Document 737ap57GZm2RLVpkQE2gaK5R

PVle -St Patented Dec. 20, 1932 1,891,541 -**3) W<' i UteCfi-esi fef aJ i *"tinur., = ' ; v, or i .*) (X*l i ;tr ,rii. IL'4.1 1* ! ;>{ . . : vn? ' -"'t * * :;* j -ht . .:. %.) 1, . -i3v<;' * v. 1 UNITED STATES PATENT OFFICE jams! M. MVJTXBB8S, OT CSMBMPOE, MASSACHUSETTS, and CAMPBELL a. MdSTO- - ACOOB AMD miMM X. BOOTH, F ANNISTON, ALABAMA, ASSIGNCAS TO SWANN .kicmurcm, arc, a ooexobation or atabami bcbthod or tboottoow MQMOimrBODrpgENYLB B. DrftWUS. BVpUMttmi M MArth It, IMS. J*1 to. Mt,M2. Oul innention relates to a method far prv- acid and water and the* adding a mixture of Sfaciagannoiutnted dirhcnyls,and jMrficu- concentrated nitric and sulfunc acids. The Jarir 1- aad 2- ahrodiphesvde, by nitrating size of the-diphenyl particles is not of special diphenyl without (the use of n solvent by the importance, though we prefer that the di A use of a nrintnre of nitric acid and sulfuric phenyl pass a 90-ntesh screen. The -ooncen- M acid, iration of this acid mixture should be avch . Sheobjectofnariwnartion istoobtain snb- that the diphenyl may remain an contact for stantiaBy aamdete wateation of diphenyl, as a long period without appreciable nitration 4- and 2- nitrodiphenyls. A bather object is taking place. Spent or mek acid is suit M <k* tee of mind ntratsig scads, in (manner able for use in suspending tbe diphepyL Bj M whereby it is punbfe to ottain substantially spent or week acids, we mean acids which oagudele aitrsfaas xxf ibe diphenyl without have been dimined from the previous nitra ihaionnatin* of an objectsenable quantity of tions, or acids male up of proportions here dirotrodiphenyls. inafter stated. S3 bs iRnous efforts at making nitrodi- We hare found that while nitration may M aheayls, awarding to such references ns are be carried out through a range of tempera k be fonnd in the literature, efforts were di- tures, in our preferred method we maintain atotod prinetpally toward producing dinitro- the temperature of the nitrating mixture at dipfaenjd and it was proposed to ass nitric from 35 to 40 C.,-during which time mixed i acid same tor this ptupoae. in carryingout aitrating acid is added. If higher tempera- w the pnsoess, the cate sf nitration was very tares are maintained, it is advisable to alter plow, and moreover presented serious diffi- the concentration of the mixed acids used. galties as a eomatercul operation. Jt was The formation of dinitrodiphenyls seems to also proposed tosabjoct tire diphenyldirectly increase at higher temperatures of the nitrat 033 to a taurtnro of 00neentested nitric and snl- ing mixture; and since the separation of di- fffupc adds, but the difficulties with such a jutoodiphenyis from aaononkrodiphenyis is procedure are that a very large quantity of very difficult, it is important to prevent the >nyl remains as such and besides both formation of the dinitrodiphenylk Ooctiag Titfodiphenylsand diaitrodipbenylsare coils or their equivalent are necessary to d in mativsly large proportions. Use contrail the temperature ofthe nitrating mix- ff preeeao* of appraasble qnsntttiss ofdinitro- tore. ffipbenyls nth nosoonitrodipheayle is very The reaction proceeds very smoothly and Objectionable because of the difficulty of eepa- quietly as the mined acid is added to the ai- f satiaa of thediaitrodipbenyls from theaaono trator. By nitrating in the manner described *(jjP qitrpiaontsns. _ The Blast satisfactory method vnth mixed acids, me find the reaction is not of: qxwonitratioe beietofoie propoetd ooe- nearly so sensitive as whan other methods Wtod, ip the aee-of a solventin nitrating, are employed, for Instance, when diphenyl then reparhtiqg the solvent. <nftrsr iiH r.: fa euEpendad in concentrated nitric seal, and We nave discovered a method of carrying sulfuric acid subsequently added thereto. 4^ Oft, the,, qitmtio*,, whereby ajonehltrodi- Moreover, by our raetnod there is less dinitro- % ylsmaj be, prodooad without producing diphenyl formed, j .; -i !