SE190652C1 - - Google Patents
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- SE190652C1 SE190652C1 SE190652DA SE190652C1 SE 190652 C1 SE190652 C1 SE 190652C1 SE 190652D A SE190652D A SE 190652DA SE 190652 C1 SE190652 C1 SE 190652C1
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Uppfinnare: J D von Mikusch-Buchberg, K H Mebes och M R Mills Prioritet begard Iran den 30 november 195 och den 7 oktober 19 (Storbritannien) Fiireliggande uppfinning hard& sig till nya kondensationsprodukter och sarskilt sadana, som uppsta vid behandling av fettsyror pa sadant salt, att de erhallna produkterna bli anvandbara i tekniska kompositioner. Nar utgangsmaterialen aro omattade, bli de erhallna produkterna sarskilt lampliga sasom torkande medel i malningsfarger, lacker, karnoljor, linoleum och liknande produkter helt eller delvis sasom ersattning for torkande oljor. Om utgangsmaterialen aro mattade, bli de resulterande produkterna exempelvis anvandbara sasom hardoljor eller mjukningsmedel och liknande. Inventors: JD von Mikusch-Buchberg, KH Mebes and MR Mills Priority asked Iran on 30 November 195 and 7 October 19 (Great Britain) The present invention relates to new condensation products and in particular those arising from the treatment of fatty acids on such salt, that the products obtained will be usable in technical compositions. When the starting materials are unsaturated, the products obtained become particularly suitable as drying agents in paints, varnishes, essential oils, linoleum and similar products in whole or in part as a substitute for drying oils. If the starting materials are matte, the resulting products become useful, for example, as hard oils or plasticizers and the like.
Enligt ett tidigare ferslag upphettas hydroxylerade olj or eller fettsyror eller omattade fettoljor eller fettsyror, vilka forst omvandlats till hydroxylerade fettolj or elder fettsyror genom en oxidationsbehandling, i narvaro av nagra fa procent borsyra under vakuum till en temperatur median 260 och 300° C. De sa.- lunda erhallna produkterna utgoras huvudsakligen av estrar. According to a previous report, hydroxylated oils or fatty acids or unsaturated fatty oils or fatty acids, which were first converted to hydroxylated fatty oils or older fatty acids by an oxidation treatment, are heated in the presence of a few percent boric acid under vacuum to a temperature of 260 and 300 ° C. .- The products thus obtained consist mainly of esters.
Enligt ett annat tidigare forslag upphettas fettoljor 1 blandning med en mindre mangd fettsyror under liknande betingelser for att astadkomma en interforestring och for att genom destination avlagsna de kortkedjiga fettsyror, som inga 1 oljan. De salunda erhallna produkterna utgora glyeerider. According to another previous proposal, fatty oils are heated in a mixture with a small amount of fatty acids under similar conditions in order to effect an interesterification and to remove the short-chain fatty acids which are not present in the oil by destination. The products thus obtained constitute glycerides.
Pet liar nu visat sig, att man ken erhalla nya kondensationsprodukter, om man upphettar icke hydroxylerade fettsyror eller blandningar, som innehalla en vasentlig mangd icke hydroxylerade fettsyror, i narvaro av en ringa mangd av en katalysator till en temperatur medlar' 220-330° C under samtidig avskiljning av bildat reaktionsvatten, Dupl. kl. 12 o: 11; 22 g: 3 tills produkten innehaller en vasentlig mangd ofortvalbart material, som har en medelmolekylvikt enligt den beraknade molekylvikten f8r en kondensationsprodukt av minst tre mol fettsyra. For praktiska andamal är det mest lampliga att anvanda en temperatur mellan 250 och 300° C. It has now been found that new condensation products can be obtained by heating non-hydroxylated fatty acids or mixtures containing a substantial amount of non-hydroxylated fatty acids in the presence of a small amount of a catalyst to a temperature of 220-330 ° C. during simultaneous separation of formed reaction water, Dupl. at 12 o: 11; 22 g: 3 until the product contains a substantial amount of non-digestible material having an average molecular weight according to the calculated molecular weight of a condensation product of at least three moles of fatty acid. For practical purposes, it is most appropriate to use a temperature between 250 and 300 ° C.
Den reaktion, som ager rum vid utforande av detta forfarande, utgores huvudsakligen av en kondensation av fria fettsyror. Reaktionsbetingelserna aro sadana, att fettsyrorna i alit vasentligt kvarhallas i eller aterforas till reaktionsblandningen, om man icke onskar avdestillera en fraktion av fettsyror med lagre molekylvikt for att erhalla en mer omattad slutprodukt. Reaktionen utfOres under sa Pang tid, att en vasentlig del av fettsyrorna omvandlas till ofortvalbart material, sasom oven narmare angivits. The reaction which takes place in carrying out this process consists essentially of a condensation of free fatty acids. The reaction conditions are such that the fatty acids in alit are substantially retained in or returned to the reaction mixture, if it is not desired to distill a fraction of lower molecular weight fatty acids to obtain a more unsaturated end product. The reaction is carried out during such Pang time that a substantial part of the fatty acids is converted into non-digestible material, as specified above.
Det liar vidare visat sig, att liknande produkter erhallas, om utgangsmaterialet mile-hailer en vasentlig mangd ur fettsyror erhallna ketoner. Sadana ketoner utgora en mellanprodukt vid kondensationen av fettsyror enligt uppfinningen. It has further been found that similar products are obtained if the starting material mile-hailer a substantial amount of ketones obtained from fatty acids. Such ketones constitute an intermediate in the condensation of fatty acids according to the invention.
De anvanda fettsyrorna kunna vara mattade men aro foretradesvis omattade. The fatty acids used may be saturated but are preferably unsaturated.
Upphettningen kan utforas under atmosfarstryck, varvid en stroll' av inert gas, t. ex. kvavgas, fores genom reaktionsblandningen, men utfores foretradesrvis under vakuum. The heating can be carried out under atmospheric pressure, whereby a stroll of inert gas, e.g. nitrogen gas, is passed through the reaction mixture, but is preferably carried out under vacuum.
Om reaktionen utfores under hOgvakuum, ar det mojligt att reaktionstemperaturen joke omedelbart uppnax omradet 220-330° C, eftersom blandningen under det forsta stadiet av reaktionen kan koka mid en lagre temperatur an 220° C, varvid fettsyror overga till a'ngfasen tilisammans med flyktiga reaktions- 2— — produkter. Alit eftersom reaktionen fortskrider, sankes fettsyrakoncentrationen i blandningen och blandningens kokpunkt okar, sa att temperaturen sa smaningom kan hojas.. If the reaction is carried out under high vacuum, it is possible that the reaction temperature immediately reaches the range 220-330 ° C, since the mixture during the first stage of the reaction can boil at a temperature lower than 220 ° C, with fatty acids transitioning to the vapor phase together with volatile reaction 2— - products. As the reaction proceeds, the fatty acid concentration in the mixture is lowered and the boiling point of the mixture increases, so that the temperature can gradually rise.
Pa grund av den avdunstning av fettsyrorna, som sker under reaktionen, utfores upphettningen lampligen under aterflode av fettsyrorna och de mer hogkokande foreningarna. Pa detta satt kan en storre del av utgangsmaterialet overforas till den slutliga kondensationsprodukten. Due to the evaporation of the fatty acids which takes place during the reaction, the heating is suitably carried out under reflux of the fatty acids and the more boiling compounds. In this way, a larger part of the starting material can be transferred to the final condensation product.
Utgangsrnaterialet kan utgoras av en fettsyra eller en blandning av fettsyror, t. ex. den blandning, som erhalles frail en fettolja eller en blandning av sadana. oljor. Talloljefraktioner, erhallna genom fraktionerad destillalion av tallolja och i huvudsak bestaende av tallfettsyra, är aven anvandbara sasom utgangsmaterial. Man har foreslagit att upphetta tallolja eller tallfettsyra till en temperatur Over 830° C i franvaro av katalysatorer. Produkter, som erhallits pa detta satt, ha lag-re jodtal an utgangsmaterialet, medan de produkter, som erhallas av talloljefraktioner enligt foreliggande forfarande, i motsats hartill ha hogre jodtal an utgangsmaterialet. The starting material may be a fatty acid or a mixture of fatty acids, e.g. the mixture obtained from a fatty oil or a mixture of such. oils. Pine oil fractions, obtained by fractional distillation of tall oil and consisting essentially of pine fatty acid, are also useful as starting materials. It has been proposed to heat tall oil or tall fatty acid to a temperature above 830 ° C in the absence of catalysts. Products obtained in this way have lower iodine numbers than the starting material, while the products obtained from tall oil fractions according to the present process, in contrast, have higher iodine numbers than the starting material.
Utgangsmaterialet kan aven utgoras av en blandning av en eller flera ketoner erhallna ur fettsyror med en eller flera fettsyror. I sadana blandningar kunna ketonerna vara harledda Iran samma eller frail andra fettsyror an de narvarande. The starting material may also be a mixture of one or more ketones obtained from fatty acids with one or more fatty acids. In such mixtures, the ketones may be derived from the same or different fatty acids from the present ones.
De ovan namnda ketonerna kunna framstallas pa varje i och for sig kant salt. The ketones mentioned above can be prepared on each per se edge salt.
Utgangsmaterialet kan slutligen innehalla andra bestandsdelar, t. ex. mono-, di- eller triglyeerider, eller hartssyror. I detta fall bor blandningen innehalla en vasentlig eller lampligen en storre mangd fettsyror och/eller ketoner framstallda ur fettsyror. Sidana andra bestandsdelar ha en benagenhet att sanka hastigheten av den onskade reaktionen, varfor en alltfor hog halt darav i utgangsmaterialet bor undvikas. Aven om de ytterligare bestandsdelarna sjalva ha tillrackliga torkegenskaper eller fa sadana egenskaper under upphettning, bor mangden av desamma icke overstiga den sammanslagna viktmangden fettsyror och ketoner erhallna ur fettsyror. The starting material may finally contain other constituents, e.g. mono-, di- or triglycerides, or resin acids. In this case, the mixture should contain a substantial or appropriate amount of fatty acids and / or ketones prepared from fatty acids. The other constituents have a tendency to slow down the rate of the desired reaction, so that an excessively high content thereof in the starting material should be avoided. Although the additional constituents themselves have sufficient drying properties or few such properties during heating, the amount thereof should not exceed the combined weight of fatty acids and ketones obtained from fatty acids.
