claims, are intended to mean: a-11 organic primary and secondary an-iines or hydramines, their salts and derivatives' or compounds, as well as substances or mixtures of substances which give rise to such amines 100 or to their salts or derivatives or corhpounds. The expression "cellulose - xaritho - fatty acid" means in the description, and claims, the products or re'action mixtures obt@Lined by treating a cellulose xanthie, acid or a cel- 105 lulose xanthate (for 'example any, forin of viscose which niay be alkaline, neutral or acid), witli a moiiohalogen derivative of a f,,ttty acid, or with a salt or derivative thereof. This expression is intended also to in- 110 cliide the salts of sucli cellulose-xantho-fatty acids, and alslo substances or mixtures of substances which give rise to such cellulosexaiitho-fatty acids or to salts thereof. The expressions "lialogen derivative of a 115 fitty acid", "monocliloracetic, acid" and the like, used in the description and el-,tiiiis mean the free acids themselves or salts or deriva. ti-ves thereof. . sed in the claims "in the 120 The expression u form of iinshaped products is intended to mean: Iftakes, powder, sand, crumbs, bits, solutions, pastes, and the like. The e,xpressioii "-cellulose thiouretliane. in which at least one hydrogen 'atom of , the 125 amido group is replaced by an alcohol radica-111 means in the description and claims: an N-alkyl-, Naryl-, or N-aralkvl-tbiourethane of the cellulose gr(,uLp, in Which the cellulose component is either cellulose itself or a 130

1,674,401, 7 conversion prodtict or coinl)oiind of cellulose; that. is to say, as far as the pi,esent invention is concei-ned, the e.xl)i-essiori includes @hose prodiiets iviiieli iiiay be obtiined by -.ictiiig witli -,i compound dei,lved from aininoni,.t in whicli at least on,B liydrocreii -.itojii of the ammoni-,i is replaced[ by in alcoliol radical, on a celltilose-xantlio-fatty icid, tli-,it i-, to s-,tv, on the products obtained by the reaction b@iween viscose ,tnd a monolia'logen-derivative of a f,.itty acid or -.i salt tliereof. 1 claim: 1. A process for the rn-,inuf,,tcture of new cellulose compounds, wliicli com ses actinpri on a cellulose-.xgntlio-fatty acid with t coiiipound derived froin ammonia in which at least ojie liy(Iro(ren atoin of the ammoni,,t i's replaced bv an-oi,ainic radical, ,ind ,it least oiie li@ clrogen atom of the amiiionia can 20 still be replaced. 2. A process for the m,,inufacture of riew cellulose conipounds. - wliieh comprises acting on a cellulose-xant,ho-fat,ty acid with a coi-npoiind derived frolii illimonia in -wliieh ';5 at least oiie hydi-o(ren atom of tlie ammonia ;n is i,el)laeed by a,n aryl grotip, and at le,,tst one bydrogen atom of the ammonia can still be replaced. 3. A process for the manuf acture of new cellulose compotinds, iihich comprises acting on a celliilose-xaiitho-fatty acid with an org,,tnic amiiie in wliicli at least one hydrogen atom of 'tlie nitrogen-hydrogen group can be replaced. 4. A process for the manufacture of new cellulose compotinds, wllicli comprises acting on ,t cellulose-xantho-fatty acid witli an Itromatic amine iii ch at least one I wlii liydrocyen atom of the iiitrogen-hydrogen 40 group ean be repl,,teed.- 5. A process foi- the manufaettire of new cellulose coriipotidds, wliieli comprises actiiig. on a celliilose-xantlio-f att, y acid with aiiiliile. 6. k process for the manufaettire of new .1 5 celltiloze conil)otinds, wbieli comprises acting on "I cellulose-xaiitlio-fatty -,teid with aii aniline. T. A pi-oi@ess for the manufactiire of i-iew celltilosecoinpoiinds, whicli comprises acting 50 on a cellulose-xanth-acetic -,icid with a coiyipound derived froni animonia in which at least one h3,drooen atom of the ammonia is replaced by an orgranic radical aiid at least one hydrogen atom of the ammonia can be 55 i-eplaced. 8. A process for the manufacture of new ceIlLilose compounds, which comprises acting on ,i cellulose-xanth-acetic acid with an orgaiiie amiiie in -whicli at least one hydrogeii 60 atom of the nitrogen-hydrogen group can be replaced. 9. A prcicess for the manufacture of now cellulose coinpoulids, which coiiiprises acting on a cellulose-xanth-acetic acid with an aromatic amine in which at least one 05 'Iiy i-oaen atom of t-he nitrogen-hydrogen grotil) ciii be replaced. 10. A proeess for the manufadttire of n.ew celltilose coiiipouiids, which ' compi-ises acting oii a eellitlosc-xaiitli-acetic acid with anilirie. 70 11. A I)i@ocess for the mantifacture of ne* colltilose coinpounds, iilliieli coinprises acting oii i celltilose.-xantli-acetic acid with an aiiiline. 12. A I)rocess for the manufacture of new 75 celltilose compounds, which con' rises adding to viscose a monolia-logen dei@ivative of a f,,itty acid, aiid actincr on the so obtained re,,tetioii mixture witl@'a compound derived fi-oni amnionia iii -%vhich at least one hy- 80 di-oo-eii atoiii of the ammonia is replaced I)y iii oi(Ya,nic r,,tdical and in which at least one Ilvdi-oo@en atom of the ammonia can be replace 13. A pi-ocess for the manufacture of new 85 celitilose compotinds, wliieh comprises addiii ose a monolialo(yen derivative of a - ;',ttttoy'%aisccid, and actiiia on the so obtained i-e.,ttion iilixtilre witli i,n oi,(Yaiiie amine in en I wliich ,it least one liydi,ogell ,ttom of the 90 iiiti-ogenliydrogeii gi-oup caii be replaced. 