*-. ; -r > fiw#, svaniitiee jot thnitrodiphenyls. j Another feature of^commercial impostanee inferred method forqaiyyiag ontour is that by our process ire are able to use or^ ^ suspend ppwdered dipheqyl io diaarj iron etutpmsnt for the construatioa "IS, WpnstS e^fiwie acid, jaiigie of the aitrator, and are cat oanfraatod with M 02653^9 TOWOLDMONOQ57423 Ww 4^" " .'"T. -m i,aei,e8 4..iwmT 'Vt'Cc^'V f* ' * !. '** ous'oorroidoh difficulties from the aration may aleo be aooompliahed by frec- ____ -Control of the reaction in our tional crystallization. jjB'fiiW, procMs is by variation in the rate of addition As an alternative method of carrying out W '^.v.r.'df the mixed add, tad hyverying the flowof our prooess, we may suspend 100 grams of Water in the hitrator cooling coils, diphenyl in a mixture comprised of100 e. e. To ustrafiveof the proportions of materials ofwater and 41 c. e. of nitric add at 1.42 sp. rtWsd and procedure, we give the fallowing: gr. Substantially no nitration of the diphe- V 'Aasuming 100 grams of diphenyl is suspend- nyl occurs in this suspension, due to the pres in spent add or a mixture comprising anoe of ao large a proportion of water there- \t` r~ v, /"< - n " aw thi&mi " We then add 118-e.. of sulphuric add 7s SulfuHfcXtifl ** **' g5 in a manner already described for the mixed Nitrioadd. ITIIIZ7' IIIZ lZZ-I'w"-S4 nitrating acids, meanwhile thoroughly agix -- ~ Ah fating the suspension, and maintain the tam TM tjerature of the mixture from between 70 to - if KSSuhstsfotisny no nitration oecura while tbe Tf8* C. When the sulphnric'add is added, it ao . . diphenyl is in the. weak add mixture. This serves to combine with the water m the inix- * ' mixture serves as a suspension medium end ture and nitration of the diphenyl proceeds. A: ` ` - The processof separation and washing is the -same as that previously described. , ^ ^ _ _. _ - While we nave described our invention in is nfilitrating aacdd in the manner about to be hut two forms, it will be obvious to those describes. ' skilled in the art that it is not so limited but is susceptible of various changes and modifi cations, without departing from the spirit ft and.the nitrating acid is added to the suspen- thereof, and we desire, therefore, that only so don. The mixed nitrating acid used per 100 such limitations shall be placed thereupon as grams of diphenyl comprises . are imposed by the prior art or as are spedfi- ..<%. . < : ||Csjr pally set forth in the appended claims. Sulfuric add W" BA,,.._ 6 w* oUimi: , . . Nitric arid 1.42 sp.gr___......i. 88.5 .L Te process of producing monomtrodi- a. , i' \ : - phenyls which consists m providing a suspen- -' '.The rate of addition is regulated according sion of diphenyl in an acid solution contain- ' to the heat generated and the ability of the ing nitric acid and of a strength below that ` cooling coils to remove the heat. Agitation at which substantial nitration of the diphenyl . gf is continued for a mart time after all of the occurs, and adding to the suspension concen- loo mixed add is added. When nitration is car- trated sulphuric acid to bring about a reac hed out by this method,the resultant product tion between.the nitric acid and the diphenyl, is approximately 97% mononitrodiphsnyls, 2. The process of producing mononitroai- hnd 8% dinitxodipbenyfc. _ - phenyls which consists in providing a suspen- ,SS Afterthe hitrating add mixture isall add- don of diphenyl in an acid solution contain- ns ed and the. mixture is agitated thereafter ing nitric acid and of a strength below that until the reaction is substantially complete at which substantial nitration of the diphenyl ' ' and substantially' ho diphenyl remains in the occurs, adding to the suspension concentrated . .1 mixture, the spent add is -drained off and sulphuric arid to bring about a reaction be- ". ft separated from the mononitrodipbenyls, fol- tween thenitric add and the diphenyl, and Uo , .- 4 > lowing Which they are washed with water, maintaining the temperature'during nitre- '- ' which is then drained otf. Water which eon- Non below^5" 43. >ii.; '..-.-tv, tains a small quantity of alkali is-then run -t_L__T_h_e pr_o_c_e_ss of p-----[u--s-i-n,,g m---e--n--o-n--i-t-r-o-d--i- .... Into the mtrator.aad the mixtare agitated to phenvlswhich t ^ asuspen- ' J -f \,ft neutralize the remaining__a__d_:d.i., This_aiilkai:line a,fon o.f dj-iphe.pyl in an acid sgolution contain- -til A w'., solution is dralhed off and washing,,s #ith wa- .in,,g'n__it_r_ic_a_c_i_d_a__n_d_o__f_a__s_tr_e_nbgethlo1w that 1 ter aretepeatedin arimilar manner, until all at which substantial nitration of the diphenyl l-Xix:------* *-- ------- J to the suspension concentrated ' tb bring about a reaction be- f M*M vrnenmiBwiwni^s naveiieeii oompiewa, me tween tne nrtnc acid and file diphenyl, main- ' M'- . water ja oarCduliy separete<i and the nitrodi- tainiag the temperature'during nitration be -- -'^i^PM'MW44at*U*4'lhentoUed to' wreumnovi.iany mite-- ftiwweeeennTTOO'' pand 7T5S<^3'.e, ndthoroughly aritat1 Sad-ping waUww -ALhxtiAp. oid1d1.m*i*b-er'-mApara1t-eJd ing the---m---i-x-t*--ure d*uri jg addition of the Aitr-A. ^ `.lL'X1*=TMlO---r..Xm-ATMlJiLwLTwtZLjmX-l the w'aterT. thepKma- .