SE182282C1

SE182282C1 -

Info

Publication number: SE182282C1
Authority: SE
Publication date: 1962-01-01

Description

Uppfinnare: A Herlow och C E Vrang Prioritet begard fran den 1 maj 1951 (Danmark) Estrar av flervarda alkoholer, exempelvis polyglycerol eller glycerol, och polymeriserade eller oxiderade eller bade polymeriserade och axiderade, omattade fettsyror ha funnit anvandning for emulgeringstekniska andamal, t. ex. [Or framstallning av plastiska fettemulsioner av typen vatten-i-olja,, lampade for bageritekniska andamal. Med de variationsmojligheter, som framstallningen av dessa estrar erbjuda, har det dock ofta visat sig vara svArt att anpassa emulgermedel av denna typ till olika av de anvandningsandamal, som erbjuda sig. Inventors: A Herlow and C E Vrang Priority requested from 1 May 1951 (Denmark) Esters of polyhydric alcohols, for example polyglycerol or glycerol, and polymerized or oxidized or both polymerized and oxidized, unsaturated fatty acids have found use for emulsifying purposes, e.g. [Or manufacture of water-in-oil type plastic fat emulsions, lamped for bakery technical purposes. With the possibilities of variation which the preparation of these esters offer, however, it has often proved difficult to adapt emulsifiers of this type to different of the uses offered.

Foreliggande uppfinning avser ett forfaringssatt att framstalla emulgermedel, genom vilka derma nackdel undanrojes. De nya emulgermedlen utgoras av modifierade estrar av polyglycerol eller glycerol och polymeriserade fettsyror med 8 kolatomer eller ddriiver i molekylen. The present invention relates to a process for producing emulsifiers by which this disadvantage is eliminated. The new emulsifiers consist of modified esters of polyglycerol or glycerol and polymerized fatty acids having 8 carbon atoms or derivatives in the molecule.

Forfaringssattet enligt uppfinningen bestar dari, att glycerol eller polyglycerol behandlas med mjalksyra under forestringsbetingelser och i sa ringa mangd, att en partiell ester av mjiilksyran och glycerol eller polyglycerol bildas, varefter denna partiella ester vidareforestras eller delvis omestras med polymeriserbara eller polymeriserade fettsyror, vilka innehalla 8 kolatomer eller darover i molekylen, resp. med glycerider eller polyglycerider av dylika syror, varvid forhallandet mellan glycerol eller polyglycerol, mjoksyra och lettsyra Or sadant, att slutprodukten kommer att innehdlla fria alkoholhydroxylgrupper, varefter produkten, om den innehaller polymeriserbara fettsyragrupper, scan icke aro polymeriserade i onskad grad, underkastas upphettning med eller utan oxidativ inverkan for polymerisering av grupper av detta slag. The process according to the invention consists in that glycerol or polyglycerol is treated with lactic acid under esterification conditions and in such an amount that a partial ester of the lactic acid and glycerol or polyglycerol is formed, after which this partial ester is further esterified or partially transesterified with polymerizable or polymerized fatty acids. carbon atoms or more in the molecule, resp. with glycerides or polyglycerides of such acids, wherein the ratio of glycerol or polyglycerol, soft acid and light acid Or such that the final product will contain free alcohol hydroxyl groups, after which the product, if it contains polymerizable fatty acid groups, scan not aro polymerized to the desired degree, without oxidative effect for polymerization of groups of this kind.

De genom forfarandet framstallda emulgermedlen ha vardefulla egenskaper, varvid i syn nerhet skola namnas deras okade hydrofilitet jamfort rued tidigare kanda liknande glycerider och den lagre viskositeten hos de emulsioner, som framstallts med deras hjalp. The emulsifiers produced by the process have valuable properties, notably their increased hydrophilicity compared with previously known glycerides and the lower viscosity of the emulsions prepared with their aid.