14. A process for the nianufacture of new celliilose compounds, which comprises addino- to viscose a monolialogen derivative of a 'fatt-y acid, and actin(y on the so obtained 95 reacti'on mixture with an aromatic amine iii -%vliieli at least one hydrogen atom of the ilitrogenhydi-ogen group can be replaced. 15. A process for the manufacture of new celltilose compounds, which comprises addin!z 100 to viscose a monolialosyen derivative of a fatty acid, and acti. no, on the so obtained reaction mixture with aniline'. 16. A I)i,ocess for the manufacture of new celltilose compounds, ivllich coiilpi-ises addin(Y 105 to viscose a nionolialo(Yen derivative of a fatty .tei(i@ aiid actin(y on tlle so obtained i-eactioji iiiixture with an aniline. 17. A process for the manufacture of new celliilose compotinds, NA-Iiich (,oinprisos adiclid(r 110 to viscose, monochloracetic acid, and actiiig on the so obtained reaction.mixture with a coiiipound dei-ived f-rom ammonia in -which at least oiie I)ycli,ocen atom of the ammonia is replaced by an oi-ganic radical and in 115' w ich at least one hydrog II cren atom of the ammonia can be replaced. 18. A proces for the manufacture of -ne-w cellulose compounds, which rises adding to vi,-cose monochloracetic = and acting 120 on the so obtained reaction n-tixture with an organic amine in which at least one hydrogen atoin of the ilitrogen-hydrogen group can be replaced. 19. A process for the manufacture of P-ew 125 cellulose compo-Linds, which comprises adding to viscose monochloracetic acid, and acting on the so' obtained reaction mixture with an

1,674,401 aromitic amine in which at least one hydrogen atom I of the amino-group can be re'placed. . 20. A ptocess for the manufacture of new cellulose compounds, which comjprises adding to visdose monochloracetic acict, and acting on the so obtained reaction mixture with aniline. 21. A process for the manufacture of new 10 cellulose compounds, which comprises adding to viscose monochloracetic acid, and acting on the so obtained reaction mixture with an aniline. 22. A process for the maniifacture of new 15 cellulose compounds, which comprises treating viscose simultaneously with a monobalogen derivative of a fatty acid, and with an orgarile amine containing at least one hydrogen atom of the nitrolen-hydrogen 20 gro@p capable of being replacecl. 23. A process for the manufacture of new @ellulo.se compounds, which compi-ises tr'eating viscose simultaneously with a monohalogen derivative. of a f atty'acid, and with .25 an aromatic amine contaiiaing at least one hydrogen atom of the nitrogenhydrog@n gr7 capable of being replaced. A process for the manufacture of new cellulose compounds, which comprises treat30 ing viscose simultaneously with monochloracetic acid, and with an organic amine containing at least one hyclrogen atom of the nitrogen-hydrogen group capable of being replaced. 35 25. A process for the manufactiire of new cellulose compounds, which comprises treating viscose simultaneously with monochlo].-acetic a@id, and with an aromatic amine containing at least one hydrogen atom of the 40 nitrogen-hydrogen group. capable of being replaced. 26. A process for the manufacture of new cellulose compounds, which comprises acting on ti cellulose-xanthofatty acid with a com46 i& in which at f the ammonia is ical, and'at least ammonia can still be replaced and isolatiiig the pioduct so obtained from. the reaction mixture; 50' 27. A process for the manufaefure of new cellulose compouELds, which comprises acting on a cellulose-xantho-fatty acid with an or. ganic amine containing at least one hydrogen atom of the nitrogen-hydro n group ca- 55 pable of be@ing replaced, -anfisolating the product so obtained from the reaction mixture. 28. A process for the manufacture of new cellulose co.mpounds, which comprises treat- 60 ing viscose with a monohalogen derivative of a fatty acid and with an oroanic arinine containin- at lea t o:)ne hydrogen@atom of the nitro(ren-Eydrogen group which can be replace7d, and isolating the j)roduct so obtained 65 fi-on-i the reaction mixture. 29. As a new product, a thio-urethane of the cellulose group, in the form of unshaped products, in which an organic radical has been substituted for at least one hydrogen 70 atom of the amino-group. 30. As a new product, an aryl-thiourethane of the cellulose group. in the forra of unshaped products. 31. As a new product, a phenyl-thiourethane of the cellulose group in the form of unshaped products. 32. As a new product,. a chqmical compound of cellulose containing nitrogeli and sulphur. so 33. As a new product, a che ' mical compound of cellulose soluble in aqueous alkalies and containing nitrogen andsulphur. 34. A thiourethane of cellulose. 35. A substituted cellulose thiourethane. 85 36. A cellulose compound containing nitrogen and sulphur in which a carbon atom is attached to the cellulose group, a sulphur atom and a nitrogen atom by different linkages. 90 37. As a new product, a thio-urethane of the cellulose group in @which an organic radical is attached to the n itrogen thereof. In testimony whereof I affix my signature. LEON LMIENFELI).