Be anvanda fettsyrorna ha lampligen for-mein RC OOH, van i R betecknar en osubsti- tuerad, langkedjig, mattad eller foretradesvis omattad alkylgrupp, vilken exempelvis inne- hailer 9 till 25 och fOretradesvis 17 till 21 kolatomer. PA samma satt dr det mest lampligt att anvanda ketoner med formeln R—C----R', 0 van i R har ovan angivna betydelse och R' liar samma betydelse som R. Da R betecknar en. omattad alkylgrupp, kan denna innehalla en-dust en dubbelbindning, sasom i oljesyra. When used, the fatty acids suitably have the form RC OOH, van in R represents an unsubstituted, long-chain, saturated or preferably unsaturated alkyl group, which for example contains 9 to 25 and preferably 17 to 21 carbon atoms. In the same way, it is most convenient to use ketones of the formula R-C ---- R ', 0 van in R have the meaning given above and R' has the same meaning as R. Since R represents one. unsaturated alkyl group, this may contain at least one double bond, as in oleic acid.
For att erhalla produkter med goda tork egenskaper bor man utfOra reaktionen 1 narvaro av minst en del omattade alkylgrupper med tva eller flera dubbelbindningar. Sasom exempel pa. sadana omattade alkylgrupper ma namnas de, vilka forekomma i linolsyra, linolensyra eller i de hoggradigt omattade syror, som ftirekomma i fiskoljor. In order to obtain products with good drying properties, the reaction should be carried out in the presence of at least some unsaturated alkyl groups with two or more double bonds. As an example of. Such unsaturated alkyl groups may be those which occur in linoleic acid, linolenic acid or in the highly unsaturated acids which occur in fish oils.
De i det foljande angivna procenttalen aro beraknade pa den anvanda viktsmangden av utgangsmaterialet, om ej annat angives. The percentages given below are calculated on the amount by weight of the starting material used, unless otherwise stated.
Den anvanda temperaturen och upphettningstiden samt den mangd ofortvalbart material, som kan erhallas, arc i viss man beroende av den typ ay fettsyror, som anvandes sasom utgangsmaterial. Vid anvfindning av fettsyror med relativt Mgt jodtal kan upphettningen utforas vid hog temperatur under lang tid under samtidig bildning av en stor mangd ofortvalbart material, t. ex. 70 till nara 100 %. Vid anvandning av fettsyror med Mgt jodtal, t. ex. Over 150, kan det a andra sidan vara nodvandigt att avbryta upphettningen vid en tidigare tidpunkt, eftersom gelatinering kan aga rum. Den bildade mangden ofortvalhart material kan i detta fall vara lagre, t. ex. 40-60 %. Av samma orsak ar det i manga fall lampligt att blanda fettsyror av olikartad typ, innan de bringas att reagera, sa att man kan astadkomma en met fullstandig kondensation av hoggra:digt omattade syror i ett steg. andra sidan kan det vid anvandning av fettsyror, vilka innehalla enskilda syror av olika typ, vara lampligt att fraktionera den ursprungliga blandningen, exempelvis genom destillation, eller att avdestillera de mest lattflyktiga och minst omattade syrorna under kondensationsreaktionen (vilket kan ske genom att aterflodeskylaren halles vid en for detta andamal lampligt hog temperatur), varigenom man erhaller en battre torkande produkt. The temperature and heating time used, as well as the amount of non-digestible material that can be obtained, depend to some extent on the type of fatty acids used as the starting material. When using fatty acids with a relatively high iodine value, the heating can be carried out at a high temperature for a long time while simultaneously forming a large amount of non-digestible material, e.g. 70 to almost 100%. When using fatty acids with Mgt iodine content, e.g. Above 150, on the other hand, it may be necessary to interrupt the heating at an earlier time, as gelatinization may take place. The amount of non-selectively hard material formed can in this case be lower, e.g. 40-60%. For the same reason, in many cases it is convenient to mix fatty acids of different types before they are reacted, so that a complete condensation of highly unsaturated acids can be achieved in one step. on the other hand, when using fatty acids which contain individual acids of different types, it may be appropriate to fractionate the original mixture, for example by distillation, or to distill off the most volatile and least unsaturated acids during the condensation reaction (which can be done by refilling the reflux condenser). a temperature extremely suitable for this purpose), whereby a better drying product is obtained.
Den grad, i vilken de fria fettsyrorna omvandlas till ofortvalbart material med de angivna egenskaperna, kan variera mom vida granger alit efter de andamal, for vilka kondensationsprodukterna enligt uppfinningen skola anvandas. For vissa andamal kan en omva:ndlingsgrad av 20-30 % vara tillracklig„ medan i andra fall kan 30-40 % vara lamp-hg. The degree to which the free fatty acids are converted to non-digestible material with the stated properties may vary widely depending on the conditions for which the condensation products of the invention are to be used. For some purposes a conversion rate of 20-30% may be sufficient, while in other cases 30-40% may be lamp-high.
Be sasom utgangsmaterial anvanda fettsyrorna kunna i vissa fall med fordel renas enligt vanliga metoder. As a starting material, use the fatty acids can in some cases be advantageously purified according to usual methods.
Den vid foreliggande forfarande anvanda katalysatorn kan utgoras av bor eller foretradesvis av en syrehaltig borforening. Lampliga oorganiska borforeningar aro borsyra och boroxid. Salter darav, t. ex. alkali- eller lampligen ammoniumpentaborat, kunna aven med fordel anvandas. Borax har emellertid endast ringa katalysatorverkan och borforeningar med oxiderande egenskaper aro icke lampliga. Sa.som organiska borf8reningar fir det mest — —3 lampligt att anvanda estrar av borsyra, t. ex. borsyratrimetylester, borsyratrietylester, borsyramannitolester, blandanhydriden av borsyra och attiksyra eller blandanhydriden av borsyra och hogre fettsyror, vilka exempelvis erhallits av en fettolja, t. ex. jordnotsolja. The catalyst used in the present process may be boron or preferably an oxygen-containing boron compound. Suitable inorganic boron compounds are boric acid and boron oxide. Salts thereof, e.g. alkali or lampium ammonium pentaborate, can also be used to advantage. However, borax has little catalytic activity and boron compounds with oxidizing properties are not suitable. As organic boron compounds, it is most convenient to use esters of boric acid, e.g. boric acid trimethyl ester, boric acid triethyl ester, boric acid mannitol ester, the mixed anhydride of boric acid and attic acid or the mixed anhydride of boric acid and higher fatty acids, which are obtained, for example, from a fatty oil, e.g. peanut oil.
Katalysatorn kan anvandas pa en lamplig barare, sasom kiseldioxid, t. ex. i form av kiselgur, diatomasejord eller silikagel. Om en buren katalysator anvandes, kan katalysatorn losas eller suspenderas i vatten och bararen tillsattes, varefter den resulterande blandningen torkas i en ugn. The catalyst can be used on a suitable carrier, such as silica, e.g. in the form of diatomaceous earth, diatomaceous earth or silica gel. If a supported catalyst is used, the catalyst can be loosened or suspended in water and the barrier added, after which the resulting mixture is dried in an oven.
Den anvanda katalysatormangden kan variera Mom vida granser, exempelvis mellan 0,1 och 10 viktprocent. I allmanhet är det mest lampligt att anvanda en katalysatormangd air nagra Id proeent, t. ex. 2-6 viktproeent. The amount of catalyst used can vary widely, for example between 0.1 and 10% by weight. In general, it is most appropriate to use a catalyst amount of air nagra Id proeent, e.g. 2-6 weight percent.
Forfarandet utfores lampligen i ett reaktionskarl av rostfritt stal, forsett med en aterflodeskylare. Deana kan antingen upphettas eller kylas, sa att fettsyror och andra hogkokande produkter bringas att aterfloda, medan reaktionsvatten och andra flyktiga produkter och gaser avdestillera. Vattnet och de Ovriga flyktiga produkterna kunna kondenseras i en kyld falla tillsammans med eventuellt meddragna, hiigkokande produkter. The process is conveniently carried out in a stainless steel reaction vessel equipped with a backflow cooler. Deana can either be heated or cooled, so that fatty acids and other high-boiling products are caused to reflux, while reaction water and other volatile products and gases distill off. The water and the other volatile products can be condensed in a cooled trap together with any entrained, high-boiling products.
Blandningen i det anvanda reaktionskarlet upphettas till en temperatur mellan 220 och 3° C. Det dr onskvart att atminstone under den senare delen av reaktionstidert halla reaktionsblandningen vid en temperatur mellan 250 och 300° C. Reaktionen kan utforas vid atmosfarstryck, t. ex. i en strom air en inert gas, sasom kvavgas, men utfores foretradesvis antingen under vakuum eller i narvaro av ett inert, med vatten oblandbart losningsmedel. The mixture in the reaction vessel used is heated to a temperature between 220 and 3 ° C. It is desirable to keep the reaction mixture at a temperature between 250 and 300 ° C at least during the latter part of the reaction time. The reaction can be carried out at atmospheric pressure, e.g. in a stream of air an inert gas, such as nitrogen gas, but is preferably carried out either under vacuum or in the presence of an inert, water-immiscible solvent.
Katalysatorn kan blandas med utgangsmaterialet eller tillsattas under upphettningen i reaktionskarlet. Den kan 5.ven placeras i kylaren. The catalyst can be mixed with the starting material or added during heating in the reaction vessel. It can also be placed in the radiator.
Aterflodeskylaren kan exempelvis packas med spiraler, Raschig-ringar eller liknande. Den kan aven regleras pa sadant satt, att en del av,fettsyrorna fa avdestillera. The backflow cooler can, for example, be packed with spirals, Raschig rings or the like. It can also be regulated in such a way that some of the fatty acids can be distilled off.
Efter upphettningen kan eventuellt oforandrad fettsyra i reaktionsblandningen extraheras med ett lampligt losningsmedel, t. ex. alkohol. Reaktionsblandningen kan alternativt destilleras i vakuum for avskiljning av oforandrad fettsyra. Aterstoden efter losningsmedelsbehandlingen eller destillationen utgor den onskade produkten. Reaktionsblandningen underkastas lampligen filtrering, tvattning med hett vatten for avskiljning av katalysatorn och torkning i vakuum fore eller efter losningsmedelbehandlingen eller destillationen. After heating, any unchanged fatty acid in the reaction mixture can be extracted with a suitable solvent, e.g. alcohol. Alternatively, the reaction mixture may be distilled in vacuo to separate unchanged fatty acid. The residue after the solvent treatment or distillation constitutes the desired product. The reaction mixture is suitably subjected to filtration, washing with hot water to separate the catalyst and drying in vacuo before or after the solvent treatment or distillation.
