SE126379C1

SE126379C1 -

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Publication number: SE126379C1
Authority: SE
Publication date: 1949-01-01

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KLASS 12o:14 EtESKRIVNiNG OFFENTUGGJORD AV KUNGL. PATENT- OCR REGISTRERINGSVERKET BEVIDAT DEN 18 AUGUST! 1749 PATENTTID FRAN DEN 28 NOV. 1947 P1.113LICERAT DEN 18 OKTOBER 194(7 Ans. den "/„ 1947, nr 1090/1947. CLASS 12o: 14 LETTER WRITTEN PUBLISHED BY KUNGL. PATENT- OCR REGISTRATION WORK AVAILABLE ON AUGUST 18! 1749 PATENT PERIOD FROM NOV 28. 1947 P1.113LICERED ON 18 OCTOBER 194 (7 Ans. On "/„ 1947, no. 1090/1947.

RIDI30 LABORATORIES INC., PATERSON, N. J., AMERIKAS FORENTA STATER. RIDI30 LABORATORIES INC., PATERSON, N. J., UNITED STATES OF AMERICA.

Sitt aft skit,* hartssyror Iran harts eller tallolja. Sit down shit, * resin acids Iran resin or tall oil.

Uppfinuare: N. L. Kalman. Inventor: N. L. Kalman.

Prieritet begard fnin den 12 december 1946 C9.ineri1as fOrenta stater). Priority was sought on 12 December 1946 (C9.ineri1as fOrenta stater).

FOreliggande uppfinning hanfor sig till ett satt att skilja hartssyror Iran blandade material, sasom talloljor och kommersielIt harts. The present invention relates to a method of separating resin acids from Iran's mixed materials, such as tall oils and commercial resin.

Sasom bekant utgor tallolja (en biprodukt Iran papperstillverkningen) en slamartad massa med mark farg och dalig lukt, och talloljan bestar vanligen av omkring 40 % harts- syror, omkring fettsyror och omkring % andra bestandsdelar och farorenin.gar, inkluderande hartskolvaten, och oxisyror, steroler, farg- och luktarnnen, smuts etc. Den speciella sammansattningen beror pa den sarskilda pappersframstallningsprocess, fran vii-ken biprodukten harror, den anvanda pappersmassans natur etc. Harts- och fettsyrabestandsdelarna aro kommersiellt vardefulla material och manga forsa ha gjorts att utvinna dessa material ur talloljan. As is well known, tall oil (a by-product of Iran paper production) is a sludge-like mass with a ground color and a bad odor, and tall oil usually consists of about 40% resin acids, about fatty acids and about% other constituents and hazards, including resin hydrocarbons and oxyacids. sterols, dyes and odors, dirt, etc. The special composition depends on the special papermaking process, from which by-product grains, the nature of the pulp used, etc. The resin and fatty acid constituents are commercially valuable materials and many have been made to extract these materials from tall oil.

Det or aven kant att kommersiella hartser, sisom gummihartser och trahartser, innehalIa avsevarda mangder fororeningar, sarskilt harts-kolvalen och fargade material. It is also possible that commercial resins, such as rubber resins and wood resins, contain significant amounts of impurities, especially the resin carbon choices and colored materials.

Foreliggande uppfinning har till sitt huvudsakliga andamal att i vasentligen ren form avskilja vardefulla bestandsdelar ur blandade material av de ovannamnda typerna, och uppfinningen hanfor sig sarskilt till isoleringen av i huvudsak rena hartssyror. The present invention has for its main object to separate in substantially pure form valuable constituents from mixed materials of the above-mentioned types, and the invention relates in particular to the isolation of substantially pure resin acids.

Kort sagt, det ovannamnda huvudsakliga andamaiet med uppfinningen uppnas genom att behandla det blandade materialet i vatskefas, t. ex. i ett losningsmedel, med cyklohexylamin. Denna bildar cyklohexylaminsalter av de i det blandade materialet nfirvarande hartssyrorna. Saltet som Or belt fast vid rumstemperatur bildar en latt avskiljbar och separeringen utfores pa vilket som heist onskat satt, sasom genom avsattfling eller filtrering. Briefly, the above-mentioned main spirit of the invention is achieved by treating the mixed material in the liquid phase, e.g. in a solvent, with cyclohexylamine. This forms cyclohexylamine salts of the resin acids present in the mixed material. The salt which solidifies at room temperature forms an easily separable and the separation is carried out in any desired manner, such as by precipitation or filtration.

Det ovannamnda forfaringssattet utgor en hogst effektiv metod for separering och resulterar i ett i huvudsak kvantitativt utbyte av cyklohexaminsaltet av hartssyrorna, vilket salt om sa onskas kan hydrolyseras for att ge i huvudsak rena syror. FOrfaringssattet är exceptionelit enkelt att tilliimpa, sfirskilt eftersorn det kan utfiiras utan flagon avsevard forhojning av temperaturen. The above process is a highly efficient method of separation and results in a substantially quantitative yield of the cyclohexamine salt of the resin acids, which salt, if desired, can be hydrolyzed to give substantially pure acids. The procedure is exceptionally easy to apply, especially since it can be carried out without significantly raising the temperature.

Vid en typisk behandling utford antingert pa ett kommersiellt harts eller pa tallolja bringas hartset eller oljan foretradesvis forst I losning I ett Iasningsmedel, sasom nafta, Tarvid en losning innehaliande 20 % av hartset eller tallolj an Or lamplig. Cyklohexylamin sattes &rater till losningen vid rumstemperatur och harts-cyklohexylaminsaltfallningen. Midas hastigt och avsatter sig om det hela far sta. In a typical treatment challenge either on a commercial resin or on tall oil, the resin or oil is preferably first brought into solution in a solvent, such as naphtha, in which case a solution containing 20% of the resin or tall oil is suitable. Cyclohexylamine was added to the solution at room temperature and the resin cyclohexylamine precipitate. Midas hurriedly and settles down if the whole thing goes awry.

Ehuru isoleringen av hartssyror ur antingen kommersiellt harts eller tallolja astadkommes I grunden pa samma satt, foreclragas vissa mindre skillnader i tekniken och behandlingen yid behandling av harts och viss annan teknik foredrages yid behandling av tallolja. I foljande mera detaljerade beskrivning av forfaringssattet enligt uppfinningen diskitteras darfor fiirfaringssattets tillarnpning pa de hada typerna av utgangsmaterial var for sig. Although the isolation of resin acids from either commercial resin or tall oil is accomplished in much the same way, certain minor differences in technology and treatment in resin treatment and certain other techniques are preferred in the treatment of tall oil. In the following more detailed description of the process set according to the invention, therefore, the application of the process set to the different types of starting materials is discussed separately.