Patented June 19, 1928. 196742401 UNI TED STATES PATENT OFFICE. LEON LILIENFELD, OF VIENNA, AUSTRIA. CELLULOSE COMPOUN3) AND PROCESS FOR MAKING SAME. No Drawing. Application filed July 23, 1924, Serial No. 727,805, and in Getmany May 19,1924. According to tlic.present invention, new celli@lose derivatives ma-y be obtained @y causing compoiinds derived from ammonia, in which an alcoliol radical is substituted for 3 at least one, hydrogen atom of the ammonia, and in which at least one hydrogen atom of the ammoiiit can be replaced, to react with the pi-odticts or reaction mixtures obtained by the actioii of t inoiaohalo(,en derivative of 10 a fatty acid on a, cellulose-:@anthic-,acid or a cellulosexanthate (viscose). The new cellulose coinpounds are iiisoluble or oiily, spariiigly soltible in water, but are soliible iia alkalies to give solutions which 0 15 addition of . an agent that neutralizes the alkali (for exan-iple an orcranic or inorganic acid, an acid salt, an animonium salt, or the like) or of a deliydratincy a-eiit (for example a salt, alcohol., or the lik@), yield precipi20 tates or coagula I which may be obtained in transparent, solid, flexible forms such as tlirea(Is, filins, Gr plates by bringing the solittioil into a suit.able form. The new cellulose derivatives dissolve also, accordino, to 25 the nqture of the alcohol radical intod@u'ced into the aininogroup, and accor'din- to the character of the celliilose co.mponent, in solutions of alkaline eartlis, in an-imonia, in organic solvents or mixtures of solvents, 30 sucli as bases (for example in manv primary, secondary and tertiary aniines of the alipliatic and aromatic series, iii j)olyaniines, i-ii quaternary bases of acyclic, cyclic aiid lieterocyclic struettire, in b@dies of tl-ie 35 (ruanidine a'nd p@,i,idine series, in, phenols; in carbon disulp@ide, in mixtures of carbon disulphide w.it,li iiiono- or polyhalogen hydroc,,trbon derivatives, in lialogen hydrins of polyhydroxyli,@ alcoliols, and the lil@e). 4o The presence of sonie water improves the sollibility of the new cellulose compounds. Their solutioiis iii suitable volatile solvents e. -. aqueolis pyridine, yield on'dryino, transarent, flexible products (such as, filiiis@ 1 45 avers, t breads or plates). In the new cellulose compounds there are obtained for the first time substances of the cellulose aroup which can be -vvorlced up into technical-products, b@ precipitation of their r)o al.kaline solutioii,13 as -well as I)y evap6i,ation of their . @OlLitions in volaiile solvents, These products are siiperior in many respects to those obtainable from tho known cellulose derivatives -",hich are soluble in 55 alli:ali, for instance, in respect of their firmness lin contact with water.- As already stated, the present invention concerns the reaction of cellulose-xanthofitty acids oi- their salts or derivatives, v-itli com pounds derive(I froiri amuionia, confain- 60 ilig - ,tn a;lcoliol radical in place'of at least one of the liydrogen ttorris of the ammonia and in whicii at least one hydrogen atoxii of the iiinnioliia cin still be replaced. liy tite exl)ression cellulose-xantho-fatty aci@ 65 (celli llose-thiontliiol-carbo-liydroxy paraffin iiion ocarboxylic acid) in the descript.ion and clain is are to be un(.Iei-stood the products or ieaction mintures -vvhich may be obtaiined by ,tctin (r on a cellulose-xantlii@ icid or a cellu- 70 t, losexantbate (a tl)ion-tliiol-carb6nic ester of cellulose , or a salt. of such ester) with a ii)oii oh,,ilo(ren dei-ivative,of i fatty acid, or a qllt or d@rivative tbereof. Tlle cellulose-xantliie acid ilesidue pres7 5 ent in the cel.lulose-xantho-fatty acid may cont ain as the cellii.lose component cellulose itsclf, or a coni,ersion product of cellulose, or ai)y suitable cel.lulose compound. As niti-o,@en compounds for the purpose 5 0 of the ijivet.'ntion there come into consideration coniliouiids qf the alip-hatic and aromatic series in which at least one hydrogen ito ni of the amnionia is replaced by an aliI)li,,it i6 or aroniatic alcohol residue, and in 85 iNIii eli thei-e is still one h3,drogen atom of the ,tnimonia which can be replaced, in the first place the primary or secondary organic anlin es or hydro-amines (oxalkyl bases). The iiitrogen compouiids may be used in the go fi-ce state, or in the form of their salts or dei @ivatives. The conditions niay be varied within wide Iiiiiit s. On this ,tccount, the inveiition is not liiiii ted to tlle details of the follolvincy de- 95 scription of its practical utilization llus4trated by -workiiig exainples) since these cletails do'not iffect the essence of 'th6 .@inv6jft tion. -d- ioo The.. cellulose-xantlio-fatty acids are a vaT-ita(-eou.,ily prepared by' actid- upon a cellulose-xantliie acid, nan-ielv an alk,,tll com1)oiiiio of ,i tliioi i-th@ol-carbinic ester@of cellulose without excess in all@ali (for exaiii . le cru(le o@ piirified foriii @of @viscose Nvhich has lo5 I)eeli iieiltralized or,iiiade acid by addition of a.-Yveali @cid), or upon an 611call:'compoiin4 of a thioi-tliiol-carbonle ester of cellulose Nvit'il Ilkali iii exe(@ss (for insiLanc6, a @rlide or purified vis I cose O'f Ilkaline reaction), 6r lip upon a compound of 6ell.ulose-xanthic a@id with -anotli@r metal (:for example, zinc)

