DD144715A1 - NEW METHOD FOR THE PRODUCTION OF FOOD EMULSIFICATORS - Google Patents

Abstract

The invention relates to a novel process for the preparation of Emulsifiers, in particular of acyclic hydroxy acid esters of Monoglycerides of saturated and / or unsaturated fatty acids, for example, of lactic, tartaric, malic or citric acid esters, because of their surfactant properties in the application Find food industry. The acyclic hydroxy acid esters are intended be prepared under mild reaction conditions and a have high hydroxy acid content and good sensory properties. The problem is solved by the synthesis of the acyclic Hydroxy acid esters by controlled transesterification of Hydroxysäuremethylbzw. ethyl esters with monoglycerides in the presence of a maximum of 1% Sodium methylate is carried out as a catalyst. The glycerol content of Monoglycerides, optionally before with aqueous alkali chloride solution washed out, is a maximum of 0.5%. Monoglycerides. and Hydroxyalkyl esters, molar ratios of 1: 1 to 6: 1, be steered at 333 to 393 K 'and 1.33 to 26) 66 kPa maximum 2 h esterified. Subsequently, the catalyst with aqueous Hydroxyacid solution, preferably citric acid solution, inactivated. The transesterification products have a largely neutral Taste, a light color and a soft to waxy consistency.

Description

New process for the production of food emulsifiers.

Field of application of the invention

The invention relates to a novel process for the preparation of food emulsifiers, in particular of acyclic hydroxy acid esters of monoglycerides of saturated and / or unsaturated fatty acids, for example milk, wine,

, 5-cinnamic or citric acid esters which, owing to their surface-active properties, are preferred in the food industry, alone or in combination with other emulsifiers, especially as emulsifying, stabilizing, wetting and anti-spattering agents and for improving structure,

viscosity, volume and freshness of food are used «

Characteristics, the known., Tecteis ^ jiej ^ Xös ^ un ^ en

It is known, acyclic hydroxy acid esters of monoglycerides of saturated and / or unsaturated fatty acids by direct esterification of glycerol or _e epichlorohydrin

15Cydroxy acids and fatty acids at temperatures of 413 - 513 K and reaction times up to 12 hours without bzv? _ö with catalysts, such as B. p-Toluensuifonsäure, sulfurous acid or phosphonous acid, as well as by esterification of hydrocyanic acids in Monogiyceride bz-w _a in mixtures of

20Monoglycerides with fatty alcohols at temperatures of 373 - 463 K, preferably 383 - 413 K and reaction times up to 10 hours * preferably 2 hours to produce

addition, acetylated acyclic hydroxy acid esters, in particular Acetylcitronensäüre- and Diacetylweinsäuröester, of monoglycerides of saturated and / or unsaturated fatty acids by conversion of the corresponding hydroxy-Ssäureanhydride with monoglycerides at temperatures of 373-443 κ and reaction times up to 3 hours receive »Depending on the molar ratios used the starting materials and the reaction conditions used are products in the various synthesis variants

Formed in which the carboxyl groups of the hydroxy acids partially or completely esterified with the alcohol groups of the glycerides raind. Driving in the synthesis of partial esters of hydroxy acids with acidic reaction products

, a relatively high HLB value (> 8) are obtained

Although they are preferably used both in oil-in-water emulsions and as anti-splash agents in margarine, the total esters of hydroxy acids are characterized by a markedly lower HLB value (66) and are preferably found in UV / oil emulsions and, in particular, in US Pat Shortening shortenings

20dung, where they mainly affect impact, collection ability and Bnulsionsstabilität positive. Total esters of the hydroxy acids are according to DE / AS 1 _f 200.79.6 by conversion of 1 mol.Citronensäure with 3 moles of monoglyceride or «mixture monoglyceride / fatty alcohol at reaction temperature« = »

25turen 423-438 K ₉ low after the US / PS 3 ₉ 012,048 by reaction of 1 mole of glycerol with 1 mole of fatty acid and a maximum of 0.62 moles of lactic acid in the presence of small amounts of calcium oxide (max · 1%) at temperatures 458-5 "i; K and according to US / PS 3 , 029, H7 by esterification of sodium lactate with