Om reaktionen utf Ores i narvaro av ett inert, med vatten oblandbart losningsmedel, bor losningsmedlets kokpunkt lampligen vara hogre an! 130° C och icke hOgre an 300° G. Under upphettningen meddrager losningsmedlet vatten, som frigjorts under reaktionen och de av losningsmedel och meddraget vatten bestaende angorna foras till en kylare, som dr forenad med em lamplig falla. Det vatten och losningsmedel, som kondenserat, skiljas frau varandra i fallan, varefter det kondenserade lOsningsmedlet aterfores till reaktionskarlet. If the reaction is carried out in the presence of an inert, water-immiscible solvent, the boiling point of the solvent should suitably be higher! 130 ° C and not higher than 300 ° G. During heating, the solvent entrains water released during the reaction and the vapors consisting of solvent and entrained water are fed to a condenser, which is combined with a suitable trap. The condensed water and solvent are separated from each other in the trap, after which the condensed solvent is returned to the reaction vessel.
Lampliga losningsmedel aro xylen, som kokar mellan 135 och 145° C och som mojliggor en upphettning till 260° C, tetralin (tetrahydronaftalen) med kokpunkten 205-215° C, som mojliggor upphettning upp till 295° C, och dekalin (dekahydronaftalen) med kokpunkten 184-191° C, som mojliggor upphettning till 290° C. Petroleumkolvatefraktioner med en kokpunkt Over 200° C utgora aven lampliga losningsmedel. Suitable solvents are xylene, which boils between 135 and 145 ° C and which allows heating to 260 ° C, tetralin (tetrahydronaphthalene) with a boiling point of 205-215 ° C, which allows heating up to 295 ° C, and decalin (decahydronaphthalene) with boiling point 184-191 ° C, which allows heating to 290 ° C. Petroleum carbonate fractions with a boiling point above 200 ° C also constitute suitable solvents.
Det vid utforande av foreliggande Vidarande erhallna destillatet eller alkoholextraktet kan anyo anvandas sasom utgangsmaterial for ytterligare en behandling, eftersom det huvudsakligen bestar av oforandrat utgangsmaterial. Om reaktionen far ske till ett stadium, vid vilket endast en ringa mangd oforandrat utgangsmaterial ingar i reaktionsblandningen, dr det icke nodvandigt att avla.gsna dess utgangsmaterial. The distillate or alcohol extract obtained in carrying out the present Further can be used as starting material for a further treatment, since it consists essentially of unchanged starting material. If the reaction is allowed to proceed to a stage at which only a small amount of unchanged starting material is present in the reaction mixture, it is not necessary to read off its starting material.
Den aterstod, som erhalles under de beskrivna reaktionsbetingelserna, utg6r den huvudsakliga produkten. Om utgangsmaterialet innehaller omattade fettsyror, har aterstoden battre torkegenskaper an motsvarande triglycerider, sankt flyktighet och Rad viskositet i jamforelse med de fettsyror, som bilda utgangsmaterialet. Forandringarna av dessa egenskaper bli tydligare med likande upphettningstid och/eller -temperatur. Analysresultat visa, att reaktionen medfor bildning av en vasentlig mangd ofortvalbart material, som skiljer sig fran de kanda fettsyraketonerna. Det har visat sig, att detta ofortvalbara material huvudsakligen är ansvarigt for de goda torkegenskaperna och visar vid isolering enastaende filmbildande egenskaper. The residue obtained under the reaction conditions described is the main product. If the starting material contains unsaturated fatty acids, the residue has better drying properties than the corresponding triglycerides, low volatility and Rad viscosity compared to the fatty acids which form the starting material. The changes in these properties become clearer with similar heating time and / or temperature. Analysis results show that the reaction results in the formation of a significant amount of non-digestible material, which differs from the known fatty acid ketones. It has been found that this non-digestible material is mainly responsible for the good drying properties and shows unique film-forming properties when insulated.
Uppfinningen innefattar aven de nya kondensationsprodukter, som erhallas enligt dessa forfaranden, sasom sfidana eller i blandning med oforandrade fettsyror. The invention also includes the novel condensation products obtained by these processes, such as spidane or in admixture with unchanged fatty acids.
Kondensationsprodukterna enligt uppfinningen utmarka sig av en. vasentlig halt, foretradesvis minst Vo, ofortvalbart material, lagt syra- och fortvalningstal, Rat jodtal enligt Wijs, j amfort med utgangsmaterialet och en. hog medel-molekylvikt. Medelmolekylvikten av den ofortvalbara delen ar grovt raknat overensstammande med eller hogre an den. beraknade molekylvikten av en teoretisk kondensationsprodukt av tre molekyler fettsyra. Om jodtalet bestdmmes enligt Wijs' metod och visar sig vara 100 eller hogre, ha kondensationsprodukterna torkande egenskaper. De ha vidare en molekylstruktur, corn innehaller 4— 190 62 — minst tre alkylkedjor, vilka likna de som inga. i fettsyrorna av de omattade oljorna. The condensation products according to the invention are distinguished by a. essential content, preferably at least Vo, non-digestible material, added acid and preselection number, Rat iodine number according to Wijs, j amfort with the starting material and a. high average molecular weight. The average molecular weight of the non-digestible moiety is roughly estimated to be equal to or higher than that. calculated the molecular weight of a theoretical condensation product of three molecules of fatty acid. If the iodine value is determined according to Wijs' method and turns out to be 100 or higher, the condensation products have drying properties. They also have a molecular structure, the corn contains at least three alkyl chains, which are similar to those which do not. in the fatty acids of the unsaturated oils.
Uppfinningen innefattar aven anvand.ning av ovannamnda produkter med ett jodtal enligt Wijs' metod av 100 eller hogre, sasom ersattningsmaterial for torkande material, t. ex. torkande oljor, oljelacker eller alkydhartser i malningsfarg, lack, linoleum och for beslakfade andamal. The invention also includes the use of the above-mentioned products with an iodine value according to Wijs' method of 100 or higher, as a replacement material for drying materials, e.g. drying oils, oil paints or alkyd resins in paint, lacquer, linoleum and for sanded andamal.
De nya produkterna kunna bIandas med vanliga sickativ, baserade pa kobolt, bly eller mangan, och kunna utspadas till onskad viskositet med terpentin, lattfotogen och/eller andra flyktiga losningsmedel. The new products can be mixed with ordinary leaks, based on cobalt, lead or manganese, and can be diluted to the desired viscosity with turpentine, light kerosene and / or other volatile solvents.
Sasom exempel pa anvandning av de nya produkterna kan namnas den for en produkt, erhallen av sojabonoljefettsyror enligt foreliggande forfarande i ett utbyte av 75,4 %. Denna produkt hade ett syratal av 8,6, ett fortvalningstal av 44,2, ett jodtal enligt Wijs' metod av 175,3 och en halt ofortvalbart material av 82,5 %. Denna produkt gay foljande resultat vid anvandning sasom barare for malningsfarg eller sasom klarlack. Viskositeten var 37 pois vid 20° G, dvs. detsamma som for en tunn standolja. En for ersattning av linolj a. lampad produkt erholls genom bland-fling av 57 g av den nya kondensationsprodukten med 33 g av en 1:1-blandning av terpentin och lattfotogen. For ersattning av oljelack framstalldes en blandning av 90 g av kondensationsprodukten och 10 g av 1:1- blandningen av terpentin och lattfotogen. Eu ringa mangd sickativ var tillracklig for att man skulle erhalla kortare torkningstid an hos kokt linolja av god kvalitet. Med exempelvis 0,1 % kobolt, raknat pa kondensationsprodukten, erfordrades 240 minuter for torkfling till f8r beroring torrt tillstand och 3011 minuter for torkning till hart tillstand. Den vid lufttorkning av den outspadda kondensationsprodukten uppkomna viktokningen var hOgre an for linstandolj a med gamma viskositet, vilket antyder en hog affinitet till syre, fastan produkten erholls av sojabonoljefettsyror med mycket lagre jodtal an linolja. Den erhallna filmens hardhet provades enligt Sward's metod och visade sig vara vasentligt hardare an en film av kokt linolja och lika hog som ett maleinathartslack, innehallande 2,3 liter olja per kg harts. Filmen var Mitre best andig mot vatten och utspadd svavelsyra an filmer av linolja och manga oljelacker. As an example of the use of the new products may be mentioned that for a product obtained from soybean oil fatty acids according to the present process in a yield of 75.4%. This product had an acid number of 8.6, a preselection number of 44.2, an iodine number according to Wijs' method of 175.3 and a content of non-digestible material of 82.5%. This product gay following results when used as a barer for paint or as a clear coat. The viscosity was 37 pois at 20 ° C, i.e. same as for a thin stand oil. A substituted product for linseed oil is obtained by mixing 57 g of the new condensation product with 33 g of a 1: 1 mixture of turpentine and latte kerosene. To replace the oil paint, a mixture of 90 g of the condensation product and 10 g of the 1: 1 mixture of turpentine and latte kerosene was prepared. A small amount of leachate was sufficient to obtain a shorter drying time than with good quality boiled linseed oil. With, for example, 0.1% cobalt, shaved on the condensation product, 240 minutes were required for drying to dry state and 3011 minutes for drying to hard condition. The weight gain obtained during air drying of the undiluted condensation product was higher than for linseed oil with gamma viscosity, which indicates a high affinity for oxygen, although the product is obtained from soybean oil fatty acids with much lower iodine content than linseed oil. The hardness of the obtained film was tested according to Sward's method and was found to be substantially harder than a film of boiled linseed oil and as high as a maleinate resin lacquer, containing 2.3 liters of oil per kg of resin. The film was Miter best spirit against water and diluted sulfuric acid than films of linseed oil and many oil paints.
Zinkvittemaljer, framstallda av kondensationsprodukterna, visade icke nagra tecken till intjockning. Zinc white enamels, produced from the condensation products, showed no signs of thickening.
Vad hetraffar daligt torkande oljor, t. ex. sillolja, bomullsolja, jordnotsolja eller rapsfroolj a, skulle aven om de mer mattade syrabestandsdelarna avlagsnades och de atersta.- ende omattade syrorna ateromvandlades: till triglycerider de resulterande produkterna ha samre torkegenskaper an produkter enligt uppfinningen, framstallda av motsvarande syror. En film, som Midas av den produkt, vilken erhalles av linol-syra, som beskrivet i foljande exempel 4, är hardare an en film av vane linol-syraglycerid, och dess hardhet dr i det narmaste lika hog som hardheten av en film av en linolensyraglycerid. What hotly hits dehydrating oils, e.g. herring oil, cottonseed oil, peanut oil or rapeseed oil, even if the more saturated acid constituents were removed and the remaining unsaturated acids were converted again: to triglycerides the resulting products have the same drying properties as products according to the invention, produced from corresponding acids. A film which is Midas of the product obtained from linoleic acid, as described in the following Example 4, is harder than a film of conventional linoleic acid glyceride, and its hardness is about as high as the hardness of a film of a linolenic acid glyceride.