2 1,674,401 witli -.t nionolialogen derivative of a fatty aci(i, or a salt or a derivative thereof (for exajliple, according to the process described iii -,Pecification No. 727,807).. The celluloseo xant,,,c acid or cellulose-xanthate m-,iy be ti-eated with the lialogenfatty acid either in dilute or concentrated solution, or as a paste, or in the forin of the product of the reaction between alkali celliilose and carbon disulio pliide befoi-c bi-in(,in(y it into solution. The celltilose-x-,intliie licid or tlle cellulose-xiincelliilrjse-xaiitlio-ftitty acid citlier in the, et-ii(le state or after purification by any ia kiiown niethod. .. It is to be iiiidei-stood tliat, where the concc I 31 text 1.)el-iiiits, the expresgions viscose , "celltilose-xanthic acid" ind "cellulose-xanthate" used in the description and claims 20 include the fori-ns of cellulose-xantliie acid or celliilosexanthate (viscose) named in the preceding @?aragrapli. The reaction between the eelliilose-xanthic a-cid or celliilosexantliate, and the balo(ren 25 derivative of the fatty acid on the one b@'nd, and that between the cellulose-xantlio-fatty acid and the organic nitro,- ,en compound oii the Qtlier hand, may be cai@ried out in two se I pai-ate operations, oi maybe combint@d into 1( one 4)perat,ion. The oi,ganic, nitro,-en compound can t.herefore be caused to react with the isolated cel lulose-xantligfatty acid, or witli tlle crude reaction mixture obtained in its preparation, or witli the cellulose-xantho35 f atty ac'id in the nascent state. That is to S,,iy, the nitrogen base may be brought intb reaction ei@lier witli the isolated ce llulosexantlio-fatty acid or a salt thereof, or witb the reaction n-xixture colitaining it, or witb 40 the cellulose-xantliie acid or cellulose-xan. thate (viscose) before, during or after addition of the halogen-fatty acid or salt or deri.yative thereof. The treatment of the 'cellulose-xantlio45 fatty aicid, or salt thereof, with the organic nitrogen compouii.d may be carried out in iieutral, alkaline or acid solution, and the cel lulose-xantlio-fatty acid may be used for the reaction in tlle solid state or in suspen50 sion, for instaiiee in alcobol. In most cases, the reaction occurs at ordipary temperature; crentle or stronger heatin,r tisually accelerates it. The amino-base may be added in excess, 5.1$ in the tlieoretical quantity, or in an amount wliieh is less than the theoretical quantity. I The formation of tlxe new cellulo--e comthe end product when the re= is carried 60 out in solution, and when the reaction mixture does n6t contain any substance which will dissolve the end-product or hinder its formation (for example a sufficieiit quahtity of alkali). This precipitate forms a es stik or soft jelly if the solutio,n of the e.ellulose-xaiithic acid, or cellulose-xantlinte, or cell ulose-kaiitlio-fatty aoid is concentrated, lind if the solution is not stirred, or is stirred oiily a little; if the solution is suitably diluted and stirred the product 8 @ P @ - 7 0 rates iii tlle forin of a fiiie or coarse precipi. tite. The final product of the reaction may be isolated for example by separatina the precipitate oi- the jelly from ille mo@ller liquor by filtei-in(r, sti-ainin(Y tlli-ougli clotli, ceiitlloroiiglily witli wtiter. As a i-ule, the jelly contracts on standiiig for some time, and sliows separatioii of liquid. The niotlier s(i liquor aiid the wasliing- 'v@ater contain as cliief I)y-product of the reaction the correspon(ling tliio-hydroxy paraffin-monocarboxjlic acid. If the pi-ecipitate is a jelly, or is ulky, if is necessary t-o-break it up before gl$ the wasliing process. In order to reniove any by-proaucts of the reaction which are insoluble oidifficultly soluble in ivater, the wasliing witli water may be followed by a wasliiii,; ivitli ale6lio.1, or first witli alcoliol im) and then witli ether, benzene or the like. The compound after wasliin(Y may then eitlier be (lissolved in the wet condfiion (if. necessary after pieviously removing tlle bulk o.,f adhering wash-li Uld by pressing, O's filtering, suction or centr @luoing), or dried. if no pi-ecipitate is formed, or if complete precipitation of the end product does not occur spontaneously, the product may be isolated, for example by treatin'g the reaction itxt mixture before or after @ompletion of the reaction with an acid or an acid salt until a precipitate is-produced, and then proceedino, as ali-eady described. lecording to their mode of formation iind ioi-, chemical beiiaviour, the new cellulose compound,.3 prodiieed tiecording to the inventicin are tliiotiretliftnes (tllio-carbamic acid estersor xantliamides) of ceuulose or of the cellulose groiip, in which at'least,on6 liydrogen 110 atom of the amido (-rroup is replaced by an alcohol radical. According to whether this alcohol radical is an alkyl, an aryl, or an arallzyl group, the now cellulose derivatives will be alkvltliiouretlianes (alkvl-tbio carbamic i i.5 acid e@ters, alkylxanthamides), or arylthiourethanes (aryi-thiocarbamic acid esters, aryl-xanthamides) or arilkyl-thiourethanes (aralkyl-thiocarbamic acid esters,, aralkylxanthamides), of @eelluloge. 120 The simplest. type of the new cellulose derivati-,,es may be represented by the folpounds manifests itself by itation of lowing formula (without however li ting mi tli.ite. (viscose) illiay be conv@rted into the,- - ti-ifu(ring o;@ the lilce-and then wasliing it the invention to thisy-- or R.N: C(SE).O.(CS.Ul$.40S-1), wherein R represents the alcoliol radical which has been introduced into the amido group. This radical may be an alkyl or oxy- i3o