Furthermore, US Pat. No. 2,970,055 discloses the short-term acidolysis of Eeutra.lfett with 0.1-3.0 % of milk or V / acid using Oj.sub.2-1 , 0 % Batriuminethylat at reaction temperatures up

35maxinial 473 K for the production of fully esterified hydroxy acid esters of moioglycerides described »

The known methods have the disadvantage that among the

- 3 - ZI 4

applied reaction conditions, such as temperatures of 373-513 K and reaction times up to 12 hours, not only total esters of the hydroxy acids used with monoglycerides or * fatty alcohols are formed, but 5s that in different quantities strongly acidic, insoluble by-products resulting in the Hydrosy acid content of In addition, the absolute content of esterified 1OHydroxyacid in the products produced by complete esterification, owing to the molar ratios of the starting substances, is relatively low.

invention

The object of the invention is the production of food emulsifiers, in particular of acyclic hydroxy acid

T5estem of monoglycerides of saturated and / or unsaturated fatty acids while avoiding high temperatures and long reaction times, wherein the food emulsifiers by a complete esterification of the carboxyl groups of Hydroxysäurenj by a .Hy hydroxy acid content and gua

Should characterize sensory properties,

The invention is the task? to develop a new process for the preparation of food emulsifiers, in particular of acyclic hydroxy acid esters of monoglycerides of saturated and / or unsaturated fatty acids,

According to the invention, the object is achieved by the synthesis of the acyclic hydrocysic acid esters by controlled transesterification of Hydrcxysäurealkyiestern with monoglycerides of saturated and / or unsaturated fatty acids in the presence of a Urueste-

The catalyst used for the transesterification reaction is Hat ri amme thy la t «

-.4 - y

According to the invention, a technical monoglyceride (ca _e 35 - 50 $> sodium monoglyceride), an enriched monoglyceride (ca · 55 - 75% hydrogen-Monoglyceriä) or a distilled monoglyceride (cs ₉ 80-95% sodium monoglyceride) 5gesättigter and / or unsaturated fatty acids with a methyl or ethyl ester of lactic, tartaric, malic or citric acid in the presence of a maximum of 1 % of sodium ethoxylate, which is previously suspended in the liquid glyceride phase, interesterified the reaction in favor of

1Oacyclisehen hydroxy acid ester of monoglyceride directed by constantly using methylene or »ethyl alcohol is removed from the reaction mixture by using reaction temperatures of 333 393 K and a vacuum of 1.33 - 26.66 kPa over a period of a maximum of 2 hours» The molar

Use ratio of the reactants monoglyceride and hydroxyalkyl acid ester is 1: 1 to 6: 1, preferably 1: 1 to 3 ί 1 ·

The monoglycerides are optionally used to remove glycerol admixtures by washing with an aqueous solution

20Alkalichlorid "Lösungj. pretreated preferably an Ilatriumchlorid solution and subsequent drying and thereby adjusted to a content of glycerol to a maximum of 0.5% "The used for the transesterification methyl or ethyl

Are 25eeter milk «·, Yfein-, malic acid or citric acid dur ^ ch esterification of the hydroxy acids with the corresponding alcohol in the presence of concentrated sulfuric acid as a catalyst and purified by distillation or crystallization _e" For the removal of the optionally in I

30den Hydroxysäurealkylestern remaining small amounts of "free hydroxy acid, dis inactivates the alkaline catalyst in the subsequent transesterification steered _8, a treatment of the dissolved in methanol or ethanol Hyäroxysäurealkylester with the strongly basic anion"

Exchanger lofatit SB? /, Which is previously converted into the bicarbonate form by pretreatment of the activated exchanger with carbon dioxide, takes place "The residual contents of free hydroxy acid thus obtained are converted into the hydroxy-

acid alkyl esters are below 0 _S 1 % " The course of the controlled transesterification can be monitored directly via the mass removal of the reaction mixture and via the determination of the distilled-off amount of alcohol." The reaction is carried out using the example of monoglyceride and methyl methacrylate. according to the formula as follows:

CH ₂ -OR CH -OH + < CH ₉ CH :) - Cooch IaOCH ₃ J 3 33 - 393 K ₅ 6h ₂ -oh CH " 1.33 - 26 , 66 kPa -0-R-OH + CHOOH -00C-CH (OH) -CH ₀