Med polymerisering av fettsyror avses harvid icke blott en egentlig polymerisering, som kan bringas att forsigga genom enkel upphettning, utan Oven, den s. k. oxidativa polymerisation som intrader, nar upphettningen verkstalles under genomblasning av luft eller syrgas och som i varje fall till en del icke är en egentlig polymerisation, utan Oven karakteriseras av att syre upptages av dubbelbindningarna, eventuellt under bildning av gyrebryggor median fettsyrekedjorna. Med fettsyror avses i allmanhet sadana [eta syror, amattade monokarbonsyror och langkedjade monokarbonsyror av annat slag, som i vanliga fall inga i fettamnen och som foretradesvis eller uteslutande besta av syror med 8 kolatomer eller darutover i molekylen. Dessa feltsyror anvandas enligt uppfinningen vanligen i blandning, t. ex. i den blandning, van i de forekomma i fettamnen av naturlig forekomst (ddribland oljor), eller i blandningar, som utvinnas av dessa genom lamplig fraktioniseringsbehandling, I. ex. kristallisation och varmpressning eller genom destillation. Dot avses a.ven fettsyror, framstallda av naturliga fettamnen eller oljor genom hydrering av i dessas fettsyraradikakr fOrekommande dubbelbindningar eller av en del av dessa, eller fettsyror, framstallda pa s. k. syntetisk vag, t. ex. genom oxidation av lampliga kolvaten. By polymerization of fatty acids is meant not only an actual polymerization which can be brought about by simple heating, but also, the so-called oxidative polymerization which occurs when the heating is effected by blowing air or oxygen and which in any case to some extent is not an actual polymerization, but Oven is characterized in that oxygen is taken up by the double bonds, possibly during the formation of gyre bridges median fatty acid chains. Fatty acids are generally understood to mean those acids, amate monocarboxylic acids and long-chain monocarboxylic acids of other kinds, which are usually not present in fatty substances and which preferably or exclusively consist of acids having 8 carbon atoms or more in the molecule. These field acids are usually used according to the invention in admixture, e.g. in the mixture used to occur in the fatty substances of natural occurrence (including oils), or in mixtures obtained therefrom by suitable fractionation treatment, I. ex. crystallization and hot pressing or by distillation. This also refers to fatty acids, produced from natural fatty substances or oils by hydrogenation of double bonds or in some of these, or in some of these, or fatty acids, produced in so-called synthetic vesicles, e.g. by oxidation of the suitable hydrocarbons.

Som exempel pa polymeriserbara fettamnen eller fettsyror kunna namnas sojaolja, senapsfroolj a, s o lro s fro olj a, ricinolj a, jordno tso lj a, sesamolja, bomullsfroolj a, valolj a och sillolj a, avensom valolja eller sillolja, som hydrerats i hogre eller lagre grad, samt deras fettsyror. Examples of polymerizable fatty substances or fatty acids are soybean oil, mustard oil, soybean oil, castor oil, peanut oil, sesame oil, cottonseed oil, whale oil and herring oil, as well as whale oil or herring oil, which are hydrogenated in higher lower grade, as well as their fatty acids.

Vid utfOrandet av forfaringssattet erhallas 2— — modifierade estrar, i vilka oxisyran ingar pa icke noga kant satt. In carrying out the procedure, 2 - - modified esters are obtained, in which the oxyacids are not exactly set.

Vid upphettning av glycerol eller polyglycerol med mj5lksyra i de sedvanliga for forest-ring anvanda mangderna under fOrestringsbetingelser, konstaterar man emellertid, att syratalet gar ned, och processen forloper pa det hela taget som en forestrings- eller omestringsprocess, t. ex. med hansyn till temperaturer, reaktionstid, mangdforhallande och vattenbortgang. However, when heating glycerol or polyglycerol with lactic acid in the amounts usually used for esterification under esterification conditions, it is found that the acid number decreases, and the process generally proceeds as a esterification or transesterification process, e.g. with regard to temperatures, reaction time, mass ratio and water loss.

Forfaringssattet skall i det foljande belysas med tillhjalp av utforingsexempel, som dock icke aro begransande for uppfinningen. The procedure will be elucidated in the following with the aid of exemplary embodiments, which, however, are not limiting of the invention.