1,674,401 3 all,.yl group, an ai-yl- oi- oyyaryl group, or an aralkyl oioxyai-all@yl gi-oup. Wliere the context pet@iiiits iii tlie, description an(I clainis, tli(@ e-,I)i,(@ssioii ",tll@yl" ineltides tlso oxyill@N,l aiid liy4lt-ox _@,illcy'l I -yl -,tii(i liv(li-ox y-l@' also oxyii -yai-YI, ttid ",ii-ztllcvl" iliciil(l(@s il,,o ox'tti-tll@',l .tiid liydi:oxvti.tll@.@,]. The react I i oiis li(@ - @(lin(@- to t.lie foi-iiiitioii of 10 tile liew celltilose Collll)ollll(ls iliay be i-epi,(,sented foi- tli(, siinplest @ype by the follo-,ving cqtiations. As iin example, are taken ,,odiiiiii celltilose xtntl),,ite, sodiuiii cliloracetate, - ,iiid aniline:- 15 Foi-iii:ttioii of celliilose-xantli-acetic acid:- (CO.Ilia.- 10.5. -i).O.(',Qt.S.Na+("I.CI12-COONa (sodium celltilose x,,knth:ite) O.CS.,.CI1200ONa+N-.iCl (,soditim cellulos'exantli-acetate) (sodiura cellulose thionthiol-cgrbon-glycollate) 20 Forination of cellulose-xaiitl i-anilide:,,YlID.-106.- I).O.CS.S.CH2COONa+C6115NIT2@ @..z-@diuin cellulose-xanth-acetate) 'ii,.Nll.(, tsodium thioglycollate) (celltilos(,xanth-anilide) (plienyl thio-urethane of cellulose). 25 The invention is iii no wav Iiinited to the eqiitttioiis given al)ove, siiiee"tliese are given onlv for the piirl)ose of illiistrittion, an(i sin@ , e ,iii exli,,iiistive atid exact stiteiiient of the elleinistrv of the reaction is iiot t siniple 30 ,ilid readily solved probleiii in view of the ini-perfect Icnowledge of.-the constitution of celli-ilose. . The invention is illustrated by the follow .1-@)g examples, the parts being by wei(rht:33 (a) 1000 parts of crude viscose (pre pared for exatnple by impre(,tnatin(r 100 parts of su@lphite-cellulose in fleece- or slieet40 form wit-h 1000-2000 parts 6f caustic soda solution of 18 per cent strength at 15-18' C., allowing the n-iixture to stand at roon-i teiiiperattire for 3-24 hours, I)ressin(r. Lintil the m,.tss weighs 300-350 parts, corniiiinuting iii 45 a shredder or the lilce. allowing.to matur e if necessary for 6- 72 hours at room tei-nperature, treatin - cr for several hours with 50-60 parts of carbon disulphide, aiid dissolviii@Ir in sufficient -%,ater to bring the total weigl-it 50 of the solution to 1000 parts), corresponding -with 100 parts of cellulose -,is parent material, are diluted, either in the freshly prepared condition, or after standiag for ,i short or long period (6 hours to 3 days). r)5 with 5000 parts of w,,iter, and then treated; whilst stirring, with dilut@ acetic ,icid (e. g. 5-10 per' cent strength) until the mixture shows a neutral or faintly alkaline reaction As soon as the hydrouen sulphide liberate5 60 during the neutralization has-escaped er@tirely or for the greater part, the viscose which has becoi-ne lioht in colour is treated with a solution of @odium monochloracetate prepared by dissolvino,, 60--100 parts 'of - mono65 chlorace'tic acid in 480-800 parts of water and neiiti-alizing the solution with powdered so(iiiii ii,l)icarboiiate. IVI)en the solutioii of sodiiiiii iiioiiocliloracetate lias been iiicorl)oiated witli the N-isco8e, the iiiixttire is stirred l@or a slioi-t tilii(@, -.tiid tlieii alloNN-e(I to staiid i(i it iooiii teiiipei-attii-e. After 6-48 liotirs staii( Iiii(y there ai-e a(ided to the niixture (Nvll i(-Il iiia3, be iietitrilize(I sliotild it react f',tiiit ly alkaline) wliilst stii-i-in(r 60-120 I)aits of anilijle. Aft(@r several ii'ours, the 75 1,(,,a ctior. pi-oduct begins to sel)ai-ate in a fiilely (livided state wlien tlle iiiixture is well @iii -i-ed, an(I finally settles to the bottom. As soon as the pre'eipitatiloii is coiiiplete, or after tilic i,,iixtiire, liis becii tillowed to stand 80 afteithe 1)i-ecil)itition for a pei-iod of froin ,@e vei'al liotirs to tlii-ee (lays, the I)i-ecipitate is separated fi-oiri ttie iii@iliei--liquoi, by de-ca;itiii(- filtei-ing, filtering under su@tion, t', 'sti'ainiii(- tlii-otigh clotti or centrifugin(,, by 85 other liquor ,c!idifyiii(y iii for instalice'witli stilpliiii-ic aeid, ex.ti-actiiig it with ether and (li"tilliil(y the etlici,, a coiisiderable quaiitity of tliioglycollic I acid can be detected (for exaiiil) le I)y the i@eaction to@vard ferric clilo- 1)( i-ide ind aiiiitioiiia or @3@ obtainillg it in the pure stat(@). 