Uppfinningen askadliggores narmare me-deist foljande exempel. Vid de i exemplen 1 till 8, 12, 13, 16 och 17 beskrivna i laboratorieskala utforda forsoken angives temperaturen av det metallbad, som omgiver reaktionskarlet. I dessa exempel var temperaturen reaktionsblandningen lagre, t. ex. mellan 20 och 30° lagre under de forsta stadierna och ungefar 10° C lagre under de sista stadierna av reaktionen. The invention is further illustrated by the following examples. In the laboratory scale challenge experiments described in Examples 1 to 8, 12, 13, 16 and 17, the temperature of the metal bath surrounding the reaction vessel is indicated. In these examples, the temperature of the reaction mixture was lower, e.g. between 20 and 30 ° lower during the initial stages and approximately 10 ° C lower during the final stages of the reaction.
De temperaturer, som angivas i de aterstaende exemplen, beteckna reaktionsblandningens temperatur. The temperatures given in the following examples denote the temperature of the reaction mixture.
Exempel 1. 110 g fettsyror, erhallna av norsk sillolja enligt Twitchellmetoden (fiskoljornas syratal 182,7 och jodtal 132,7) och 2,75 g kristallia borsyra inforas i en 250 ml kolv, Over vilken en fraktioneringskolonn är anordnad i vertikalt lage. Denna kolonn ar forbunden med en vakuumpump via en luftkyld kylare, som Or parallellkopplad med fraktioneringskolonnen, och ett fOrlag vid kylarens andra ande. Fraktioneringskolonnen ar packad med spiraler av rostfritt stal, llaschig-ringar av glas eller liknande. Example 1. 110 g of fatty acids obtained from Norwegian herring oil according to the Twitchell method (acid number of fish oils 182.7 and iodine number 132.7) and 2.75 g of crystalline boric acid are introduced into a 250 ml flask, over which a fractionation column is arranged in a vertical layer. This column is connected to a vacuum pump via an air-cooled radiator, which is connected in parallel with the fractionation column, and a source at the other end of the radiator. The fractionation column is packed with spirals of stainless steel, llaschigings of glass or the like.
Efter evakuering av apparaten till cirka 2-3 mm Hg upphettades kolven langsamt i ett metallbad, tills badtemperaturen var 290° C. Upphettningen utf5rdes inom 60, minuter, tills badets temperatur var 210° C. Den fortsattes sedan ytterligare 150 minuter, varvid badtemperaturen hojdes frail 210 till 290° C. Badet holls vid det sistnamnda gradtalet under 3 timmar. Fraktioneringskolonnen upphettades till cirka 175° C genom elektrisk motstandsupphettning. Vid en badtemperatur frau ungefar 210° C och uppat borjade en del material att destillera till forlaget. Material, som inkom i fraktioneringskolonnen, horjade kondensera vid en lAgre badtemperatnr. El-ter 3 timmars upphettning vid 290° C lick reaktionsblandningen avsvalna. 31,3 g fettsyror och en ringa mangd vatten och lagkokande sonderdelningsprodukter avdestillerade, medan 64,4 g erhollos som aterstod i reaktionskarlet. Den fasta borsyran, som ingick i aterstoden, avfiltrerades, medan Aterstoden annu var varm. En del material haltade fast vid fyllningen I aterflodeskoIonnen och utvanns genom extraktion med lattfotogen. Den viskosa aterstoden, som hade syratalet 10 och inneholl 81,3 % ofortvalbart material, utspaddes med lattfotogen. 0,3 % Pb och 0,066 % Mn tillsattes i form av naftenatsickativ. Nar ett tunt sldkt av den salunda framstallda lacken utsattes for luftens inverkan, torkade den till klibbfritt tillstand pa mindre an en dag. — —a Fettsyrorna av sardinolja och tran gay vid behandling enligt ovan beskrivna exempel varierande mangd (50 till 80 %) áterstoci i form av oljeartade vatskor med goda torkegenska- per. After evacuating the apparatus to about 2-3 mm Hg, the flask was slowly heated in a metal bath until the bath temperature was 290 ° C. The heating was performed within 60 minutes until the bath temperature was 210 ° C. It was then continued for another 150 minutes, raising the bath temperature. frail 210 to 290 ° C. The bath is kept at the latter degree for 3 hours. The fractionation column was heated to about 175 ° C by electric resistance heating. At a bathing temperature of about 210 ° C and above, some material began to distill to the publisher. Materials that entered the fractionation column began to condense at a lower bath temperature no. After heating for 3 hours at 290 ° C, the reaction mixture was allowed to cool. 31.3 g of fatty acids and a small amount of water and boiling boiling partitioning products were distilled off, while 64.4 g of erhollose which remained in the reaction vessel. The solid boric acid, which was part of the residue, was filtered off, while the residue was still hot. Some material limped to the filling in the backwater column and was recovered by extraction with latte kerosene. The viscous residue, which had an acid number of 10 and contained 81.3% of non-digestible material, was diluted with latte kerosene. 0.3% Pb and 0.066% Mn were added in the form of naphthenate siccatives. When a thin layer of the thus produced lacquer was exposed to the action of the air, it dried to a tack-free state in less than a day. - —a The fatty acids of sardine oil and tran gay in treatment according to the examples described above varying amount (50 to 80%) of atherosclerosis in the form of oily water shoes with good drying properties.
Vid ett liknande f5rsok, som emellertid utfordes med anvandning av endast 0,3 vikt- procent borsyra, avdestillerades en storre del av reaktionsblandningen, sa att endast ungefar 38 % ãterstod blev kvar i reaktionskarlet. In a similar experiment, which is, however, challenged with the use of only 0.3% by weight of boric acid, a large part of the reaction mixture was distilled off, so that only about 38% of the residue remained in the reaction vessel.
Denna aterstod hade syratalet 16,5, och torkade efter sickativering pa 6 timmar till en icke klibbig och hard film. This residue had an acid number of 16.5, and dried after leaching for 6 hours to a non-sticky and hard film.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor shvida sickativen darror Toro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for paints and varnishes in that the Toro siccatives were built on the basis of cobalt, lead and manganese compounds.
Exempel 2. 110 g silloljefettsyror (syratal 182, jodtal 142,7) och 6,6 ammoniumpentaborat upphettades i 60 minuter i den i exempel 1 beskrivna apparaten till en badtemperatur av 210° C, darpa mom 150 minuter till en badtemperatur av 290° C och slutligen 60 minuter vid en badtemperatur av 290° G. Efter avkylning erhollos 55,5 g aterstod i reaktionskarlet. Denna aterstod hade samma konsistens som en hogviskos standolj a. Example 2. 110 g of herring oil fatty acids (acid number 182, iodine value 142.7) and 6.6 ammonium pentaborate were heated for 60 minutes in the apparatus described in Example 1 to a bath temperature of 210 ° C, darpa 150 minutes to a bath temperature of 290 ° C and finally 60 minutes at a bath temperature of 290 ° G. After cooling, 55.5 g of residue were recovered in the reaction vessel. This residue had the same consistency as a high viscosity stand oil a.
Efter utspadning med lattfotogen filtrerades aterstoden for avskiljning av den fasta katalysatorn, varefter aterstoden tvattades med hett vatten for avskiljning av losta borsyrafOreningar. Nar den resulterande produkten behandlades enligt exempel 1, erh011s en komposition med goda torkegenskaper. En tunn film av demm komposition var under normala temperatur- och ljusbetingelser torr for berOring pa 3,5 timmar och i det narmaste fri fran klibbighet efter 24 timmar. After dilution with light kerosene, the residue was filtered to separate the solid catalyst, after which the residue was washed with hot water to separate loose boric acid compounds. When the resulting product was treated according to Example 1, a composition having good drying properties was obtained. A thin film of this composition was under normal temperature and light conditions dry to the touch for 3.5 hours and almost free of stickiness after 24 hours.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor savida sickativen darfOr voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes, while the sealants therefor were built on the basis of cobalt, lead and manganese compounds.
Exempel 3. Tekniska, destillerade linoljefettsyror (jodtal 165) upphettades langsamt I apparaten enligt exempel 1, tills badtemperaturen var 290° C, tillsammans med 6 viktprocent borsyra. Upphettningen fortsattes, tills cirka 25 % av det ursprungliga materialet hade avdestillerat sasom vatten (ungefar 7 %) och fettsyror (ungefar 18 %). Aterstoden torkade efter tillsats av sickativ och utspadning pa 3,5 timmar till en, praktiskt taget klibbfri och farglOs film och var lamplig sasom ersattningsmedel for kokt linolja vid framstallning av malningsfarger eller for anvandning sasom klarlack. Example 3. Technical, distilled linseed oil fatty acids (iodine value 165) were slowly heated in the apparatus of Example 1, until the bath temperature was 290 ° C, together with 6% by weight of boric acid. Heating was continued until about 25% of the original material had distilled off as water (approximately 7%) and fatty acids (approximately 18%). The residue dried after the addition of siccative and dilution for 3.5 hours to a substantially tack-free and colorless film and was suitable as a substitute for boiled linseed oil in the manufacture of paint paints or for use as clearcoat.
Vid ett liknande forsok uttogos prey under upphettningen av reaktionsblandningen vid en badtemperatur av 215, 245, 260, 275 och 290° C. Jodtalet for dessa prov var 167,2, 177,8, 179,9, 179,7 resp. 190,5 och brytningsindex 1,1674, 1,4700, 1,4730, 1,4793 resp. 1,9405. Det sista provet hade en viskositet av 3,4 pois medan det narmast fOregfiende en dast hade en viskositet av 0,9 pois. Den starsta delen air destillatet med lagre jodtal avgick under den tidigare delen av upphettningspe- rioden, vilket orsakade hbjningen av aterstodens jodtal till cirka 180. Efter ytterligare ungefar en timmes upphettning vid en bad- temperatur av 290° C hade aterstoden gelatinerat. Sadana geler kunna med fordel anvandas mom lackindustrien och narbeslaktade industrier, t. ex. vid framstallning av lino- leum och vissa malningsfarger. In a similar experiment, prey was taken out while heating the reaction mixture at a bath temperature of 215, 245, 260, 275 and 290 ° C. The iodine value for these samples was 167.2, 177.8, 179.9, 179.7 and 179.7, respectively. 190.5 and refractive index 1.1674, 1.4700, 1.4730, 1.4793 respectively. 1.9405. The last sample had a viscosity of 3.4 pois while the nearest enemy had a viscosity of 0.9 pois. The largest part of the air distillate with lower iodine value resigned during the earlier part of the heating period, which caused the residual iodine value to increase to about 180. After another approximately one hour of heating at a bath temperature of 290 ° C, the residue had gelatinized. Such gels can be used to advantage in the paint industry and closely related industries, e.g. in the production of linoleum and certain paint colors.