-.tA Thwehrp_.ircothcetTiadTsnsoifs.tpsriondpurcoinvgidiinnognacmanistrpoedoi-.. 1* '< J-'-" solution of mixed tutrit bf a strength approk,11 * ` bifid from a previous *1 L -if at whith rubstan- 4m , 0265350 TOWOLDMONOQ57424 by frac- 100 c. & v 1.42 sp. . e diphe- ' be pres it thereiric odd rs 4 mixed Uy gibe ternn'TO'1 to d|ld, it to he biz- rooeeds. g is the ition m o those ted bat modifie spirit it Ofldy oo ipoa os specifi- itrodi- oe uspenmtain./ that phenyl onoeD- loo . reachenyl. itrodiispenntain- 105 v that >henyl trated >n be l, and lio nitre- 1,801,543 ftiel nitration of the diphenyl occurs, agitat taining a temperature of approximately 40 ing the mixture, and adding thereto a mixture Cj in tiie mixture during nitration, draining oi concentrated nitric and sulphuric acids, on spent acids following nitration, washing and the temperature between aaid mononitrodiphenyls with water contain 15* and*40 C. during nitration. ing a small quantity of an alkali, then wash- 1 P, The prooeas of producing mononitrodi- ing said alkali from the mononitrodiphenyls phenyl which consists in prov.ding a suspen- mna heating said mononitrodiphenyls to re aion of diphenyl in a solution of mixed nitric ` move any water adhering thereto. and sulphuric adds of a strength approxi 11. The process of producing mononitro- mating that of spent add from a previous diphenyl which consists in suspending pow nitration and below that at which substan dered diphenyl in a weak solution of nitric tial nitration of the diphenyl occurs,agitating acid in water, and adding concentrated sul the mixture, adding thereto a nitrating mix phuric acid to the solution. ture of concentrated nitric and sulphuric 12. The process of producing mononitroadds, and maintaining the temperature dur diphenyl which consists in suspending pow ing nitration below that at which substantial dered diphenyl in a weak solution of nitric quantities of dinitrodiphenyl is formed. acid in water, adding concentrated sulphuric 6. The process of producing mononitrodi- acid to the solution, agitating the solution phenyl which consists in providing a suspen while adding the sulphuric acid, and main sion of diphenyl in a solution of nitric and taining the temperature below 75 C. sulphuric acids comprising approximately In witness whereof we affix our signatures. 45% to sulphuric acid, 24% nitric acid and 80% water, agitating the mixture, adding thereto a mixture of concentrated nitric ana ERNEST H. HUNTRESS. CAMPBELL R. McCULLOUGH. CHARLES F. BOOTH. sulphuric acids, maintaining the temperature during nitration below 40 CM and separating the mononitrodiphenyls from the mixture. 7. The process of producing mononitrodi phenyls which consists in forming a sus pension of diphenyl in a solution of nitric and sulphuric acids of a concentration pro- dudng substantially no nitration, and add ing thereto a mixture of concentrated nitric ana sulphuric acids. 8. The prooeas of producing mononitrodi phenyls which consists in forming a suspen sion of diphenyl in a solution of nitric and sulphuric scids of a concentration producing substantially no nitration, adding thereto a mixture of concentrated nitric ana sulphuric acidsr and controlling the temperature dur ing nitration so that it does not exceed 40 C. 9. Ihe herein described process of making mononitrodiphenyls substantially free from dinitrodiphenyl, which consists in suspend ing diphenyl in a spent solution of nitric and sulphuric acids, adding a mixed concen trated nitrating add thereto, agitating said mixture during aaid addition, cooling said mixture to prevent overheating, separating spent acid following nitration, washing ni trated product to remove acid, and drying nitrated product to remove water therefrom. 10. The herein described process of making mononitrodiphenyls substantially free from dinitrodiphenyl which'consists in suspend ing powdered diphenyl in a mixture of nitric and sulphuric acids of.such a Concentration that substantially no nitration occurs, agitat-. ing said diphenyl acid mixture, adding a mix- Vture of .concentrated nitric tad sulphuric taids to term mononltro compounds of di-. phenyl while exhausting bald acids tb *p. proximately the Otatoctmtkrtfax the Imd in * Cp ..^rtuch srip drohpqyl was ^upended, main- 0265351 >*> TOWOLDMONOQ57425