'rlie pi-(@,cipit-ate NNhicli has been separit ed from the iiiother liqtior is tliorou-lily ivaslied witb water and dri(@d at atiiiospli eric or redueed pressure, if desired 9,3 after one or iiiore ti-eatineiits with alcohol,, or witli alcohol followed by ether. Th e fiiial prodtict is a powdery substance, esl)eei ally after gi-iiidiiig, insolu'ble or practically insollible in water, alcohol or ether but soluble in the follo@ving solvents, for examp le: dilute caustic , ,@a,, (for instance caustic soda of 1-10 I)er cent strength), aqueo us amrnoiiia (for instance 10-25 per cent), ctllylamirie, especially iii presence of 105 some water, ' dietliylaniiii'e, especi,,Illy iri prese nce, of son-ie wat(@r, ethylene dian-iine, guanid ine, especially irl presence of some watei-, qliaternary bases, aniliiie, piperidine, espec. "ally iii pr@'s lice of some -vater e , p@ri@ 110 din. especially in presence of soii-ie water, aiiionochlorh'ydr.iii, a-dichlorhydrin, especially in presence of. sojiie water, etliylenechlo@ liydrii-i, especially ivhen mixed witli water, plienol especially in presence of soin(@ 113 water, and the like. A suspeusoii of the substance in water has a neiitral reaction to-",ards litmus W hen the substance is beated for 4-6 bours qt 200- C. tinder pressure wit-li Sul- 1,20 plitii-ic acid of 2 pet- cent, sti-encyth hydrogen sulpbi de and aniline are split off; the latter may be detected by all the known reactions for aniline in an etliereal 6xtract of the reaction liqiiid wlien t-Iiis has been made alkaline. On heat;ng under pi-essure for several hours at 150-1800@ C. with ammonia of. ' 25 per cent strenath, the substance decomp'o's'.e's' witli liberati@-n of bydro(ren sulphide and aniline . On heating ihe s-ubstance for eight l'O

1,674,401 hours at 150-170' C. with liydrochloric acid of 1-2 per cent strength, liydi-ogen sulpliide and aniline can -be detected in the mixture, but no glycolic acid (on oxidation with nitric acid). At the saine time, sanil)les of a celliilosc-xantliacetic a(-id and of a celltilose glycolic acid when hate(I iin(ler the s,iiii(@ coi)(litions yield a considei-able quaiititi of irlycolic acid. it) ii (,@TL@iiientai-y anaylsis gave the followino, results:- Calctilated for C,.H_.@Nsolo Fouii(I (Cullr..NH.CS.O. (Cl2llio,Ou) 4i). 67 47. 81 48. @t 5.44 r); :12 5.13 6.97 7.15; 6.95 N 3.05 3.25; 3. 0(; Ash: 0. 28% Taking into account the fact that the substance analyzed was not specially purified,' 2(i the above fig: res are in @,,ood agreement with those Of phenyl-tliio-@rethane of cellulose or of a body of the cellulose class @eellulose-xanth-anilide, phenyl-thiocgrbamic acid ester of cellulose). 2;) Wlien a solti't-ion of the substance in dilute caustic soda (for example of 1-10 _per cent strengtl-i) is spread on a. glass plate and treated with a suitable precipitating bath (e. g. a solution of ammonium chloride of 3o 20 per cent strengtli, dilute sulphuric acid, or aqueous a@etic a@id) ' , there is, obtained a skin, strong when wet, and transparent and shining when dry. A solution of the cellulose-xanthanilide 35 in an aqueous solution of pyridine of 70-80 per cent streiigth yields on drying, a transparent, flexible film, having a notable resistance towards water. Its useful properties are not destroyed even by heating for several 4o days at 60' C. (b) The procedure is as in Example 1 (a), with t-he vari,,ition that 150-250 parts of aniline are tised. The large excess of aniline does not modify appreciably the properties 4.i and solubility of the product, but . renders careful purikeation necessary, since in presence of a lar(yo quantity of aniline, tangible amounts of diphenyl-thiourea, and eventually also of dphenyi urea are sometimes bo formed as by-pi-oducts. Th6 cellulosexanth-anilide mav be freed froin these aromatic ureas bv thoroughly washing it with water, and e@tractino,, it'with solvents for these Slibstances, for instance alcobol, ether, -i's or the I ike. (e) The procedure is as in Example I (a), *ith the modification that only 30-40 parts of aniline are used. There is no appreciable alteration in the properties of solubility of oto the product. (d) The procedure is as in Examples 1 (a , I (b) or I (c), with the modification that there are used only 30-.40 parts of monochIGracetic acid, dissolved in 320-400 Fiarts oc, of water. The cellulose-xanth-anilide so obtained dissolves readily in diltite caustic soda@ but does not dissolve in a(lueous pyridine as readily as does the product of Example 1 (a). 70 (e) The procediire is as in Examples I (a), 1 (b), 1 (e) or 1 (d), with the excel@tion that tlle aniline is added inimediitte.y or soon after (for exatyiple 10 minittes to 1 liour) the sodii.,m inonocilloracetate bas 75 been incorporated in the viscose. (f) The procedure is as in Examples 1 (a), 1 (b), 1 (c), 1 (d) or 1 (e), -,vith the exception that 200-500 p-,trts of nionocliloracetic acid dissoivc(l in 1600-4000 I)arts of 80 witter and neuti,,qlized with powdered @odium bicarbonate are used. (g) The pi-ocedure is as in Examples I (a), 1 (b), 1 (c), 1 (d), 1 (e) or 1 (f), wikh the exception that fi-om the beginning 85 ihe reaction mixtiire is Icept at 8 to 120 C. uiitil tbe, tiddition of aniline takes, place. (It) The procedure is as in Examples 1 (a), 1 (b) @ 1 (c), 1 (d), 1 (e), 1 (f) or 1 (.q), with the variation that the viscose is '90 mti@le faintly acid or distinctly acid by addition of dilute acetic acid. The properties of solubility of tlle product are not altered by tilis modification. (i) The procedtire is as in Exam I es 95 1 (a), 1 (b), 1. (c),. I (d), 1 (e)i I (f), 1 @ig'), or 1 (A), with the exception that the soda celliilose is reduced tc; 200 parts by pressinand is sulphidized by me,,Ins of 20-25 parts of cirbon-disulphide. 