Betraffande forfaringssattet tillampat vid separeringen av hartssyror fran kommersiella hartser skall f5rst namnas att forfaringssattet kan tillampas ph vilka som heist i handeln forekommande vanliga hartsprodukter, SaS0111 de olika kvaliteterna av traharts och de olika kvaliteterna av gummihartser eller till och med direkt pa talloljeharts. Uppfinningen Or aven tillampbar, och i sjalva verket speciellt fordelaktig, liar den tillampas pa olika speciellt behandlade hartsprodukter, sasom disproportionerade hartser. Som exempel pa ett disproportionerat harts skall hanvisas Lill produkten enligt det amerikanska patentet 2 395 278. Vid sadana speciellt behandlade hartsprodukter anvandes ofta en hOg temperatur vid specialbehandlingen, och sadana h5- ga temperaturer tendera att astadkomma mer eller mindre dekarboxylering med atfoljande okning av mangden narvarande hartskolva- 2-- —, ten. For manga andanial är narvaron av hartskolvaten ofordelaktig, t. ex. emedan den- na narvaro sanker produktens sraaltpunkt avsevart under den narvarande hartssyrans smaltpunkt. Regarding the procedure applied in the separation of resin acids from commercial resins, it should first be mentioned that the procedure can be applied to any commercially available common resin products, SaS0111 the different grades of resin and the various grades of rubber resins or even directly on pine oil. The invention is also applicable, and in fact particularly advantageous, it is applied to various specially treated resin products, such as disproportionate resins. As an example of a disproportionate resin, the product of U.S. Pat. No. 2,395,278 is to be cited. In such specially treated resin products a high temperature is often used in the special treatment, and such high temperatures tend to cause more or less decarboxylation with consequent increase in the amount present. hartskolva- 2-- -, ten. For manga andanial, the narvaron of the resin flats is disadvantageous, e.g. because this presence lowers the special point of the product considerably below the melting point of the present resin acid.

Forfaringssattet enligt foreliggande uppfinfling äi mycicet—effektivt for- separering av hartssyrorna fran vilka som heist av de oVan- namnda hartserna, och metoden ger en produkt, vilken for praktiska andamal ãr hell fri fran hartskolvaten och andra fororeningar. The process according to the present invention is in the mycicute — efficiently pre-separating the resin acids from which are raised by the above-mentioned resins, and the method gives a product which, for practical purposes, is completely free from the resin cobs and other impurities.

Nar forfaringssattet tillampas pa ett disproportionerat harts, t. ex. ett harts Sou], beharid- lats enligt det ovan anforda patentet, ha de erhallna i huvudsak rena hartssyrorna en mycket hogre smaltpunkt an det disproportionerade materialet. When the procedure is applied to a disproportionate resin, e.g. a resin Sou], treated according to the patent cited above, the obtained substantially pure resin acids have a much higher melting point than the disproportionated material.

Vid behandling av nh.got av de ovannamnda hartserna foredrageS att forst bringa hart- -set i losning i ett organiskt losningsmedel. When treating any of the above resins, it is preferred to first dissolve the resin in an organic solvent.

Ett stort antal olika losningsmedel kunna anvandas for detta andanahl, eftersom harts-cy- klohexylaminsaltet Sr i huvudsak olOsligt i manga olika losningsmedel och darfor latt kan utfallas och avskiljas fran losningen. A large number of different solvents can be used for this solution, since the resin-cyclohexylamine salt Sr is substantially insoluble in many different solvents and can therefore be easily precipitated and separated from the solution.

Lampliga losningsmedel omfatta alifatiska kolvaten, sasom nafta, mineral spirits_ och petroleumeter, ketoner, shsom aceton, och al- koholer, shsom etylalkohol. Vid behandling av oljeharts kan den narvarande terpentinen tjana som en del av det anvanda losningsmedlet. Hartsets koncentration i den ursprungligen framstallda lOsningen kan aven variera Over ett tamligen vidstrackt omrade, I. ex. upp till 40 %. Vanligen befinnes frail. 15 till % astadkomma en losning av tillrackligt Mg 'OSkositet for att mOjliggOra latt separering av harts-cyklohexylaminfallningen. Nar reaktionen utf8res vid forhojda temperaturer kunna nagot hogre koncentrationer anyandas. Suitable solvents include aliphatic hydrocarbons such as naphtha, mineral spirits and petroleum ether, ketones, such as acetone, and alcohols, such as ethyl alcohol. When treating oil resin, the present turpentine can serve as part of the solvent used. The concentration of the resin in the originally prepared solution may also vary over a fairly wide range, e.g. up to 40%. Usually frail are found. Provide a solution of sufficient Mg 'OScosity to allow easy separation of the resin-cyclohexylamine precipitate. When the reaction is carried out at elevated temperatures, slightly higher concentrations may occur.

Temperaturen vid reaktionen mellan cyklohexylaminen och den behandlade losning- en kan variera Over ett tamligen vidstrackt omrhde ehuru rumstemperatur vanligen Sr tillfredsstallande. The temperature of the reaction between the cyclohexylamine and the treated solution can vary over a fairly wide range, although the room temperature is usually satisfactory.

Den an.vanda mangden cyklohexylamin bör naturlighis vara minst sh. stor som erfordras for att neutralisera alla de narvarande hartssyrorna, d. v. s. ett ekvimolekylart forhallande och lampligen anvandes nagot overskott for att tillforsakra reaktion med alla de tillgrangliga hartssyrorna. The amount of cyclohexylamine used should, of course, be at least sh. large which is required to neutralize all the present resin acids, i.e. an equimolecular ratio and apparently some excess was used to ensure reaction with all the available resin acids.