Exempel 4. Vid behandling ay ett linolsyrakoncentrat av saffloroljefettsyror enligt ex- empel 1 erholls en aterstod i ett utbyte av ungefar 65 % i form av en forhallandevis viskos olja, som efter tillsats av torkmedel gay en klibbfri film pa ungefar 7 timmar. 01-Jan hade ett syratal av 30,7, ett fortvalnings- tal av 6,1, 20 % karbonylsyre, bestamt enligt Knight och Swern, Journal of the American Oil Chemists Society, 26, 366-370 (1949), ett hydroxyltal av 0 och inneholl 73,4 % of8rtvalbart material med en molekylvikt av ungefar 900, bestamd enligt Mattiello, Protective and Decorative Coatings, del V sid. 194-195, John Wiley and Sons, New York (1947). Den var till storsta delen oloslig i etylalkohol, ace-ton och attiksyra men loslig i alifatiska och aromatiska kolvaten, t. ex. lattfotogen eller bens en. Example 4. Upon treatment with a linoleic acid concentrate of safflower fatty acids according to Example 1, a residue is obtained in a yield of about 65% in the form of a relatively viscous oil, which after addition of desiccant gays a tack-free film of about 7 hours. 01-Jan had an acid number of 30.7, a preselection number of 6.1, 20% carbonyl acid, determined according to Knight and Swern, Journal of the American Oil Chemists Society, 26, 366-370 (1949), a hydroxyl number of 0 and contained 73.4% of non-biodegradable material with a molecular weight of approximately 900, determined according to Mattiello, Protective and Decorative Coatings, Part V p. 194-195, John Wiley and Sons, New York (1947). It was largely insoluble in ethyl alcohol, acetone and acetic acid but soluble in aliphatic and aromatic hydrocarbons, e.g. lattfotogen or bens en.
Produkten visade en anmarkningsvard jodtalsokning. Koncentratet hade fore upphettningen jodtalet 180 bade enligt Wijs' och enligt Woburn's metod, medan produkten efter upphettningen hade jodtalet 211 enligt Wijs' metod och 234 enligt Woburn's metod. Den ofortvalbara delen av produkten (73,4 %) hade annu hogre jodtal, namligen 224 enligt Wijs' och 250 enligt Woburn, och ett cliental enligt Ellis-Jones av 10,3. The product showed a remarkably high iodine value increase. Prior to heating, the concentrate had an iodine value of 180 both according to Wijs 'and Woburn's method, while the product after heating had an iodine value of 211 according to Wijs' method and 234 according to Woburn's method. The non-selectable part of the product (73.4%) had an even higher iodine value, namely 224 according to Wijs' and 250 according to Woburn, and a cliental according to Ellis-Jones of 10.3.
Den ofortvalbara delen av aterstoden, erhallen genom extraktion med 15sningsmedel efter fortvalning, hade annu battre torkegenskaper in produkten i sin helhet, genom att den efter tillsats av sickativ och efter utspadning torkade till en mycket hard film, som var lika hard som en film av kinesisk traolja och hade god vatten- och alkalibestandighet. The non-digestible portion of the residue, obtained by extraction with solvents after pre-digestion, had even better drying properties in the product as a whole, in that after the addition of siccative and after dilution it dried to a very hard film, which was as hard as a Chinese film. trawl oil and had good water and alkali resistance.
Det fettsyredestillat, som hade tillvaratagits i forlaget och utgjorde ungefar 22 -viktprocent av materialet, bestod till storsta delen av ofOrandrad men fororenad linolsyra och kande artvandas pa nytt. Destillatet hade eti syratal av 143,0 ett fortvalningstal av 190,6 och ett jodtal av 170,8. Cirka 6 % vatten hade samlat sig i en kyld falla i vakuumledningen. The fatty acid distillate, which had been recovered in the publishing house and made up about 22% by weight of the material, consisted for the most part of unchanged but contaminated linoleic acid and could be re-hydrated. The distillate had an acid number of 143.0, a preselection number of 190.6 and an iodine number of 170.8. About 6% water had accumulated in a cooled trap in the vacuum line.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor savida sickativen darfOr voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes, while the sealants therefor were built on the basis of cobalt, lead and manganese compounds.
Exempel 5. 110 g bomullsfrooljefettsyror, erhallna genom teknisk destillation av genom fOrtvalning av bomullsfroolj a erhallna fettsy- 6- 190 651 - ror, behandlades i en rundbottnad kolv. Fraktioneringskolonnen var anordnad Over kolven och packad sasom beskrivet i exempel 1. Den inneholl aven 6,6 g borsyra i form av stycken erhallna genom anbringandet av hogt tryck pa en uppslamning av finpulveriserad, kristallin borsyra och en ringa mangd vatten i en tablettpress med efterfoljande torkning vid ungefar 70.0 C, i en ugn. Efter evakuering av apparaten upphettades reaktionskarlet sasom I exempel 2. Pa detta satt erholls en aterstod, som vagde 47 g och som efter tillsats av fortunningsmedel och torkmedel ph 3,5 timmar torkade till en hard, elastisk och klibbfri film med goda ytoverdragningsegenskaper. Example 5. 110 g of cottonseed oil fatty acids obtained by technical distillation of fatty acids obtained by preselection of cottonseed oil were treated in a round bottom flask. The fractionation column was arranged over the flask and packed as described in Example 1. It also contained 6.6 g of boric acid in the form of pieces obtained by applying high pressure to a slurry of finely powdered, crystalline boric acid and a small amount of water in a tablet press with subsequent drying. at about 70.0 C, in an oven. After evacuation of the apparatus, the reaction vessel was heated as in Example 2. This gave a residue which weighed 47 g and which, after the addition of diluent and desiccant for 3.5 hours, dried to a hard, elastic and tack-free film with good surface coating properties.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor sâvida sickativen darfor voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes insofar as the leachates therefor were built on the basis of cobalt, lead and manganese compounds.
Exempel 6. 110 g av en oljesyra med 97 % renhetsgrad, innehallande 2 till 3 % mattade fettsyror, behandlades med 6,6 g borsyra, som fordelats i en fraktioneringskolonn sasom i exempel 5. Upphettningstiden och -temperaturen voro desamma som i exempel 2. Forutom 6,4 g av ett fettsyradestillat, som hade jodtalet 52 och som huvudsakligen bestod av en blandning av oljesyra och palmitinsyra, tillvaratogs 7,7 g av ett vattenhaltigt destillat. Huvudmangden material, som kvarblev i kolven, tvattades med hett vatten for avskiljning av losta borforeningar. Efter derma rening hade aterstoden brytningsindex 1,4776, syratalet 58,1, fortvalningstalet 85,6, jodtalet 132,9 och en medelmolekylvikt av 661, medan oljesyra har brytningsindex 1,4580, syratatet 198,5, fortvalningstalet 199,3 och jodtalet 88,0. Fastan oljesyran fore behandlingen var fri fran ofortvalbart material, inneholl aterstoden 44,7 % sadant material. Aterstoden var loslig i eter och lattfotogen men oloslig i alkohol och attiksyra. Totalt uppkom en viktforlust av 2,%, raknat pa utgangsmaterialet. Denna viktforlust berodde pa bildning av gasformiga sonderdelningsprodukter. Example 6. 110 g of a 97% purity oleic acid, containing 2 to 3% saturated fatty acids, were treated with 6.6 g of boric acid, distributed in a fractionation column as in Example 5. The heating time and temperature were the same as in Example 2. In addition to 6.4 g of a fatty acid distillate, which had the iodine value 52 and which consisted mainly of a mixture of oleic acid and palmitic acid, 7.7 g of an aqueous distillate were recovered. The bulk of the material remaining in the flask was washed with hot water to separate loose boron compounds. After this purification, the residue had a refractive index of 1.4776, an acid number of 58.1, a preselection number of 85.6, an iodine value of 132.9 and an average molecular weight of 661, while oleic acid has a refractive index of 1.4580, an acid number of 198.5, a preservative number of 199.3 and an iodine value of 88. , 0. Although the oleic acid before treatment was free of non-digestible material, the residue contained 44.7% of such material. The residue was soluble in ether and light kerosene but insoluble in alcohol and acetic acid. In total, a weight loss of 2% occurred, based on the starting material. This weight loss was due to the formation of gaseous particulate products.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor savida sickativen dad& voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes, while the sedatives were built on the basis of cobalt, lead and manganese compounds.
Exempel 7. 110 g jordnOtsoljefettsyror (syratal 197,6, jodtal 98,7) upphettades under vakuum i en kolv, forsedd med en kolimn, som inneholl Raschig-ringar tillsammans med stycken av borsyra, erhallna genom pressning och torkning av fuktad pulveriserad borsyra. En luftkyId aterflodeskylare anordnades ovanfor denna kolonn. Fraktioneringskolonnen upphettades pa elektrisk vag till 200° C och vakuum upphavdes da och da under ett ogonblick, sá att destillat, som eventuellt samlats i den ovre delen av den upphettade kolonnen, kunde rinna tillbaka till kolven. Denna upphettades langsamt i ett bad, vars temperatur hojdes till 296° C och h011s vid detta gradtal en timme. Ph grund av att en aterflodeskylare anvandes, erholls icke nagot annat destillat an en vattenhaltig fraktion, som vagde ungefar 8 g och som kondenserade i en kyld falla I vakuumledningen. Aterstoden utgjorde ungefar 90 %, inberaknat de prov, som da och da togos for att folja hojningen av halten ofortvalbart. Aterstoden hade efter det jodtalet och sankningen av syratalet, orsakad genom hojningen av avslutade forsoket jodtalet 123,8 och syratalet 70,6. Den inneholl 20,6 % av en fettsyrafraktion (jodtal 94,4, syratal 175,5), som kunde avskiljas genom en timmes upphettning under vakuum vid 290° C. Aterstoden, som hade goda torkegenskaper erholls under dessa betingelser i form av en polymer, icke flyktig produkt. Example 7. 110 g of petroleum fatty acids (acid number 197.6, iodine value 98.7) were heated under vacuum in a flask equipped with a carbon black containing Raschig rings together with pieces of boric acid obtained by pressing and drying moistened powdered boric acid. An air-cooled backflow cooler was arranged above this column. The fractionation column was electrically heated to 200 ° C and a vacuum was applied from time to time for a moment so that distillates which may have accumulated in the upper part of the heated column could flow back to the flask. This was slowly heated in a bath, the temperature of which was raised to 296 ° C and kept at this degree for one hour. Due to the use of a reflux condenser, no distillate other than an aqueous fraction weighing about 8 g and condensing in a cooled trap was obtained in the vacuum line. The remainder was about 90%, including the samples taken from time to time to monitor the increase in the content undeliverably. After that, the residual iodine number and the decrease in the acid number, caused by the increase in the completed experiment, had the iodine number 123.8 and the acid number 70.6. It contained 20.6% of a fatty acid fraction (iodine number 94.4, acid number 175.5), which could be separated by one hour heating under vacuum at 290 ° C. The residue, which had good drying properties, was obtained under these conditions in the form of a polymer , non-volatile product.
