentration of perborate solution at conversion to 1.2500 7.5 87.28.6 solution ofFEE reaction persuccinicacid 2.0 10,0 1.3 --- -- 0. 5, 6 7.7 Eacample 4 60 3.i. :6, 4 s:71.6 Four solutions of hydrogen peroxide of 7 Wol- i. 6.6 ii. ume concentration were prepared by dilution of commercial 100 volume solution. To each Sol- 65 Eacample 7 situ hydroxide was added in the follow- A solution of sodium perborate of 0.0125 vol g h ume concentration was prepared by dissolving the Solution A-0.5 mole per mole of hydrogen per- salt in water at 120° F. Phthalic anhydride in the oxide stoichiometric amount necessary to form mono Solution B-1.0 mole per mole of hydrogen per- to perphthalic acid was then added to the alkaline Oxide solution. At the end of five minutes analysis of Solution C-1.25 moles per mole of hydrogen per- the solution showed that the percentage yield oxide was substantially 50.0%, the final pH being 5.1. Solution D-2.0 moles per mole of hydrogen per- It was not necessary to cool the reaction mixture, oxide 7s but the phthalic anhydride was thoroughly dis

6 2,877,088 persed throughout the solution by vigorous stir group consisting of the organic peracids and ring. their alkali-forming salts which comprises re Wherever throughout this specification and the acting, in an aqueous reaction medium, the an appended claims reference is made to a peracid hydride of an organic acid Selected from the group or to peracids it is intended to include within the which consists of acetic acid, Succinic acid, and scope of that term the salt of the peracid or per phthalic acid, and a dilute Solution of an inor acids. As previously explained, in aqueous Solu ganic peroxygen compound said solution having tions these constitute full equivalents of each a volume concentration ranging from 0.006 Wol other, the particular form in which the peracid ume to 12.5 volumes, there being present in said radical appears being dependent essentially only O aqueous reaction medium sufficient alkali to in on the pH of the aqueous solution. Sure a final pH, at the conclusion of the reaction, As various changes might be made in our proc falling within the range 8.0 to 1.0. ess without departing from the spirit of the in 4. The method of preparing a member of the vention, it is our intention that the invention group consisting of peracetic acid and its alkali be not restricted to precise details, conditions and 15 forming salts which comprises reacting, in an amounts given as illustrative of the preferred em aqueous reaction medium, acetic anhydride and bodiments thereof except as necessitated by the an inorganic peroxygen compound said Solution appended claims and prior art. having a volume concentration ranging from 0.006 We claim: volume to 12.5 volumes, there being present in 1. The method of preparing a member of the said reaction medium sufficient alkali to insure group consisting of the organic peracids and their a final pH, at the conclusion of the reaction, alkali-forming salts which comprises reacting, in falling within the range 8.0 to 1.0. an aqueous reaction medium, the anhydride of a 5. The method of preparing a member of the carboxylic acid and an alkaline solution of an group consisting of monopersuccinic acid and its inorganic peroxygen compound having a volume 25 alkali-forming salts which comprises reacting, concentration ranging from 0.006 Volume to 12.5 in an aqueous reaction medium, succinic anhy Volumes, there being present in said aqueous re dride and an inorganic peroxygen compound said action medium sufficient alkali to insure a final solution having a volume concentration ranging pH, at the conclusion of the reaction, falling from 0.006 volume to 12.5 volumes, there being within the range 8.0 to 11.0. 30 present in said reaction medium sufficient alkali 2. The method of preparing a member of the to insure a final pH, at the conclusion of the re group consisting of the organic peracids and their action, falling within the range 8.0 to 11.0. alkali-forming salts in aqueous Solutions of Vol 6. The method of preparing a member of the ume concentration ranging from 0.006 Volume to group consisting of monoperphthalic acid and its 12.5 volumes which comprises reacting, in an alkali-forming salts which comprises reacting, in aqueous reaction medium, the anhydride of a an aqueous reaction medium, phthalic anhydride carboxylic acid and a dilute solution of an in and an inorganic perOXygen compound Said SO Organic peroxygen compound Selected from the lution having a volume concentration ranging group which consists of hydrogen peroxide, so from 0.006 volume to 12.5 volumes, there being dium peroxide, and SOdium perborate, said soul 40 present in said reaction medium sufficient alkali tion having a volume concentration ranging from to insure a final pH, at the conclusion of the re 0.006 volume to 12.5 volumes, and there being present in said aqueous reaction medium suff action, falling within the range 8.0 to 11.0. cient alkali to insure a final pH, at the conclusion JOSEPH. S. REICHERT. of the reaction, falling within the range 8.0 to 11.0. 45 SAMUEL A. McNEIGHT. 3. The method of preparing a member of the ARTHUR, A. ELSTON.