Sedan harts-eyklohexylidfallningen sakerstains och avskilts tvattas den lampligen en eller flera ganger med ytterligare losningsme- del, sa att den befrias fran spar av fororefinger, och fallningen hydrolyseras darefter for att utvinna S ena sidan hartssyrorna och andra sidan cyklohexylaminen. Hydrolys kan utforas enligt vilken. som heist av de kan- da metoderna, I. ex. genom anvandning av klorvatesyra eller svavelsyra. Vid ett typiskt fall d5 klorvatesyra anvandes, anvandes syran vattenlosning och de hydrolyserade hartssy- rorna utskiljas latt eller kunna filtreras, vat.- efter syrorna tvattas med vatten och ge en ren hartssyraprodukt. Cyklalexylaminen kan utvinnas genorn kand teknik Iran klorvatesyralosningen och den lian darefter anvandas .nytt. After the resin-eyklohexylide precipitate is saccharified and separated, it is suitably washed one or more times with additional solvents, so that it is freed from traces of fororefinger, and the precipitate is then hydrolyzed to recover S on the one hand the resin acids and the other cyclohexylamine. Hydrolysis can be performed according to which. as heist of the known methods, I. ex. by using chloroacetic acid or sulfuric acid. In a typical case where hydrochloric acid is used, the acid is used as an aqueous solution and the hydrolysed resin acids are easily separated or can be filtered, water after the acids are washed with water to give a pure resin acid product. Cyclalexylamine can be extracted by the prior art technology Iran chloroacetic acid solution and the lian thereafter used .new.

Naftan eller-annat losningsmedel som ursprungligen anvandes for att framstalla 18sningen av det fox behandling avsedda hartset kvarhhller de ofortvalbara bestandsdelarna losning, sarskilt hartskolvatena, sS att denna losning efter separering, av harts-cyklohexyliclen fran densamma kan behandlas ytterligare, sh att naftan och de ofortvalbara bestandsdelarna utvinnas Enligt en teknik for detta andamal kan losningsmedlet (med de ofortvhlbara bestandsdelarna i lasning dari) tvattas med utspadd vattenhaltig natriumhydroxid for att sakerstalla eliminering av eventuellt narvarande sura bestandsdelar, varefter naftan avdestilleras. Nar denna teknik tillampas ph ett ursprungligt material bestaende vasentligen av en storre andel av hartssyror och en mindre andel av hartskolvaten, ger separeringen av den. ofortvalbara fraktionen fran naftan eller annat anvant los-. ningsmedel relativt rena hartskolvdten. The naphtha or other solvent originally used to prepare the solution of the fox-treated resin retains the non-optional constituents of the solution, especially the resin flasks, so that this solution, after separation, of the resin-cyclohexylicene therefrom, can be further treated, and the naphthane and The constituents are recovered. According to a technique for this purpose, the solvent (with the indistinguishable constituents in loading therein) can be washed with dilute aqueous sodium hydroxide to ensure elimination of any present acidic constituents, after which the naphtha is distilled off. When this technique is applied to an original material consisting essentially of a larger proportion of resin acids and a smaller proportion of the resin carbonates, the separation of it gives. non-digestible fraction from naphtha or other used los-. relatively pure resin flask.

Betraffan.de forfaringssattet enligt uppfinningen tillampat p5 separeringen av hartssyror frhn tallolja skall farst framhallas att en av de primara skillnaderna mellan detta utgangsmaterial (tallolja) och ett vanligt harts Sr, att tallolj an innehaller fettsyror sow en vasentlig bestandsdel. Forfaringssattet enligt uppfinningen Sr emellertid effektivt for att avskilj a hartssyrakomponenten frail tallolj a, oberoende av narvaron av fettsyrakomponenten. Regarding the process according to the invention applied to the separation of resin acids from tall oil, it should first be pointed out that one of the primary differences between this starting material (tall oil) and an ordinary resin is that tall oil contains fatty acids and an essential component. However, the process set according to the invention is effective in separating the resin acid component from tall oil, independently of the presence of the fatty acid component.

Forst bringas talloljan i losning i ett losningsmedel, som kan vara vilket som heist av de oven shsom anvandbara for behandling av harts angivna. Losningens koncentralion kan aven vara likadan som den vid be-handling av harts anvanda, ehuru det kan namnas, att fettsyrabestandsdelarna i talloljan utgora en flytande komponent, sa att nSgot hOgre koncentrationer av talloljan i losningen kunna anvandas utan att resultera i shdan Overdriven Okning i viskositet att separeringen av harts-cyklohexylaminfallningen hindras. First, the tall oil is brought into solution in a solvent, which may be any of the above which are useful for treating resin. The concentration of the solution may also be the same as that used in the treatment of resin, although it may be mentioned that the fatty acid constituents in the tall oil form a liquid component, so that slightly higher concentrations of the tall oil in the solution can be used without resulting in excessive excess viscosity. that the separation of the resin-cyclohexylamine precipitate is prevented.

Liksom vid behandlingen av harts sattes eyklohexylaminen till losningen av tallolja vid rumstemperatur, ehuru om sh. onskas temperaturen kan varieras nagot. As in the treatment of resin, the eyklohexylamine was added to the solution of tall oil at room temperature, although if sh. the desired temperature can be varied somewhat.

Ehuru det joke är avgorande, Sr det vanligen onskvart att filtrera talloljelosningen fore behandlingen med cyklohexylamin av den orsaken att tallolja vanligen innehaller avse-varda mangder fasta fororeningar, sasom smuts, sand och oxisyror. Although this joke is crucial, it is usually unwise to filter the tall oil solution prior to treatment with cyclohexylamine for the reason that tall oil usually contains significant amounts of solid contaminants, such as dirt, sand and oxyacids.

Vid behandling av tallolja Sr den mangd cyklohexylamin, som sattes till losningen, foretradesvis tillracklig for att reagera ej en- — —3 dast med alla de narvarande hartssyrorna utan aven med alla de narvarande fettsyrorna. Nagot litet overskott utover denna mangd ar Onskvart for att tillforsakra fullstandig reaktion. In the treatment of tall oil, the amount of cyclohexylamine added to the solution is preferably sufficient to react not only with all the present resin acids but also with all the present fatty acids. Somewhat small excess beyond this amount is Onskvart to ensure complete reaction.