R κ fatty acid acyl radical

After completion of the transesterification, the catalyst is inactivated by addition of an aqueous citric acid solution. A process for the preparation of said hydroxyacid

The ester of monoglycerides was previously unknown. " It is surprising that under the given reaction conditions, the transesterification is unexpectedly simple and with high yields of acyclic hydroxy acid esters of monoglycerides and only with the formation of small amounts of fatty acid methyl "- or

The esterification products are characterized by a largely neutral taste, a light color and a soft to waxy consistency; * Compared with the partial ester products of hydrosilicic acids, prepared by esterification, the new method "

These products have a markedly improved antiulcer activity and a stronger interaction with amylose. By washing out the reaction products. with an aqueous alkali metal chloride solution, if necessary, small amounts of unreacted hydroxyacid

25 Alkyl esters and catalyst residues are removed »The process of the method is described in more detail in the following examples

9HhF; -13 / 3 * 81 2ii2

Atisfiihrungsbeispiele

Example 1: In a three-necked flask with KPG stirrer, boiling capillary and vacuum connection 1 mol of technical monoglyceride saturated and / or unsaturated fatty acids (monoglyceride content ca "50 %% glycerol content 0.4 %) with 1 mol of tartaric acid (free tartaric acid content ) in Presence of 0.5 % of sodium methylate suspended in the liquid glyceride phase, transesterified on a water bath at 253 K in a vacuum of 2.67 kPa in 2 hours. "To complete the esterification reaction

"The catalyst is inactivated by addition of 30 ml of a 25% aqueous citric acid solution. The reaction product has a neutral taste, a yellowish color and a soft paste consistency."

In game 2t In a three-necked flask with KPG stirrer, boiling I5kapillare and vacuum port 2 moles of distilled MoBoglycerid saturated fatty acids (monoglyceride content ca "ϊ 90% Glycerol content 0.3%) (containing 1 mole triethyl citrate content of free citric acid ^ 0.1 %) in the presence of 1 % sodium methylate previously suspended in the 2-oar glyceride phase, transesterified on the water bath at 373 K in a vacuum of 4.0 kPa in 2 hours. "To complete the esterification reaction, the catalyst is replaced by the addition of 65 ml of a 20 Inactivated Citric Acid Solution "After washing with a saturated solution of 25 sodium chloride, the reaction product has a neutral taste, a whitish color and a waxy consistency.

lSLi 19 / B

Claims (4)

Comply with ...; 1 »A new process for the preparation of Lebensniittelemulgatoren, in particular of acyclic hydroxy acid esters of monoglycerides of saturated and / or unsaturated fatty acids, for example of milk," Wein-, cinnamic or Citricensäureestem, characterized in that a technical, enriched or distilled monoglyceride saturated and / or unsaturated fatty acids, which may contain a maximum of 0.5 percent glycerol and is optionally pretreated, "with a hydroxyalkyl hydroxyalkylester in vacuum at 1.33 to 26.66 kPa and a temperature between 333 and 393 K within a few hours in the presence of 0.5 -1.0 percent sodium methoxide, which is previously suspended in the liquid · monoglyceride phase, using a molar ratio of monoglyceride to hydroxy acid alkyl ester of 1! 1 to 6: 1 _t preferably to 3: 1 transesterified, followed by the addition of an aqueous solution of a catalyst Hydroxy acid inactivated and the Reacti washed with an aqueous alkali chloride solution ", 2 · hay method according to item 1, characterized in that the monoglyceride for removal of glycerol admixtures by washing with an aqueous alkali chloride solution, preferably a sodium chloride = · solution, brought to a maximum glycerol content of 0.5 % and dried » ^F 3 * Hay method according to item 1, characterized in that the monoglyceride is preferably esterified with a methyl or ethyl ester of lactic, tartaric, cinnamic or citric acid, wherein in the polybasic acids all carboxyl groups are esterified over a period not exceeding 2 hours , preferably at 2.66 to 6.66 kPa and at 353 to 373 K, is reacted » 4. Hay process according to item 1, characterized in that the inactivation of the catalyst was preferably carried out with a solution of citric acid in water