Exempel 1. Example 1.

Glycerol foretras under sedvanliga foretringsbetingelser, t. ex. genom uppvarmning till 245-2600 i narvaro av en katalysator, exempelvis natriumhydroxid. Foretringen avbrytes, nar foretringsprodukten har en genomsnittlig sammansattning, svarande mot pentaglycerol-oktaglycerol. Darefter tillsittes mjolksyra i en mangd av t. ex. 10 % av polyglycerolmangden och behandlas under vanliga forestringsbetingelser. Om polyglycerolen salunda i fiirvag innehaller natriumhydroxid, är det ej nodvandigt att tillsatta en ytterligare forestringskatalysator, men i ovrigt kunna alla for dylika forestringsprodukter vanligen anvanda katalysatorer finna anvandning. Under uppvarmningen konstaterar man, att det bortgar vatten och att syratalet gar ned till ett Mgt varde. Den salunda erhallna prod ukten begagnas darefter for omestring med polymeriserad triglycerid under vanliga betingelser. For omestringen kan anvandas 10 delar av den med mjolksyra behandlade polyglycerolen pa 100 delar av den polymeriserade triglycerid en . Glycerol is preferred under customary etherification conditions, e.g. by heating to 245-2600 in the presence of a catalyst, for example sodium hydroxide. The etherification is stopped when the etherification product has an average composition corresponding to pentaglycerol-octaglycerol. Then lactic acid is added in a quantity of e.g. 10% of the amount of polyglycerol and is treated under normal esterification conditions. If the polyglycerol thus contains sodium hydroxide freely, it is not necessary to add an additional esterification catalyst, but otherwise all catalysts commonly used for such esterification products can find use. During the heating, it is found that it removes water and that the acid number goes down to a Mgt value. The product thus obtained is then used for transesterification with polymerized triglyceride under normal conditions. For the transesterification, 10 parts of the lactic acid treated polyglycerol of 100 parts of the polymerized triglyceride can be used.

Exempel 2. 100 delar glycerol och 0,7 delar natriumhydroxid foretras genom uppvarmning till 240250° G i koldioxidatmosfar under kraftig omroring, tills vattenbortga.ngen visar, att pentaglycerol bildats. 378 delar pentaglycerol och 112,5 delar mjolksyra forestras vid 110° C under omroring i vakuum under loppet av 9 timmar. Forestringsprocessen kontrolleras genom bestamning av fortvalningstal och syratal. Denna produkt betecknas i fortsattningen som pentaglycerolmjolksyraester. 90 delar pentaglycerolmjolksyraester omestras under omroring vid 220° C med 1000 delar sojaolja polymeriserad i vakuum vid 300° C till en viskositet av e:a 3000 Cp/50° G. Reaktionstid 5 timmar. Example 2. 100 parts of glycerol and 0.7 parts of sodium hydroxide are preferred by heating to 240,250 ° G in a carbon dioxide atmosphere with vigorous stirring until the water removal shows that pentaglycerol has formed. 378 parts of pentaglycerol and 112.5 parts of lactic acid are esterified at 110 ° C with stirring in vacuo for 9 hours. The esterification process is controlled by determining the prefalling number and acid number. This product is hereinafter referred to as pentaglycerol lactic acid ester. 90 parts of pentaglycerol lactic acid ester are transesterified with stirring at 220 ° C with 1000 parts of soybean oil polymerized in vacuo at 300 ° C to a viscosity of about 3000 Cp / 50 ° G. Reaction time 5 hours.

Exempel 3. 90 delar pentaglycerolmj olksyraester (se exempel 2) omestras med 1100 delar sojaolja i vakuum under omroring vid 200° C. Reaktionstid 3 timmar. Denna produkt polymeriseras i vakuum vid 300° C under loppet av 30 timmar. Reaktionsprodukten har en viskositet av mer an 1000 Cp vid ° C. Example 3. 90 parts of pentaglycerol lactic acid ester (see Example 2) are transesterified with 1100 parts of soybean oil in vacuo with stirring at 200 ° C. Reaction time 3 hours. This product is polymerized in vacuo at 300 ° C for 30 hours. The reaction product has a viscosity of more than 1000 Cp at ° C.