Efter cyklohexylaminbehandlingen utfaller harts-cyklohexyliden och kan avskilj as, och det bar markas att de narvarande fettsyrorna aro sadana, att deras cyklohexylaminsalter aro antingen flytande eller ha tillracldig loslighet I nafta eller annat anvant losningsmedel for att forbliva i lasning. De fororena sâlunda icke harts-cyklohexylidfallningen Efter avskiljningen är det Onskvart att tvatta och filtrera harts-cyklohexylidfallningen, liksom fallningen som erhallits Iran hartsbehandlingen. Darefter Iran hydrolys anvandas far att utvinna de rena hartssyrorna och cyklohexylaminen. After the cyclohexylamine treatment, the resin cyclohexylide precipitates and can be separated, and it should be noted that the fatty acids present are such that their cyclohexylamine salts are either liquid or have sufficient solubility in naphtha or other used solvent to remain in loading. The contaminants thus do not contaminate the resin cyclohexylide precipitate After separation, it is advisable to wash and filter the resin cyclohexylide precipitate, as well as the precipitate obtained from the Iran resin treatment. Then Iran hydrolysis is used to extract the pure resin acids and cyclohexylamine.

Den efter hartsbestandsdelarnas avskiljning aterstaende losningen eller filtratet junehailer fettsyraeyklohexylaminsalterna liksom de ofartvalbara bestandsdelarna av talloljan. Detta filtrat eller denna losning kan darefter behandlas for att separera dess olika bestandsdelar, on ett faredraget forfaringssatt far denna behandling är att hydrolysera filtratet, t. ex. med vattenhaltig klorvatesyra. Denna hydrolys resulterar i separering av filtratet i tva skikt, ett vatten,skikt innehallande eyklohexylaminen och det andra skiktet av nafta eller annat losningsmedel innehallande de ofortvalbara bestandsdelarna och fettsyran. Naftaskiktet behandlas darefter med ett fortvalningsmedel. Natriumhydroxid är effektiv for detta andamal, och den resulterande fettsyratvalen kan latt separeras Iran naftalosningen, och tvalen tvattas och hydrolyseras darefter far aft giva de i huvudsak rena fettsyrorna. The solution or filtrate remaining after the separation of the resin constituents junehailer the fatty acid cyclohexylamine salts as well as the non-digestible constituents of the tall oil. This filtrate or solution can then be treated to separate its various constituents, a dangerous method of this treatment is to hydrolyze the filtrate, e.g. with aqueous hydrochloric acid. This hydrolysis results in the separation of the filtrate into two layers, one water, layer containing the cyclohexylamine and the other layer of naphtha or other solvent containing the non-digestible constituents and the fatty acid. The naphtha layer is then treated with a preservative. Sodium hydroxide is effective for this purpose, and the resulting choice of fatty acid can be easily separated from the naphthalene solution, and the solution is washed and hydrolysed to give off the substantially pure fatty acids.

Naftallisningen kan efter separering av fettsyrorna avdrivas for att kvarlamna de °fortvalbara materialen, sasom steroler och hartskolvaten. \rid behandlingen av tallolj or soder uppfinningen salunda ej endast for isoleringen av i huvudsak rena hartssyror darur utan aven av I huvudsak rena fettsyror, vilka bestandsdelar aro kommersiellt vardefulla material. After separation of the fatty acids, the naphthalization can be evaporated to leave the perishable materials, such as sterols and the resin flasks. Thus, in the treatment of tall oil or soda, the invention is present not only for the isolation of substantially pure resin acids therefrom but also of substantially pure fatty acids, the constituents of which are commercially valuable materials.

Det avses aven att moderluten, d. v. s. losningen efter utfallning och ayskiljning ay hartscyklohexyliden kan endast befrias fran losningsmedel och anvandas som sadan, utan hydrolys av cyklohexylaminsalterna av fettsyrorna, och utan ytterligare separeringssteg. Detta material kan exempelvis anyandas som rostskyddsmedel och det kan aven anvandas direkt i farger och andra kompositioner. It is also contemplated that the mother liquor, i.e. the solution after precipitation and separation of the resin cyclohexylide, can only be freed from the solvent and used as such, without hydrolysis of the cyclohexylamine salts of the fatty acids, and without further separation steps. This material can, for example, be used as an anti-corrosion agent and it can also be used directly in paints and other compositions.

De nedan lamnade exemplen aro uppdelade i tyá grupper namligen: Grupp A — Exempel pa behandling av olika hartser. The examples given below are divided into ten groups, namely: Group A - Examples of treatment of different resins.

Grupp B — Exempel pa behandling av tallol j a. Group B - Example of treatment of tall oil j a.

Grupp A — Hartser. Group A - Resins.

I denna grupp lamnas exempel pa behandling av vanligt kommersiellt harts liksom olika disproportionerade hartser och av rá gummihartsolja. Det lamnas forst en grupp av exempel ph behandlingar tillampade pa disproportionerade hartser. This group includes examples of the treatment of ordinary commercial resin as well as various disproportionate resins and of crude rubber resin oil. First, a group of examples of ph treatments applied to disproportionate resins is left.

Exempel 1. Example 1.

` Vid detta exempel anvandes ett disproportionerat harts, som framstallts enligt det amerikanska patentet 2 395 273, som utgangsmaterial, vilket material hade ett syratal av 148. Disproportionerat harts frarnstalldes genom att underkasta WW traharts varmehe-- handling vid 225° C under fern timmar, medan SON-gas bubblades igenom det med en hastighet av 2 % per timme raknat ph hart: sets vikt. Det disproportionerade materialet hade ett syratal av 148 och ett jodtal av 62,7.- 100 g av detta disproportionerade harts lostes i 400 g nafta och under omroring av losningen yid rumstemperatur tillsattes 27,2 .g cyklohexylamin, vilken mangd representerade ett molarforhallande av cyklohexylamin fill mangden hartssyror narvarande i det disproportionerade mat erialet av 1: 1. En fanning bildades hastigt och efter att ha stall Over natten avfiltrerades fallningen och tvattades flera ganger med nafta. Fallningen torkades darefter och gay 101,8 g hartscyklohexylid. In this example, a disproportionate resin prepared according to U.S. Patent 2,395,273 was used as the starting material, which material had an acid number of 148. Disproportionate resin was prepared by subjecting the heat treatment of WW trahart at 225 ° C for four hours. while SON gas was bubbled through it at a rate of 2% per hour shaved ph hart: set weight. The disproportionate material had an acid number of 148 and an iodine value of 62.7.-100 g of this disproportionate resin was dissolved in 400 g of naphtha and while stirring the solution at room temperature 27.2 g of cyclohexylamine were added, which amount represented a molar ratio of cyclohexylamine fill the amount of resin acids present in the disproportionate food range of 1: 1. A fanning formed rapidly and after standing overnight, the precipitate was filtered off and washed several times with naphtha. The precipitate was then dried and gay 101.8 g of resin cyclohexylide.