Ett liknande resultat erholls, nar stycken av smolt boroxid av ungefar artstorlek fordelades i fyllningen I fraktioneringskolonnen. A similar result was obtained when pieces of smolt boron oxide of approximately species size were distributed in the filling in the fractionation column.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor savida sickativen dad& voro uppbyggda ph basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes savida sickatives dad & were built up ph base of cobalt, lead and manganese compounds.
Exempel 8. En blandning av 40 % neutral olj a och 60 % fria fettsyror, erhallen under alkaliraffinering av rapsfroolja och med ett syratal av 112 och ett jodtal av 126,8, behandlades med 6 % borsyra i den apparat och pa det satt som beskrivits i exempel 2. Aterstoden, som utgjorde 77 viktprocent av den ursprungliga fettforeningen, var en viskos olja med jodtalet 146,1. Efter tillsats av utspadningsmedel och metalltorkmedel visade en film efter 19 timmars torkning endast ringa klibbighet. Example 8. A mixture of 40% neutral oil and 60% free fatty acids, obtained under alkali refining of rapeseed oil and having an acid number of 112 and an iodine value of 126.8, was treated with 6% boric acid in the apparatus and in the manner described in Example 2. The residue, which accounted for 77% by weight of the original fat compound, was a viscous oil with an iodine value of 146.1. After the addition of diluents and metal desiccants, a film after 19 hours of drying showed only low tack.
Den erhallna produkten var lamplig sasom utgangsmaterial for tacker och fernissor sâvida sickativen darfor voro uppbyggda ph basis av kobolt-, My- och manganforeningar. The product obtained was suitable as a starting material for tacks and varnishes insofar as the siccatives were therefore built up of ph base of cobalt, My and manganese compounds.
Exempel 9. 500 g separerade fiskoljesyror upphettades vid 240-260° C med 2 % borsyra och 80 ml xylen i en trehalskolv, forsedd med en mekanisk omrorare, termometer och en vattenfalla. Den hastighet, med vilken vat-ten frigjordes, och inverkan pa den analytiska konstanterna framga av folj ande tabell: Upphett- Uppsam- ningstid lat vatten Syratal i Um.imi 0 0 183,8 184 1,4659 61/2 8,0 160,7 181 1,468 13/4 11,2 135,7 159 1,4734 21 1/2 14,7 108,4 138 1,4783 28½ 17,1 91,9 11,4818 36 18,76,8 107 1,4852 Vatten fran katalysatorn: 4,3 ml Reaktionsvatten = 14,2 ml = 2,8 %. Example 9. 500 g of separated fish oleic acids were heated at 240-260 ° C with 2% boric acid and 80 ml of xylene in a three-necked flask equipped with a mechanical stirrer, thermometer and a waterfall. The rate at which the water was released and the effect on the analytical constants are shown in the following table: Heating- Collection time lat water Acid number in Um.imi 0 0 183.8 184 1.4659 61/2 8.0 160 , 7 181 1,468 13/4 11.2 135.7 159 1.4734 21 1/2 14.7 108.4 138 1.4783 28½ 17.1 91.9 11.4818 36 18.76.8 107 1, 4852 Water from the catalyst: 4.3 ml Reaction water = 14.2 ml = 2.8%.
Den salunda erhallna produkten befriades fran xylen, filtrerades, tvattades och torkades under vakuum vid 90° C samt extraherades med etylalkohol. Egenskaperna av extraktet och aterstoden Toro: Fortval- ningstal Brytnings- index vid 25°C Aterstod - 190 Extrakt Ursprungliga syror Utbyte GO % 40% Syratal 194 152,183,8 Fortvalningstal 56 176 184 Jodtal 148,114,2 131, Ofortvalbart material 37,5 % 652 -7 Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor savida sickativen darfOr voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product thus obtained was freed from xylene, filtered, washed and dried under vacuum at 90 ° C and extracted with ethyl alcohol. Properties of the extract and the residue Toro: Saponification number Refractive index at 25 ° C Residue - 190 Extract Original acids Yield GO% 40% Acid number 194 152,183.8 Saphoration number 56 176 184 Iodine number 148,114.2 131, Non-digestible material 37.5% 652 -7 The product obtained was suitable as a starting material for lacquers and varnishes, while the leachates were built on the basis of cobalt, lead and manganese compounds.
Exempel 12. 220 g jordnotsoljefettsyror och 6,6 g borsyra upphettades 16 timmar i en evakuerad kolv vid 220° C. En kolonn, forsedd med Raschig-ringar, anordnades Over kolven och den undre delen av kolonnen upphettades till 175° C. Denna kolonn tjanade sasom aterflodeskylare for fettsyrorna men tillat vatten och andra sonderdelningsprodukter att avdestillera. Den salunda erhallna produkten hade fortvalningstalet 163,5, jodtalet 110,6 och brytningsindex n = 1,4720. Produkten upphettades tre timmar tillsammans med den fortfarande narvarande borsyran vid atmosfarstryck i en rundbottnad kolv vid 290° C, varvid en svag koldioxidstrom samtidigt fick passera genom reaktionsblandningen. Slutprodukten hade fOrtvalningstalet 83,3, jodtalet 127,1 och brytningsindex n g 1,4812. Den hade torkande egenskaper. Example 12. 220 g of peanut oil fatty acids and 6.6 g of boric acid were heated for 16 hours in an evacuated flask at 220 ° C. A column, equipped with Raschig rings, was placed over the flask and the lower part of the column was heated to 175 ° C. served as a backflow condenser for the fatty acids but allowed water and other probing products to distill off. The product thus obtained had the preselection number 163.5, the iodine number 110.6 and the refractive index n = 1.4720. The product was heated for three hours with the still present boric acid at atmospheric pressure in a round bottom flask at 290 ° C, allowing a weak stream of carbon dioxide to pass through the reaction mixture simultaneously. The final product had the preselection number 83.3, the iodine number 127.1 and the refractive index n g 1.4812. It had drying properties.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor savida sickativen darfor voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes, and the sedatives were therefore built on the basis of cobalt, lead and manganese compounds.
Exempel 13. 12,4 % fettsyror av jordnotsolja, huvudsakligen bestiende av mattade sa- dana, avdestillerades under vakuum. 248 g ay aterstoden, som hade syratalet 191,8, fortvalningstalet 195,8 och jodtalet 122,9, upphetta- des timmar i narvaro av 20 g magnesiumoxid vid 330° C, varvid motsvarande keton erholls. Ketonen tvattades med utspadd svavelsyra for sonderdelning av magnesiumtvalarna och underkastades sedan en sluttvattning med vatten, tills den reagerade neutralt. Den hade syratalet 3,0, fortvalningstalet 3,5, jodtalet 126,8 och karbonyltalet 86,1. 70 g av denna keton och 40 g jordnOtsoljefettsyror upphettades med 2 % borsyra under 3 timmar upp till 290° C i ett kart, fOrsett med aterflodeskolonn. Blandningen Mills 4,5 timmar vid denna temperatur, sa att fettkondensatet aterflodade och reaktionsvattnet avlagsnades. Blandningen upphettades sedan ytterligare en timme utan aterflOde med uppsamling av kondensatet i ett flirlag. Den erhallna aterstoden vagde efter avskiljning ay borsyran 97 g och hade syratalet 1,5, fortvalningstalet 14,1 och jodtalet 168,5. Den torkade med hjalp ay ett sickativ till en elastisk film pa 2 dagar. Example 13. 12.4% fatty acids of peanut oil, consisting mainly of matte ones, were distilled off in vacuo. 248 g of the residue, which had an acid number of 191.8, a preselection number of 195.8 and an iodine number of 122.9, were heated for hours in the presence of 20 g of magnesium oxide at 330 ° C, whereby the corresponding ketone was obtained. The ketone was washed with dilute sulfuric acid to probe the magnesium whey and then subjected to a final watering with water until it reacted neutrally. It had an acid number of 3.0, a preselection number of 3.5, an iodine number of 126.8 and a carbonyl number of 86.1. 70 g of this ketone and 40 g of petroleum fatty acids were heated with 2% boric acid for 3 hours up to 290 ° C in a refill column. The mixture was milled for 4.5 hours at this temperature, then the fat condensate was refluxed and the reaction water was removed. The mixture was then heated for another hour without reflux with collection of the condensate in a multilayer. The residue obtained, after separation with the boric acid, weighed 97 g and had an acid number of 1.5, a preselection number of 14.1 and an iodine number of 168.5. It dried with the help of a siccative to an elastic film in 2 days.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor sá- vida sickativen dad& voro uppbyggda pa basis ay kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for paints and varnishes insofar as the siccatives were built on the basis of cobalt, lead and manganese compounds.
Exempel 14. 20 kg solrosoljefettsyror, erhallna vid fOrtvalning av solrosolja, och med syratalet 160, fortvalningstalet 196 och jodtalet 127, upphettades med 0,4 kg borsyra av teknisk kvalitet under ett vakuum av 15 till 25 men Hg i en apparat, som bestod av rost- Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor sa.- vida sickativen darfor voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. Example 14. 20 kg of sunflower fatty acids, obtained by preselection of sunflower oil, and having the acid number 160, the preselection number 196 and the iodine number 127, were heated with 0.4 kg of technical grade boric acid under a vacuum of 15 to 25 but Hg in an apparatus consisting of rust- The product obtained was suitable as a starting material for paints and varnishes, insofar as the sedatives were therefore built on the basis of cobalt, lead and manganese compounds.