100 2. . The procedure is as in any of the Exampl.es I (a) to 11 (i) with th@ exception t-bat instead of aniline there is used aii equivalent ios amount of ortho--toluidine. The celltilose-xa-ntho-toluidides obtained correspond in their appearance, ]properties -.iiid solubilities with the anilides described in Example 1. Tbe'films obtained from so- lio Iiitions in caustic alkali or pyridine are very resistant to-vyards water. 3. Instead of the aniline used in any of the ii5 Examples 1 a) to 1 (i) there is used an equivalent amount of ethylamine or of methylamine. The reaction proceeds more occurs in small be brolcen up by 1:!u drying, dis-olves in diltite causti and in an aqueous solution of pyridine of 90 per cent strength. The soluflon in pyridine i23 yields on drying a clear, flexi ble film. 4. The rocedure is as in any of the Examples 1 (a) to 1 (i), with themodification 130

l,e74,401 that instead of aniline there is added to the cellulose-xanth-acetic acid an equivalent amount of diethylamine. The reaction ocetirs r(@markably quickiv. The diethyl-thioiiretbane of cellulose which separates in a finely divided state is insoluble or barely soluble in caustic soda solution of 1-10 per cent strength after washing and diying. It is readily soluble in aqueous pyridiiie of 90 T)er 10 cent sirengtli, (riving a soltition ivhiell yie.ds on (Irying a lustroiis transpal-ent skin which is flexible and is resistant towards water. 5.. 13 Instead of the aniline used in Example 1, there is used an equivalent amount of phenyl-ethylamine (C,H,.CH,.CH@.NH,). 20 The cellulo-e-phenyl-ethyl-thiourethanc, sep arates in flakes shottly after the addition, and, after wash ' and drying, is insoluble in in caustic soda .Ofution, but dissolves readily in an aqiieous solution of p 'dine of 90 yr' 25 per cent strength, to a solution whiell yields on drying a clear, ltistrous, flexible film, which Lg very resistant towards water. 6. 30 The procedure only differs from that of the preceding examples in that-the viscose is not netitralized before addition of the monochloracetic ,icid; the reaction rnixture is neutralized or made f,,tintly or distinctly acid, ,i;i for example, with dilute acetic acid before the addition of the aniline or other amiiie. Generally spealiing the products so ob. tained exhibit the same properties and solubilities as do those prepared from viscose 40 which has been neutralized, or made faintly or distinet'..y acid.- It is also possible to Nvork by iiot neutralizing the viscose either before addition of the monochloracetic a,cid or before addition 45 of the aniline or other amine; in the latter case the reaction with aniline occurs more slowlv, -,tnd the final product is pre(:ipitated after a longer interval of time and in a less finely divided condifion., 50 (a) 1000. parts of viscose prepared according to the method described in Example 1, corresponding with 100 part-s of cellulose as 55 parent material, are diltited with 2000 parts of water, and treated with the soluti.on pi@epared bv dissolving 65-70 parts of monochloraceiie acid in 260-280 parts of water and ne-utralizina the acid with solid sodiunl (so bicarbonate. A:Iter standing for 4-48 hoiirs, the liquid mixture is iieutralized with Acetic acid of 10 per cent strength, 60-120 parts of aniline are a4ded, itnd tlie mixtiire stirred. The product corn'mences to separate after 05 a few hours, and settles to the bottom; it may be separated from t-be mother-liquor citlier soon after the precil@itation is comI)Icte, or after staiidin- for 1-3 days, Bnd iii.,iv then be worked "tip as described in Ex,tinple 1. 70 I'lic celltilose,-xantli-anilide forms a more or less fine poNN'der after drying, and possesses I)roperties an(I soltibilities similar to tb(,,s- of the product desel-ibed in Examr',@ I (b) The proceduj,,e is as in Example 7 (a), witli the (liffereiiee that there are used onlv 50-60 pai,ts of monocliloracetic acid dis'- solved in 200 parts of water and neutralized with soli(i soditim bicarbonate. 80 The cellulose@xanth-anilide so obtained is a powd-ry or flaky substanc@; it is soluble in dilute caustic soda, foF example of 1-10 per cent strength, but is less soluble in ,,,queou s pyi-idine of 70-80 per cent strength 85 than is the product of Example 7 (a). CqIctll.,tted for Found Collr,.NH.CS.O. (C,,H,,O,,) @ C,H,NSOM N 1 78 1. 72 s 4: 07 4. 