De i cyklohexyliden narvarande hartssyrorna representerade 79,8 % av det totala SONhartsmaterialet som tagits under behandling. Detta representerade 00,8 % av de i utgangsmaterialet narvarande hartssyrorna. Det inses salunda att utbytet Or kvantitativt for praktiska andamal. The resin acids present in the cyclohexylide represented 79.8% of the total SON resin material taken during treatment. This represented 00.8% of the resin acids present in the starting material. It will thus be appreciated that the exchange is quantitative for practical purposes.

Hartscyklohexyliden hydrolyseras darefter genom att blandas med 400 cm' av ett lagkokande alifatiskt kolvatelosningsmedel, 200 cm' vatten och 100 cm° koncentrerad HC1. Denna blandning omrOrdes tills tvâ klara skikt bildades och lick darefter sta. Losningsmedels- och vattenskikten separerades och losningsmedelsskikten tvattades med vatten tills all mineralsyra avlagsnats. Losningsmedlet avlagsnades sedan under vakuum, och kvarlamnade 71,9 gay ett fast harts med ett syratal ay 177,3 och ett jodtal av 51,5. The resin cyclohexylide is then hydrolyzed by mixing with 400 cm 3 of a low boiling aliphatic hydrocarbon solvent, 200 cm 3 of water and 100 cm 3 of concentrated HCl. This mixture was stirred until two clear layers formed and then stood. The solvent and water layers were separated and the solvent layers were washed with water until all the mineral acid had been deposited. The solvent was then removed in vacuo to leave 71.9 g of a solid resin with an acid number of 177.3 and an iodine value of 51.5.

Exempel 2. Example 2.

Denna behandling utfardes aven pa disproportionerat harts. Den utforda behandlingen var densamma som beskrivits ovan for exempel 1, bade med avseende pa den ursprungliga SOrdisproportioneringsbehandlingen och med ayseende pa bildningen ay hartscyklohexylid, hydrolys etc. Utgangsmaterialet var emellertid i detta fall gummiharts i stallet for traharts sasom i exempel 1 och hade ett syratal av 150 och ett jodtal av 94. 12637g — Vid detta exempel var utbytet av hartssyror 75,5 % ph basis av det totala material som tagits under behandling, och 93,2 % pa basis av de narvarande hartssyrorna. Syratalet for de genom hydrolysen utvunna hartssyrorna var 170,3 och fodtalet var 84,6. This treatment was also performed on disproportionate resin. The challenge treatment was the same as described above for Example 1, both with respect to the original SOd disproportionation treatment and with respect to the formation of resin cyclohexylide, hydrolysis, etc. However, the starting material in this case was rubber resin instead of resin as in Example 1 and had an acid 150 and an iodine value of 94. 12637g - In this example, the yield of resin acids was 75.5% ph on the basis of the total material taken during treatment, and 93.2% on the basis of the present resin acids. The acid number of the resin acids obtained by the hydrolysis was 170.3 and the foot number was 84.6.

Exempel 3. Example 3.

En behandling liknande den ovan beskrivna utfordes pa gummiharts, som forut underkastats disproportionering genom anvandning av svavel. Vid disproportioneringsbehandlingen enligt fOreliggande exempel upphettades WW gammiharts under tva och en halv timmar vid en temperatur av 200° C, i narvaro av 10 % svavel. Det disproportionerade materialet hade ett syratal av 152 och ett jodtat av 74,6. 200 g av det•disproportionerade naaterialet blandades med ett lagkokande alifatiskt kolVatelOsningsmedel och med 53,6 g cyklohexylamin, d. v. s. den mangd., som erfordrades, for att reagera med alla i det disproportionerade materialet narvarande hartssyrorna. HartscykIohexylidfallningen som bildades avfilfrerade, och hartssyrorna i cyklohexyliden omfattade 87,s % av de i fiat totala behandling underkastade materialet narvarande hartssyrorna. Hartssyrorna utvunnos ur cyklohexyliden genom hydrolys med 10 % vattenhaltig och efterfoljande forangning av Itisningsmedlet, och dessa hartssyror hade ett syratal av 167,2 och ett jodtal av 35,2. A treatment similar to that described above is challenged on rubber resin which has previously been subjected to disproportionation by the use of sulfur. In the disproportionation treatment according to the present example, WW gamma resin was heated for two and a half hours at a temperature of 200 ° C, in the presence of 10% sulfur. The disproportionate material had an acid number of 152 and an iodine content of 74.6. 200 g of the disproportionate feedstock were mixed with a low boiling point aliphatic hydrocarbon solvent and with 53.6 g of cyclohexylamine, i.e. the amount required to react with any of the resin acids present in the disproportionate material. The resin cyclohexylide precipitate that formed was filtered off, and the resin acids in the cyclohexylide comprised 87% of the material subjected to the present resin in total treatment. The resin acids were recovered from the cyclohexylidene by hydrolysis with 10% aqueous and subsequent evaporation of the detergent, and these resin acids had an acid number of 167.2 and an iodine value of 35.2.

Exempel 4. Example 4.

Vid detta exempel separerades i huvudsak rena hartssyror fran kornmersiellt WW Ira-harts med ett syratal av 165 och ett jodtal av 134. 200 g traharts bringades 1 losning i 800, cm nafta och 61,o g cyklohexylamin tillsattes, vilken mdngd var den som teoretiskt erfordrades f6r att reagera med alla de narvarande hartssyrorna. CykIohexyliden avfiltrerades och gay 218 g av saltet. Den erhallna cyklohexyliden inneholl en hartssyramangd lika med 87,2 % av det totala materialet som tagits. under behandling, vilket motsvarade 98 % av de i -utgangsmaterialet narvarande hartssyrorna. In this example, substantially pure resin acids were separated from granular WW Ira resin having an acid number of 165 and an iodine value of 134. 200 g of resin were brought in solution in 800 cm 3 of naphtha and 61, and cyclohexylamine was added, which amount was theoretically required to react with all the present resin acids. The cyclohexylide was filtered off and gay 218 g of the salt. The cyclohexylide obtained contained a resin acid amount equal to 87.2% of the total material taken. during treatment, which corresponded to 98% of the resin acids present in the starting material.