Exempel 10. 180 g destillerade kokosnotoljefettsyror ur avfallsblandningar erhallna vid margarintillverkning upphettades med 3,6 g borsyra och 20 ml xylen vid 240-260.° C i en apparat av samma slag som den i foregaende exempel anvanda. Forsoket fortsattes 63 timmar utan avdragning av prey for analys. Den totalt avgivna vattenmangden var 12,5 ml, motsvarande 10,8 ml eller 6,0 % reaktionsvatten. Produkten renades pa sedvanligt satt och hade foljande egenskaper: Ursprungliga syror Efter behandlingen Jodtal (Wijs) 16,2 38,8 Brytningsindex (25° C) 1,4438 1,4763 Syratal 241,2 37,7 Fortvalningstal 242 58, OfOrtfalbart 0 % 47 % Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor savida sickativen darfor voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. Example 10. 180 g of distilled coconut oil fatty acids from waste mixtures obtained in margarine production were heated with 3.6 g of boric acid and 20 ml of xylene at 240 DEG-260 DEG C. in an apparatus of the same kind as that used in the previous example. The experiment was continued for 63 hours without deduction of prey for analysis. The total amount of water released was 12.5 ml, corresponding to 10.8 ml or 6.0% reaction water. The product was purified in the usual manner and had the following properties: Original acids After the treatment Iodine number (Wijs) 16.2 38.8 Refractive index (25 ° C) 1.4438 1.4763 Acid number 241.2 37.7 Pre-digestion number 242 58, OfFardable 0% 47% The product obtained was suitable as a starting material for lacquers and varnishes, while the sedatives were therefore built on the basis of cobalt, lead and manganese compounds.
Exempel 11. 750 g jordnotsoljefettsyror behandlades med 16 g borsyra och 120 ml tetrahydronaftalen i den i exempel 9 beskrivna apparaten, varvid temperaturen h011s mellan 260 och 290° C, tills vatten icke mer avgick. Efter 46 timmar hade 56,5 ml vatten tillvara- tagits, motsvarande 6,0reaktionsvatten. Example 11. 750 g of peanut oil fatty acids were treated with 16 g of boric acid and 120 ml of the tetrahydronaphthalene in the apparatus described in Example 9, the temperature being between 260 and 290 ° C, until water no longer escaped. After 46 hours, 56.5 ml of water had been recovered, corresponding to 6.0 reaction water.
Produkten renades pa sedvanligt salt och foljande analytiska konstanter faststalldes: Ursprungliga syror Efter behandlingen Syratal 197,7 6,2 Fortvalningstal 198 12 Brytningsindex (25° C) 1,4603 1,499 Jodtal (Wijs) 98,6 124,9 Ofortvalbart material 85% Hela produkten utspaddes med halva sin vikt lattfotogen och forsattes med 0,5 % bly och 0,05 % kobolt i form av naftenaten. Den resulterande produkten torkade pa. 24 timmar till en kontinuerlig film med en ringa best& ende klibbighet. 8— — MU. stal och var av samma slag som den .apparat, vilken anvandes vid tillverkning av ista:ndolja och alkydhartser. Den bested av en .gasuppvarmd kokare, som rymde 50 liter och var forsedd med omrorare, en anordning for tagning av prov under vakuum och en aterflOdeskylare, anordnad Over kokaren °eh forbunden med en rorkylare, som lutade ned mot ett forlag. Upphettningen foretogs under 3 timmar, tills temperaturen h5jts till 260° C, fortsattes ytterligare 4,5 timmar till en temperatur av 290° C och sedan ytterligare 4 timmar vid 290° C. Darvid tillvaratogos 5,5 kg fettsyra och 0,8 kg vatten i forlaget. The product was purified on the usual salt and the following analytical constants were determined: Original acids After the treatment Acid number 197.7 6.2 Sampling number 198 12 Refractive index (25 ° C) 1.4603 1.499 Iodine number (Wijs) 98.6 124.9 Non-digestible material 85% Whole the product was diluted with half its weight of light kerosene and continued with 0.5% lead and 0.05% cobalt in the form of naphthenates. The resulting product dried on. 24 hours for a continuous film with a low lasting stickiness. 8— - MU. steel and was of the same type as the apparatus used in the manufacture of icing oil and alkyd resins. It consisted of a gas-heated boiler, which held 50 liters and was equipped with a stirrer, a device for taking samples under vacuum and a reflux condenser, arranged above the boiler and connected to a tube cooler, which was inclined towards a publisher. The heating was carried out for 3 hours, until the temperature was raised to 260 ° C, continued for a further 4.5 hours at a temperature of 290 ° C and then for a further 4 hours at 290 ° C. 5.5 kg of fatty acid and 0.8 kg of water were recovered. in the publisher.
Den erhallna aterstoden vagde 13,7 kg och tvattades upprepade ganger med kokande vat-ten. Efter torkning vid 100° C under vakuum och filtrering pa en filterpress hade aterstoden foljande egenskaper: Syratal7, Fortvalningstal86 Jodtal (Wijs)143 Ofortvalbart material32 % Viskositet165 pois vid 20° C Efter tillsats av 0,3 % My oeh 0,02 % mangan i form av naftenat torkade a'terstoden till klibbfritt tillstand pa 90 minuter och standigt pa 150 minuter till en god, vattenIfestandig, laekliknande film. The resulting residue weighed 13.7 kg and was washed repeatedly with boiling water. After drying at 100 ° C under vacuum and filtration on a filter press, the residue had the following properties: Acid number7, Prevalence number86 Iodine number (Wijs) 143 Non-digestible material32% Viscosity165 pois at 20 ° C After addition of 0.3% My and 0.02% manganese in in the form of naphthenate, the residue was dried to a tack-free state for 90 minutes and continuously for 150 minutes to a good, water-resistant, leak-like film.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor sa.- vida sickativen darfor voro uppbyggda pa basis av kobolt-, bly- och manganf5reningar. The product obtained was suitable as a starting material for lacquers and varnishes, insofar as the leachates were therefore built on the basis of cobalt, lead and manganese compounds.
Exempel 15. I den i exempel 14 beskrivna apparaten upphettades 20 kg av en fraktion, erhallen av sojabonoljefettsyror (syratal 203,5, fortvalningstal 206,3, jodtal enligt Wijs 140,2 och ofortvalbart material 2,8 %) och 0,4 kg teknisk borsyra under ett vakuum av 13-20 mm Hg till 260° C under 10 timmar och till 290° C inom ytterligare 2 timmar. De fettsyror, som avdestillerade under denna upphettning, aterfordes kontinuerligt till reaktionskarlet. Upphettningen fortsattes darpa 4 timmar vid en temperatur mellan 260 och 290° C, varvid emellertid det erhallna destillatet tillvaratogs i ett forlag. P detta satt erh011os 0,6 kg av ett fettsyradestillat och 17,4 kg av en aterstod, som hade samma karaktar som standolja: Efter avkylning av aterstoden till ungefar 100° C avlagsnades den fortfarande narvarande borsyran genom upprepad kokning med nagra fa kg vatten och avskiljning av tvattvattnet. Aterstoden hade en viskositet av 194 pois vid 120° C, syratalet 7,3, fortvalningstalet 17,9, jodtalet 154,1 (enligt Wijs) och inneholl 86 % ofortvalbart material. Example 15. In the apparatus described in Example 14, 20 kg of a fraction, obtained from soybean oil fatty acids (acid number 203.5, preselection number 206.3, iodine number according to Wijs 140.2 and non-digestible material 2.8%) and 0.4 kg were heated. technical boric acid under a vacuum of 13-20 mm Hg to 260 ° C for 10 hours and to 290 ° C within a further 2 hours. The fatty acids which distilled off during this heating were continuously returned to the reaction vessel. The heating was continued for 4 hours at a temperature between 260 and 290 ° C, however, the distillate obtained was collected in a publishing house. This contained 0.6 kg of 0.6 kg of a fatty acid distillate and 17.4 kg of a residue, which had the same character as stand oil: After cooling the residue to about 100 ° C, the still present boric acid was removed by repeated boiling with a few kg of water and separation of the wash water. The residue had a viscosity of 194 pois at 120 ° C, an acid number of 7.3, a preselection number of 17.9, an iodine number of 154.1 (according to Wijs) and contained 86% of non-digestible material.
Efter tillsats av ett bly/mangannaftenatsickativ (0,3 % bly och 0,02 % mangan) och utspadning med en blandning av terpentin och lattfotogen (1:1) till en konsistens av 1,5 pois vid 20° C erh011s en produkt med goda tork egenskaper, som var anvandbar for framstallning av malningsfarger. En film av denna produkt var torr gentemot beroring efter ungefar 5 timmar och fullstandigt torr efter 7,5 timmar. After adding a lead / manganese naphthenic desiccant (0.3% lead and 0.02% manganese) and diluting with a mixture of turpentine and latte kerosene (1: 1) to a consistency of 1.5 pois at 20 ° C, a product with good drying properties, which were useful for the production of paint paints. A film of this product was dry to the touch after about 5 hours and completely dry after 7.5 hours.
Den erhallna produkten var lamplig sasom utgangsmaterial f6r lacker och fernissor savida sickativen darfi3r voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes, and the leachates were therefore built on the basis of cobalt, lead and manganese compounds.
Exempel 16. 100 g jordniitsoljefettsyra med syratalet 197,7 och jodtalet 99,6 upphettades med 3,5 g borsyratrimetylester. Den sistnamnda f6reningen hade framstallts av 1 mol borsyraanhydrid och 6 mol metylalkohol samt var renad genom destillation. Reaktionskomponenterna upphettades i en 250 ml rundbottnad kolv av Jena-glas, pa vilken en aterflodeskylare, som kunde upphettas och var fylld med spiraler av V2A-stal, var anordnad. Upphettningen foretogs vid atmosfarstryck upp till 140° G mom 30 minuter. Darefter evakuerades kolven till 2-3 mm Hg mom 40 minuter, dvs. sit fort som destillationen av metylalkoholen tillat. Example 16. 100 g of peanut oil fatty acid having an acid number of 197.7 and an iodine value of 99.6 were heated with 3.5 g of boric acid trimethyl ester. The latter compound had been prepared from 1 mole of boric acid anhydride and 6 moles of methyl alcohol and was purified by distillation. The reactants were heated in a 250 ml round bottom flask made of Jena glass, on which a reflux condenser which could be heated and filled with V2A steel coils was placed. The heating was carried out at atmospheric pressure up to 140 ° G for 30 minutes. The flask was then evacuated to 2-3 mm Hg for 40 minutes, ie. sit fast as the distillation of the methyl alcohol allowed.
Nar flagon metylalkohol icke mer avgick, underkastades blandningen foljande behandling: Forst upphettades badet inom 20 minuter till 200° C och sedan mom 150 minuter till 290° C, holls vid denna temperatur under 270 minuter och slutligen under 30 minuter, varunder den fettsyra, som kondenserat i aterflodeskylaren, icke lick aterga till reaktionskolven utan fordes till ett forlag, forbundet med den andra anden av aterflodeskylaren. Under hela behandlingen upprattb.olls ett vakuum av ungefar 2-3 mm Hg. Aterflodeskylaren upphettades vid borjan till en temperatur av 200° C och till 225° C vid a.vdestillationen av fettsyrorna. When the flake methyl alcohol was no longer released, the mixture was subjected to the following treatment: First, the bath was heated to 200 ° C within 20 minutes and then to 290 ° C for 150 minutes, kept at this temperature for 270 minutes and finally for 30 minutes, during which the fatty acid condensed in the backflow condenser, did not lick return to the reaction flask but was fed to a publisher connected to the other end of the backflow condenser. During the whole treatment a vacuum of about 2-3 mm Hg is established. The reflux condenser was initially heated to a temperature of 200 ° C and to 225 ° C during the distillation of the fatty acids.