08 vu Solut-ions of the siibstance in caustic soda yield on pi-ecipitation with an acid, transparent, lustrous, flexible fi,ims. Solutions of the substance in pyridine yield flexible skins -on drying. (e) The procediire is as in 7 (a) or 7 (b), but witli the modification that there are added to the viscose only 30 patts, of monochloracetic acid which litve been . dissolve@d in 120 parts of ivater and neutralized. The phenyl-thioiirethane of cellulose so obtaineci dissolves readily in dilute'caustic soda, but is les.9 soluble in p r'd' than is the product obtained in 7 @ta@l [clrne7 (b). There may be iise',d le@ss aniline (fo,i- ex- 105 ample 30-40 parts) or more aniline than is used in 7 (a), 7 (b) or 7 (c), witliolit causing any a-ppreciabl.e vtria,tion in the produet. In this example, also, the aniline. inay be ,idded to the reaction mixture immediately 110 or soon after the addition of the, sodiuin monochloracetate. The procedure is as irl Examples 7 (a), 115 (b) or 7 (c), with the difference that the viscose is netitralized -with dilute acetic acid before the addition of the sodium chloracetate. 9. 120 1000 parts of. vise6se prepared as described in Example 1 are neutralized, withotit previouslv diltiting, bv means of. a solution of @ectic acid ol 10 per eent 125 strength, and there is then added, whilst stirring, the solution prepared by dissolving 80-90 parts of monochloracetic, acid in 240-300 parts of water and neutralizing with powered sodiu'm bicarbonate. 130

1,674,401 There are added whilst stirring, either directly afterwards, or after an interval of 10 minutes, 30-60 parts of aniline, Whereupon the mixture is either stirred until precipitation begins or,is c4:)mpleted@ or it is allowed to stand. In the first case, the product separates as flakes or small pieces; in the second case, it solidifies to a gelatinous mass) which omdually contrac.ts with io separation of the mother-liquor. The precipitate (if a jelly it is first broken up or cut up), is wasliecl and worked up as de@ scribed in Example 1. The cellulose-xanth-anilide dissolvesreadis ily to clear solutions in caiistic socla solution of 2-10 per cent strengtli and in aqueous yridine of 70 per cent strengtli. p 'In tli @ forqoing examples, there mty be used instead of monochloracetic aeid an 20 equivalent amount of a halo-en derivative of a hornologue of acetic acict, for instance a-br,omopropionic acid, xbrombutyric acid, or bromosuceinic acid. The products so @obtained resemble those obtained by @sing 25 lp_onoclilorticetic acid. The motlier-liquor contains instead of thi6glycolic acid the cori,esponding thiohydroxy paraffni-mono- carbox lie acid (for example thio lactic acid, thio@oxy-a-butyric acid or the thio-malic so acid or the, like). Instead of using crude viscose, there may be, used in the foregoino, examples viscose which has been purifieiy by any suitable nietbod, for example by precipitating it, with 35. a saturated solution of common salt, and washing the precipitate with a salt solution of 10 per cent strength. Furthermore, in the foregoing examples, instead of bleached or unbleached sulphite40 cellulose there may be used as the parent material for preparing the c-,llulose-xiinthic acid or cellulose-xanthate, any other bleaclied or unbleached cellulose (such as cotton or linters), or a material containin- cellulose, 45 or a conversiort-product of cellul@'se (for example a hydratized or hydrolyzed cellulose or oxycellulose obtained for example by mercerization witli strong lye, and washing if necessary; by trrinding in presence of water; 50 by the action of a stron- mineral acid, zinc ,halide, or an amnioniac-,il solution of copper oxide; or bv any other method), oi- a cellulose derivaiive which contaiiis a free hydroxyl group to enable it to be converted 1-5 into he thion-thiol-carbonic acid ester (for example an alkyl, oxyalkyl 4)r hydroxyalkyl derivativ,e of cellulose, a cellulose-liydroxy paraffin monocarboxylic acid, tind the like). In the description and claims, wherever (10 the context permits, the expression "cellulose", alone'or in combination with "xanthic acid" II.&anthate", "xantho-fattyacid", "xanthic 'acid ester", "thiocarbamic acid ester", or "thiouretha,nell is used in each combina65 tion for shortness and includes cellulose itself and the conversion products and derivatives referred to in the preceding paragraph. 10. 100 pa s of air-dri6d cellulose-xa nthacetic rt To vcd p@epared as in Example 1 of my copending application No. 727,807 ar6 dissolved.in 4000-5000 parts of an aqueous solution of aniline of 0.5 per cent strength, there are then added to the solution 50-100 75 parts of aniline, and the mixture is stirred. After -,t short while (about 20 minutes to one liour) the solution becomes thick and slimy, but shortly afterwards again becomes a thin llqiiid, wliereupon it. gi@ows turbid and milky, go and the separation of the cellulose-xanthanilide soon begins. After about 10-48 hours, the white precipitate lias settled to the bottom, and may be separated from the mother-liquor and 95 -worked up ag in t-he previous examples. An etliereal extract of the mother-liqti6r shows tin intense reaction of thio-glycolic acid. The properties, sdlubility, alid elementary composition pf the cellulose-xanth-anilide 90 resemble tho@e'of the product obtained in Example 1 (a). The expression "amine", "organic amine", "aliphatic amine", i'aroma c amine 17 46 a;niline", and the like used in the description and 95