Hartscyklohexyliden hydrolyserades ph det ovan beskrivn:a allmanna sattet med 33 % vattenhaltig HC1-18sning och kristalliserades ur alkohol, samt gay' en hartsprodukt med ett syratal av 184,s och ett jodtal av 108,s. The resin cyclohexylide was hydrolyzed according to the general procedure described above with 33% aqueous HCl solution and crystallized from alcohol, as well as a resin product having an acid number of 184, s and an iodine value of 108, s.

Exempel 5. delta exempel utfordes cyklohexylaminbehandlingen pa WW gummihartsolja. For behandlingsandamal sattes 3993 cm' terpentin till en sats av 1331 g av hartsoljan och dayefter irordes den teoretiska mangden (362 g) cyklohexylamin, d. v. s. den mangd som erfordrades for att reagera med alla de narva rande hartssyrorna under antagande att den ursprungliga. hartsollan bestod av 80. % fasta bestands.delar. Derma behandling utfordes vid rumstemperatur shsom i de andra exemplen ovan och gay hastigt en hartscyklohexylidffillning, vilken tVattades med petroleumeter och vilken (tanner bydrolyserades genom alt blanda raaterialet "nett petroleumeter och 50 % HCE-vattenlbsning. Efter skiktbildning sepa, rerades vatten- oeh lOsningsmedelsskikfen och. losningsrnedlet forangades fra'n hartssyrorna vilket gay en produkt aired ett syratal av 177,5 och ett j.odtali av 122;3.. D'enna hartssyraprodukt representerade- 45,7 % av den behand- underkastade ursprungliga hartsoljan. Example 5. In this example, the cyclohexylamine treatment of WW rubber resin oil is challenged. For treatment purposes, 3993 cm 3 of turpentine were added to a batch of 1331 g of the resin oil, and then the theoretical amount (362 g) of cyclohexylamine, i.e. the amount required to react with all the irritating resin acids, was assumed to be the original. the resin sol consisted of 80% solids. This treatment is challenged at room temperature as in the other examples above and a resin is rapidly precipitated with a resin cyclohexylide filling, which was washed with petroleum ether and which (tanner was co-hydrolyzed by mixing the raw material "net petroleum ether and 50% HCE aqueous solution".). The solvent was evaporated from the resin acids, which product yielded an acid number of 177.5 and an iodine value of 122.3. This resin acid product represented 45.7% of the treated original resin oil.

Exempel 6. Example 6.

Delta exempel utf5rdes ph samma allinanna salt som beskrivits ovan i. exempel 5 med undantag av att 3510 cilia petroleumeter satfes till en sats ay 1170 ghartsoljan ffire behand- lingen med cyklohexylaminen. Den tillsatta anangden: cyklohexylamin var 306 g. Den fardiga hartssyraprodukten hade ett syratal av 180;2 och ett iodtal av 147,3 och utdorde 55,7 % av den ursprungligen under behandling tagna hartsoljan. These examples were carried out on the same all-salt as described above in Example 5, except that 3510 cilia of petroleum ether were added to a batch of 1170 g of the resin oil before the treatment with the cyclohexylamine. The added amount: cyclohexylamine was 306 g. The finished resin acid product had an acid number of 180; 2 and an iodine value of 147.3 and accounted for 55.7% of the resin oil originally taken under treatment.

Grupp B — Exempel 7. Group B - Example 7.

Vid detta exempel tillampades eyklohexylaminseparerin,gen enligt up.pfinningen: pd en raffinerad tallolja. S.Alundra,. tastes 200 g av talloljan i 400 g av elf lagkokarnle kolvatelosningsmedel och g av cyklohexylaminen tillsattear d. v. s, en tillracklig mangd for att reagera: med alma de narvarande syrabestandsdelarna ( bade hartssyrorna och fettsyrorna), Bekaa:111qm utfordes vid rumstemperatur och hartseykl'ohexylidfallningen bildades hastigt och avfiltrerades. Faliningen tvattades med 10 % cyklohexylaminlosning i en ytterligare mangd av samma liasningsmeder och slutligen med ytterligare satser av sj alva losningsmecl, let tills filfratet var klart„ och alit flItratet threnades med moderluten. Den erhallna hartscyklohexyliden tnneholi hartssyror lika med 44,2 % av del totala tallottematerialet som ursprungligen tagfts under behandling, vilket molsvarade den mangd hartssyror som vanligen är narvarande i tallolja. In this example, the cyclohexylamine separation gene of the invention was applied to a refined tall oil. S.Alundra ,. taste 200 g of tall oil in 400 g of eleven cochlear carbonate solvents and g of the cyclohexylamine added i.e., a sufficient amount to react: with all the present acid constituents (both the resin acids and the fatty acids), Bekaa: 111qm is challenged at room temperature and resin xylid quickly and filtered off. The falinate was washed with 10% cyclohexylamine solution in an additional amount of the same leaching agents and finally with additional batches of the actual solution medium, until the filtrate was clear and the filtrate was drained with the mother liquor. The resulting resin cyclohexylidene tnneholi resin acids equal 44.2% of the total tallot material originally taken during treatment, which was equivalent to the amount of resin acids usually present in tall oil.

Cyklohexyliden hydrolyserades med 33 % HCI-losning enligt den ovan beskrivna tekniken och gay en hartssyraprodukt med ett. syratal av 185,3 .oe,h ett jodtal av 120,8. The cyclohexylide was hydrolyzed with 33% HCl solution according to the technique described above to give a resin acid product with one. acid number of 185.3 .oe, h an iodine value of 120.8.

Modervatskart tillsammans med do damned forenade filtraten behandlades darefter for utvilining av andra bestandsdelar. SAlunda neutraliserades derma losning med % HC1- vattenlosning for att bringa pH-vardet till 6,5. Efter skiktbildning avsogs syravattenskiktet oak losningsmedelsskiktet tvattades med vat- — — ten tills det var fritt Iran mineralsyra (pH 7). LOsningen torkades darefter Over Na,S00 och underkastades destillation yid 100° C med tillrackligt yakuum for att aydriva losningsmedlet hastigt (60-80 mm Hg). Destillationsaterstoden bestod av en ambrafargad viskos olja innehallande fettsyran och kolyatena, vars mangd var 46,4 % ay den totala talloljan som ursprungligen underkastats behandling. Fettsyra- och kolvatebestandsdelarna i detta material kunna separeras pa kanda sat. Motherwater maps together with do damned united filtrates were then treated for elimination of other constituents. Thus, this solution was neutralized with% HCl aqueous solution to bring the pH to 6.5. After layer formation, the acid water layer was filtered off and the solvent layer was washed with water until it was free of Iran mineral acid (pH 7). The solution was then dried over Na, S00 and subjected to distillation at 100 ° C with sufficient vacuum to drive the solvent rapidly (60-80 mm Hg). The distillation residue consisted of an amber viscous oil containing the fatty acid and the coliates, the amount of which was 46.4% ay of the total tall oil originally subjected to treatment. The fatty acid and hydrocarbon constituents of this material can be separated in a known manner.