Exempel 4. 90 delar glycerol och 112,5 delar 80-procentig mjalksyra saint 0,5 delar natriumhydroxid forestras vid 110° G i vakuum under omroring under lappet av 6 timmar. Forestringsprocessen kontrolleras genom bestamning av fortvalningstal och syratal. Denna produkt benamnes nedan glycerolmjolksyraester. 110 delar glycerolmjolksyraester och 1000 delar sojaolja, soni är oxiderad till gelatine-ring yid 240° C och upplost i samma mangd opolymeriserad sojaolja, forestras vid 190° C i 8 timmar under vakuum. Example 4. 90 parts of glycerol and 112.5 parts of 80% lactic acid and 0.5 parts of sodium hydroxide are esterified at 110 ° C in vacuo with stirring for 6 hours. The esterification process is controlled by determining the prefalling number and acid number. This product is hereinafter referred to as glycerol lactic acid ester. 110 parts of glycerol lactic acid ester and 1000 parts of soybean oil, soni are oxidized to gelatinization at 240 ° C and dissolved in the same amount of unpolymerized soybean oil, esterified at 190 ° C for 8 hours under vacuum.

Den. enligt forfaringssattet framstallda produkten ar anvandbar fOr framstallning av goda emulsioner av typen vatten-i-olja, sarskilt sadana som lamps sig for bageritekniska andamal. Salunda kunna under anvandning av enligt uppfinningen framstallda estrar framstallas plastiska emulsioner for inrullning eller inknadning i deg, eller flytande emulsioner for sprutning eller smorjning av bakplatar eller baliformar, eller skiljeemulsioner fOr bakning av sammanklibbade (sammanskeddade) brOd. The. the product prepared according to the process is useful for the preparation of good emulsions of the water-in-oil type, especially those which are suitable for bakery technical purposes. Thus, using esters prepared according to the invention, plastic emulsions can be prepared for rolling or kneading into dough, or liquid emulsions for spraying or lubricating baking trays or baliforms, or separating emulsions for baking glued (joined) breads.

Harmed aro dock anvandningsomradena for de enligt uppfinningen framstallda estrarna icke uttomda, i det att forfaringssattets egentliga fOrdel mera generellt bestar dari, att med tillhjalp av detsamma stallas stabiliserande och emulgerande amnen till fOrfogande, vilka i jamforelse med de narmast motsvarande Hada amnena ha en modifierad sammansattning och modifierade egenskaper, sd att mOjligheterna att genom variation av sammansattningen erhalla specifika emulgeringseller stabiliseringsmedel fOr specifika andamal okas pa ett, sasom det visat sig, vardefullt satt. However, the fields of application of the esters prepared according to the invention are not exhaustive, in that the actual advantage of the process more generally consists in providing, with the aid of the same, stabilizing and emulsifying substances which, in comparison with the most similar modalities, have at their disposal and modified properties, so that the possibilities of obtaining specific emulsifying or stabilizing agents for specific purposes by varying the composition are increased in a way that, as it turns out, is valuable.

Claims

Patent claim: Procedure for the production of an emulsifier, with e.g. a. the property of being able to produce more fluid emulsions than other emulsifiers, characterized in that glycerol or polyglycerol is treated with lactic acid under esterification conditions and to such an extent that a partial ester of the lactic acid and glycerol or polyglycerol is formed, after which this partial ester is formed or partially transesterified with polymerizable or polymerized fatty acids, which contain 8 carbon atoms or more in the molecule, resp. with glycerides or polyglycerides and the like acids, the ratio of glycerol or polyglycerol, lactic acid and fatty acid being such that the final product will contain free alcohol hydroxyl groups, after which the product, if it contains polymerizable fatty acid groups which are not polymerized to the desired degree, subjected to heating with or without oxidative effect for polymerization of groups of this kind Stockholm 1963. Kungl. Boktr. P. A. Norstedt & Saner. 620080