Den erhallna aterstoden vagde 54,g. I narvaro ay blymangantorkmedel (0,3 % bly och 0,02 % mangan i form av naftenat) torkade en film av denna aterstod till mot beroring torrt tillstand pa 4,5 timmar och med en sing kvarstaende klibbighet pa 24 timmar. Aterstoden hade syratalet 29,6, fortvalningstalet 63,9, jodtalet (Wijs) 131 och en halt ofortvalbart material ay 73,5 %. Den erhallna aterstoden vagde 54, g. In the presence of lead manganese desiccant (0.3% lead and 0.02% manganese in the form of naphthenate), a film of this residue dried to a dry state of contact for 4.5 hours and with a slight stickiness of 24 hours. The residue had an acid number of 29.6, a preselection number of 63.9, an iodine number (Wijs) of 131 and a content of non-digestible material of 73.5%.
Med undantag fOr nagra fa kristaller yid kolvens ovre kant var aterstoden fri frau fast borsyra. Den kunde befrias fullstandigt fran denna syra genom tvattning med vatten, men detta var icke nodvandigt, eftersom narvaro av losliga borsyraforeningar icke vasentligt paverkar aterstodens egenskaper som torkande material. En liknande produkt erhons vid anvandning av borsyramannitolester sasom katalysator i stallet for borsyratrimetylester. With the exception of a few crystals at the upper edge of the flask, the residue was free from solid boric acid. It could be completely freed from this acid by washing with water, but this was not necessary, since the presence of soluble boric acid compounds does not substantially affect the properties of the residue as a drying material. A similar product is obtained when using boric acid mannitol ester as a catalyst instead of boric acid trimethyl ester.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor shvida sickativen darfor more uppbyggda pa basis ay kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes in that the sizing agents were therefore built on the basis of cobalt, lead and manganese compounds.
Exempel 17. 27 g jordnotsoljefettsyror med syratalet 197,7 och jodtalet 99,6 upphettades — —9 med 6,6 g bortriacetat i den apparat, som skull e anvandas for den. efterfaljande behandlingen. Blandningen upphettades en. timme vid 100 till 140° C, varefter den frigjorda attiksyran avdestillerades. N detta sail erhollos ungefar 28 g av blandanhydriden av borsyra och jordnotsoljefettsyrorna. En bland-fling av denna produkt och 73 g linoljefettsyra med syratalet 198,6 och jodtalet 137,1 upphettades till 200-290° C enligt exempel 16 med undantag for att avdestilleringstiden maste avkortas frail 30 till 10 minuter, eftersom produkten syntes vara hogviskos redan fore destillationen. Aterstoden hade syratalet 43,9, fortvalningstalet 70,2 och jodtalet (Wijs) 173,2. Example 17. 27 g of peanut oil fatty acids having an acid number of 197.7 and an iodine value of 99.6 were heated to -9 with 6.6 g of boron triacetate in the apparatus to be used for it. subsequent treatment. The mixture was heated one. hour at 100 to 140 ° C, after which the liberated attic acid was distilled off. In this sail, about 28 g of the mixed anhydride of boric acid and the peanut oil fatty acids were obtained. A mixture of this product and 73 g of linoleic fatty acid having an acid number of 198.6 and an iodine value of 137.1 was heated to 200-290 ° C according to Example 16 except that the distillation time had to be shortened from 30 to 10 minutes, since the product appeared to be highly viscous already. before distillation. The residue had an acid number of 43.9, a preselection number of 70.2 and an iodine number (Wijs) of 173.2.
Pa grund av produktens hoga viskositet var det omajligt att faststalla den exakta halten ofortvalbart material. Vid lufttorkning efter tillsats av ett bly-mangansickativ visade sig produkten bli beroringstorr pa 60 minuter och fullstandigt torr pa 80 minuter. Due to the high viscosity of the product, it was impossible to determine the exact content of non-digestible material. Upon air drying after the addition of a lead-manganese siccative, the product was found to be touch dry in 60 minutes and completely dry in 80 minutes.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor savida sickativen dadar voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for lacquers and varnishes, while the sedatives were built on the basis of cobalt, lead and manganese compounds.
Exempel 18. 165 g jordnotsoljefettsyra (syratal 197,7, jodtal 99,7). och 10 g bortriacetat upphettades 2 timmar till 150° C i en 500 ml kolv i en standardiserad vattenbestamningsapparat med hjalp av ett oljebad. Den frigjorda attiksyran avdestillerades och avlagsnades fran vattenavskiljaren. 50 ml dekalin ifylldes genom aterflodeskylaren. Eftersom 16 ml erfordrades for att fylla vattenavskiljaren, inkom 34 ml dekalin i rea.ktionskarlet. Example 18. 165 g of peanut oil fatty acid (acid number 197.7, iodine number 99.7). and 10 g of boron triacetate were heated for 2 hours at 150 ° C in a 500 ml flask in a standardized water determination apparatus using an oil bath. The released attic acid was distilled off and removed from the water separator. 50 ml of decalin was filled through the reflux condenser. Since 16 ml was required to fill the water separator, 34 ml of decalin was added to the reaction vessel.
Denna blandning kokades under aterflode och atmosfarstryck. Det frigjorda vattnet samlade sig i vattenavskiljaren, medan dekalinen aterflodade. Under avskiljning av 11 ml vat-ten och totalt cirka 15 ml dekalin steg blandningens kokpunkt langsamt, sa att upphett- ningsbadets temperatur var 250° C efter 2 timmar, 260° C under en timme och 270- 280° C under 30 timmar. Efter avslutad be-handling erh011s 140 g aterstod, som inneholl 9,8 ml kvarhallen dekalin. Denna Aterstod utgjordes av en losning och bade faljande egenskaper. Vardena mom parentes beteckna aterstodens egenskaper i franvaro av dekalin Syratal 9,8 (10,4) Fortvalningstal 16,(17,5) Jodtal (enligt Wijs' metod) 106,(113,1) Ofortvalbart material 79,0 % (83,8 %) Efter tillsats av 0,3 % bly och 0,02 % mangan i form av naftenatsickativ blev aterstoden torr gentemot berOring pa 6 timmar och fullstandigt torr pa 24 timmar Den erhallna produkten var lamplig sasom utgangsmaterial far lacker och fernissor sá vida sickativen darfor voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. This mixture was boiled under reflux and atmospheric pressure. The liberated water collected in the water separator, while the decal returned. During separation of 11 ml of water and a total of about 15 ml of decalin, the boiling point of the mixture rose slowly, so that the temperature of the heating bath was 250 ° C after 2 hours, 260 ° C for one hour and 270-280 ° C for 30 hours. At the end of the treatment, 140 g of residue were obtained, which contained 9.8 ml of decalcine. This Residue consisted of a solution and both falling properties. Vardena mom parentes denote the properties of the residue in the absence of decal Acid number 9.8 (10.4) Prevalence number 16, (17.5) Iodine number (according to Wijs' method) 106, (113.1) Non-digestible material 79.0% (83, 8%) After the addition of 0.3% lead and 0.02% manganese in the form of naphthenate leachate, the residue became dry to the touch in 6 hours and completely dry in 24 hours. The product obtained was suitable as starting material for paints and varnishes as far as leaching were built on the basis of cobalt, lead and manganese compounds.
Exempel 19. 20 kg destillerade talloljefettsyror med syratalet 194,3, fortvalningstalet 196,9, jodtalet (enligt Wijs) 131,5 och en hartshalt av 2 Vo upphettades med 0,4 kg borsyra av teknisk kvalitet i den apparat, som beskrivits i exempel 14, med mekanisk omroring under ett vakuum av 4-12 mm Hg. Temperaturen hojdes under 2 timmar till 230° C, pa ytterligare 10 timmar till 260° C och halls mellan 260 och 290° C under 14 timmar. De fettsyror, som avdestillerade, aterinfOrdes i karlet. Mot slutet av reaktionen avdestillerade endast ringa mangd fettsyror. Efter avslutad upphettning erhollos 17,5 kg aterstod, som tvattades med 5X20 kg hett vatten, tills borsyran avlagsnats. Aterstoden torkades sedan i vakuum och filtrerades med en filterpress. Example 19. 20 kg of distilled tall oil fatty acids having an acid number of 194.3, a prefalling number of 196.9, an iodine value (according to Wijs) of 131.5 and a resin content of 2 Vo were heated with 0.4 kg of technical grade boric acid in the apparatus described in Example 14, with mechanical agitation under a vacuum of 4-12 mm Hg. The temperature was raised for 2 hours to 230 ° C, for a further 10 hours to 260 ° C and kept between 260 and 290 ° C for 14 hours. The fatty acids which distilled off were reintroduced into the vessel. Towards the end of the reaction, only a small amount of fatty acids distilled off. After completion of heating, 17.5 kg of residue were recovered, which was washed with 5x20 kg of hot water until the boric acid was removed. The residue was then dried in vacuo and filtered with a filter press.
Den salunda erhallna produkten hade syratalet 6,0, fortvalningstalet 13,2, jodtalet (Wijs) 155,9, halt ofOrtvalbart 92,1 % och en viskositet av 91,5 pois vid 20° C. The product thus obtained had an acid number of 6.0, a preselection number of 13.2, an iodine number (Wijs) of 155.9, a content of 92.1% and a viscosity of 91.5 pois at 20 ° C.
Efter tillsats av 0,3 % bly och 0,02 % mangan i form av naftenatsickativ och utspadning med lattfotogen till en viskositet av 1,5 pois vid 20° C blev en film av denna produkt torr gentemot beroring pa 6 timmar och fullstandigt torr pa 8 timmar. After addition of 0.3% lead and 0.02% manganese in the form of naphthenate desiccant and dilution with light kerosene to a viscosity of 1.5 pois at 20 ° C, a film of this product became dry to the touch in 6 hours and completely dry in 8 hours.
Den erhallna produkten var lamplig sasom utgangsmaterial for lacker och fernissor sa.- vida sickativen dadar voro uppbyggda pa basis av kobolt-, bly- och manganforeningar. The product obtained was suitable as a starting material for paints and varnishes, insofar as the siccatives were built on the basis of cobalt, lead and manganese compounds.
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