Exempel 8. Example 8.

Detta exempel visar tillampningen ay tekniken enligt foreliggande uppfinning fOr att skilja hartssyror fran blandade material ayen nar endast mycket sma mangder hartssyror ursprungligen aro narvarande. tallolja upphettades forst under flera timinar till en temperatur ay 300° C, i naryaro ay 1 % fosforsyra, vilket resulterade 1 omfattande dekarboxylering ay de naryarande hartssyrorna. Detta dekarboxylerade material destillerades darefter och gay ett destillat med ett syratal ay 118,6. 250 g ay destillatet lostes i en lika stor yikt ay ett lagkokande alifatiskt kolvatelosningsmedel och 66 g cyklohexylamin irordes vid rumstemperatur, vilken mangd var tillracklig for att reagera med de narvarande syrabestandsdelarna. Detta resulterade i bildning av en ringa mangd failning, vilken ayfiltrerades och tvattades med 1 % losning ay cyklohexylamin i samma 15sningsmedel. Fallningen tvatfades ytterligare med ytterligare mangder av samma Iiisningsmedel enbart tills filtratet var klart. Den totala mangden cyklohexylid var da 444 g. This example demonstrates the application of the technique of the present invention to distinguish resin acids from mixed materials when only very small amounts of resin acids are originally present. Tall oil was first heated for several hours to a temperature of 300 ° C, in naryaro ay 1% phosphoric acid, resulting in extensive decarboxylation ay of the naryaro resin acids. This decarboxylated material was then distilled and a distillate having an acid number of 118.6. 250 g of the distillate were dissolved in an equal amount of a low-boiling aliphatic hydrocarbon solvent and 66 g of cyclohexylamine were stirred at room temperature, which amount was sufficient to react with the present acid constituents. This resulted in the formation of a small amount of failure, which was filtered off and washed with 1% solution of cyclohexylamine in the same solvent. The precipitate was further washed with additional amounts of the same solvent only until the filtrate was clear. The total amount of cyclohexylide was then 444 g.

Hartscyklohexyliden hydrolyserades darefter ur etylalkohol genom anyandning av koncentrerad HCI. Den olosliga cyklohexyliden spjalkades och hartssyrorna lostes hastigt i etylalkoholen. Syrorna i ran form utfallde.s darefter genom tillsats ay yatten tills alkoholen och syrorna yisade sig vara vita och kristalliniska on hade ett syratal ay 187,5 och en smaltpunkt ay 158-162° C. The resin cyclohexylide was then hydrolyzed from ethyl alcohol by inhalation of concentrated HCl. The insoluble cyclohexylide was cleaved and the resin acids were rapidly dissolved in the ethyl alcohol. The acids in the crude form were then precipitated by addition to the water until the alcohol and acids turned white and crystalline and had an acid number of 187.5 and a melting point of 158-162 ° C.

Moderluten eller -losningen med de clamed forenade filtraten surgjordes med 10 c,'"0 HC1- vattenlosning och efter skiktbildning separerades losningsmedels- och vattenskikten. Losningsmedelsskiktet tvattades darefter med Nat-ten tills det var fritt fran mineralsyra och losningsmedlet forangades darefter under vakuum kvarlamnades en ambrafargad viskos olja utgorande ungefar 89 % ay det totala talloljedestillat som underkastats behandling. The mother liquor or solution with the clamed combined filtrates was acidified with 10 c, 20 HCl aqueous solution and after layering the solvent and water layers were separated. The solvent layer was then washed with Nat until free of mineral acid and the solvent was then evaporated in vacuo. amber viscose oil constitutes approximately 89% of the total tall oil distillate subjected to treatment.

Den viskosa oljeaterstoden behandlades (lard ter med Oyerskott ay metylalkohol i naryaro ay H2S0, for att fOrestra fettsyrakomponenten. Denna blandning upphettades under aterflOde till 7° C och efter langyarig kylning Mldades tya skikt. Det undre skiktet (alkohol olosligt) inneh011 det rnesta ay kolyatena och metylestern. Det 5vre alkoholskiktet inneholl icke forestrade syror och kolvate. Dessa tVâ skikt separerades och det alkohollosliga materialet tvattades med utspadd alkali for att eliminera spar av fri fettsyra och darefter torkades yatskan Over Na2S0,. Detta material kan latt behandlas vidare f Or att separera kolvateoch fettsyraesterbestandsdelarna enligt kand teknik. Alkohollosningen anyandes daref ter f8r efterfoljande forestringssatser. The viscous oily residue was treated (lard ter with Oyerskott ay methyl alcohol in naryaro ay H2SO, to esterify the fatty acid component. This mixture was heated under reflux to 7 ° C and after long-term cooling Melted tha layers. The lower layer (alcohol is insoluble) contained The upper alcohol layer contained non-esterified acids and carbonates. These two layers were separated and the alcohol-soluble material was washed with dilute alkali to eliminate traces of free fatty acid and then dried over Na 2 SO 4. This material can be further treated to separate. the carbohydrate and fatty acid ester constituents according to the prior art.The alcohol solution is then applied to subsequent esterification batches.

Exempel 9. Example 9.

Ra tallolja lostes i nafta och behandlades med cyklohexylamin yid rumstemperatur, varvid mangden cyklohexylamin aterigen var tillracklig for att reagera med alla syrabestandsdelarna i talloljan. Hartssyrorna i den erhallna hartscyklohexylidfallningen utgjorde 44,5 % av den totala under behandling Lagna talloljan, vilket motsvarade den i tallolja nor-malt naryarande mangden hartssyror. Efter hydrolys och utyinning av hartssyrorna befunnos de ha ett syratal ay 182,2. Crude tall oil was dissolved in naphtha and treated with cyclohexylamine at room temperature, the amount of cyclohexylamine again being sufficient to react with all the acid constituents in the tall oil. The resin acids in the obtained resin cyclohexylide precipitate accounted for 44.5% of the total pine oil processed during treatment, which corresponded to the amount of resin acids normally present in tall oil. After hydrolysis and elution of the resin acids, they were found to have an acid number of 182.2.

Exempel 10. Example 10.

Della exempel utfordes pa liknande satt som ovanstaende exempel 9. Behandlingen utfordes pa raffinerad tallolja, men den liar anvanda mangden cyklohexylamin var tillracklig Mr att reagera med de narvarande hartssyrorna. Detta sakerstallde ayen hastigt hartscyklohexylidfallningen. De i cylklohexyliden naryarande hartssyrorna utgjorde 43,% av den behandling underkastade talloljan, vilket motsyarade ungefar den mangd hartssyror som normalt är narvarande i tallolja. Cyklohexyliden hydrolyserades och gay en hartssyraprodukt med ett syratal av 185,3. Some examples are challenged in a manner similar to Example 9 above. The treatment is challenged on refined tall oil, but the amount of cyclohexylamine used was sufficient to react with the present resin acids. This rapidly stopped the resin cyclohexylide precipitation. The resin acids present in the cyclohexylidene accounted for 43% of the treatment subjected to tall oil, which counteracted approximately the amount of resin acids normally present in tall oil. The cyclohexylide was hydrolyzed and a resin acid product having an acid number of 185.3.

Exempel 11. 300 g tallolja lostes 1 1500 cm' nafta och 100 g cyklohexylamin tillsattes vid rumstemperatur under omroring. Aterigen bildades cyklohexyliden och utfalldes och efter att ha fatt sta Over natten avfiltrerades fallningen. De i cyklohexyliden n.aryarande hartssyrorna representerade 39 % av den totala under be-handling tagna talloljan. Example 11. 300 g of tall oil were dissolved in 1500 cm 3 of naphtha and 100 g of cyclohexylamine were added at room temperature with stirring. Again the cyclohexylidene formed and precipitated and after standing overnight the precipitate was filtered off. The resin acids present in the cyclohexylidene naryar represented 39% of the total tall oil taken under treatment.

Forutom den ovanstaende separeringen av hartssyrorna visar foreliggande exempel ayen en nagot annan teknik far separering av de bestandsdelar som atersta i moderluten efter ayskiljning av hartssyrorna. In addition to the above separation of the resin acids, the present example shows a somewhat different technique for separating the constituents which remain in the mother liquor after separation of the resin acids.

Salunda behandlades moderluten med SO2gas, vilken gas bubblades genom losningen under flera timmar. Detta resulterade i spjalkning ay fettsyracyklohexylaminsaltet, och cyklohexylarninen avskilj des som cyklohexylaminsulfat som utfalldes ur losningen och avfiltrerades. Thus, the mother liquor was treated with SO 2 gas, which gas was bubbled through the solution for several hours. This resulted in cleavage of the fatty acid cyclohexylamine salt, and the cyclohexylamine was separated as cyclohexylamine sulfate which precipitated from solution and was filtered off.

Efter tyattning for att eliminera eyentuella spar av SO2 avdunstades naftan fran moder- 6— — luten under vakuum vid 100° C, vilket gay en ambrafargad olja motsvarande ungefdr 59 % av det totala ramaterial som underkastats be-handling. Denna aterstod upplostes pa nytt i en lika volym nafta och behandlades med en 2 % 1-12S0,-vattenlosning vid en temperatur av 0-5° C. ILSOi-losningen tillsattes droppvis under omriiring. En. ringa mangd svart gum- miEfter a-vsattning avhalldes nafta- losningen och tvattades med vatten tills den var neutral. Losningsmedlet avdunstades darefter och dterstoden destillerades sedan under vakuum. Fordropparna upptogos vid en temperatur av 184° C och bestodo huvudsakligen av kolvaten. Huvuddelen av destillatet gick over vid en angtemperatur mellan 184 och 220° C. (77,8 % av heIa mangden) och utgjorde en gul olja med ett syratal av 192,5 och ett jodtal av 125,5. Detta bestod huvudsakligen av fettsyror, och denna fraktion inneholl endast 0,s % ofortvalbart material. After drying to eliminate any traces of SO2, the naphtha was evaporated from the mother liquor under vacuum at 100 ° C, which gave an amber-colored oil corresponding to about 59% of the total raw material subjected to treatment. This residue was redissolved in an equal volume of naphtha and treated with a 2% 1-12 SO 4 aqueous solution at a temperature of 0-5 ° C. The ILSO 4 solution was added dropwise with stirring. One. small amount of black rubber After de-irrigation, the naphtha solution was discarded and washed with water until neutral. The solvent was then evaporated and the residue was then distilled under vacuum. The pre-droplets were taken up at a temperature of 184 ° C and consisted mainly of the hydrocarbons. The majority of the distillate passed over at an angular temperature between 184 DEG and 220 DEG C. (77.8% of the total amount) and was a yellow oil having an acid number of 192.5 and an iodine value of 125.5. This consisted mainly of fatty acids, and this fraction contained only 0.5% of non-digestible material.

Claims

Patent claim:

Salt to separate resin acids from resin or tall oil, characterized in that the material is treated in liquid phase with cyldohexylamine, and that separation of the resulting resin acid cyclohexylamine salt is carried out at a temperature at which delta salt is solid. -

Salt according to claim 1, characterized in that the material is brought into solution in an organic solvent, in which resin acids are soluble but in which cyclohexamine salts of resin acids are substantially insoluble. 2. A kit according to claim 1 or 2, characterized in that the temperature at which the cyclohexylamine salt is separated is close to room temperature.

Salt according to claim 1, 2 or 3, characterized in that the treated material is resin.

4. A set according to claim 1, 2 or 3, characterized in that the treated material is disproportionate resin.

5. Salt according to any one of the preceding claims, characterized in that the treated material is tall oil resin.

Set according to claim 1 or 2, characterized in that the treated malaria is tall oil.

7. A claim according to any one of the preceding claims, characterized in that the separated cyclohexylamine salt is hydrolyzed to give substantially pure boric acids.

A salt according to claim 1 for separating resin acids and fatty acids from tall oil, characterized in that the tall oil is treated in solution in a solvent with the cyclohexylamine in an amount sufficient to react with substantially all of the present resin acids and fatty acids. Salt according to any one of the preceding claims, characterized in that the material is dissolved in acetone. Stockholm 194

9. Kungl. Boktr. P. A. l, .7orstedt & Winer 490089