CS256689B1 - Process for the production of calcium salts of acidic phospholipids - Google Patents

Abstract

The solution concerns a method of producing calcium salts of acidic phospholipids by neutralizing the product of phosphorylation of fatty acid diacylglycerols with a dispersion of calcium hydroxide at elevated temperature. The essence of the solution is the gradual neutralization of the product with a molar ratio between phosphatidic and bis(diacylglycerol)phosphoric acids of 3:1 to 20:1 with a dispersion of calcium hydroxide in triacylglycerols, while the temperature of the reacting mixture does not exceed 100 °C. Calcium salts of acidic phospholipids can be used as biologically active and improving additives in the food industry, in agriculture and other industrial sectors.

Description

The invention relates to a process for the production of calcium salts of acidic phospholipids by progressively neutralizing the phosphorylation product of fatty acid diacylglycerols containing a mixture of phosphatidic acids (PA) and bis (diacylglycerol) phosphoric (BDP) calcium hydroxide dispersions at temperatures up to 100 ° C.

The preparation of calcium salts of phosphatidic and bis (diacylglycerol) phosphoric acids has so far been difficult to solve from a technological point of view and therefore they are not yet produced in the world. Said phospholipids are dissolved in the phosphorylation product in an aprotic medium consisting predominantly of triglycerides of fatty acids (TG). It is well known that in aprotic solvents, acids and bases do not ionize and therefore cannot interact with the transfer of protons to ionic salts. In addition, as the polarity of the environment decreases, the association of amphiphilic phospholipid molecules (PA, BDP) increases to form micellar formations in which acid groups are turned away from the solvent and their association is thus suppressed by steric effects. These are particularly evident at higher concentrations of bis (diacylglycerol) phosphoric acids, which by their bulky hydrophobic chains shield not only the polar group itself but also the phosphate groups of the lower-molecular phosphatidic acids.

In such systems, it is only possible to assume the presence of free-linking complexes between base (B) and acid (HA) formed without proton transfer, eg by hydrogen bridges (B ... HA). In the presence of small amounts of protogenic components (such as water or partial acylglycerols) and at lower temperatures, H-binding associates of different compositions may also form, e.g. (BH ^ ⁺ ^ .... A ^ ^) n, (ΒΗ (HA) and others. The formation of salts and the formation of loose complexes vary considerably in energy. While charge transfer is associated with the release of a considerable amount of heat, the formation of H-binding associates represents a substantially lower, virtually non-measurable energy benefit.

The amount of heat released during neutralization is therefore a measure of ionic salt formation.

The degree of neutralization, i.e. the ratio between proton transfer salts and looser complexes, is an important measure of product quality. The presence of acidic groups, whether free or complexed, results in poor stability, manifested by acid-catalyzed disproportionations of PA and BDP to undesirable by-products. In principle, neutralization to form more stable ionic salts can be achieved by adding more polar solvents to the system prior to neutralization, or by the addition of so-called proton vectors.

However, such solutions are both technologically and economically and chemically unsuitable.

Polar solvents would have to be non-toxic, inexpensive, easily removable from the product for intended applications (in the food and animal nutrition industries) and not react with any of the components of the system; such solvents, as far as we know, do not yet exist. Also, the addition of a plurality of proton vectors, such as water or lower organic acids, is not a very convenient route. Such vectors react with PA and BDP to produce less valuable products and greatly reduce the stability of the final product. Bases for preparing the calcium salts of phosphatidic and bis (diacylglycerol) phosphoric acids are calcium oxides, hydroxides and carbonates. >

The calcium oxide reacts only after conversion to the hydroxide by the addition of water, and some of the added water is adversely used in the above-mentioned side reactions. Also, calcium carbonate is not a suitable base? it is reactive only after the addition of water and, in addition, large volumes of carbon dioxide are formed during the reaction, which creates a very stable and voluminous foam. Calcium salts can also be prepared by reaction between PA + BDP and calcium acetate, but the acetic acid formed is difficult to remove from the product and at higher temperatures acetolysis of the bound fatty acids causes partial cleavage of the phosphate group from phospholipids.

These disadvantages are overcome by the process according to the invention, in which the product of phosphorylation of diacylglycerols of C 10 -C 24 fatty acids in a chain containing 30 to 80 wt. of phosphatidic and bis (diacylglycerol) phosphoric acids in a molar ratio of 3: 1 to 20: 1 and heated to 60 to 90 ° C are gradually added 20 to 60¾ (w / w) calcium hydroxide slurry in the 10 to 24 carbon chain triglycerides , at a temperature of 50 to 80 ° C at a rate such that the temperature of the reaction mixture does not exceed 100 ° C? after addition of total ^; the amount of suspension required for neutralization is then stirred at 70-95 ° C until neutral. Commonly manufactured products in which the ratio of PA: BPA is less than 3, (e.g.

AO 173 220 and 203 421) do not react under these conditions and form only acidic, poorly stable complexes. A higher content of more polar phosphatidic acids results in increased accessibility of the phosphate groups to the effect of the proton vector, in this case water molecules, which occlude common commercial types of calcium hydroxide.

Since the neutralization itself takes place only at the interface, perfect dispersion of the insoluble base in the triglycerides is advantageous. This form is also advantageously employed in controlled dosing of the neutralizing agent into the reacting mixture, thus allowing the temperature at neutralization to be maintained at an optimum level. In addition, the dispersing medium (TG) appropriately adjusts the viscosity of the product and allows it to be further processed to its final shape, for example by powdering on crystallization towers or by flocculation on cooled rollers or belts. The rapid rise in temperature after the addition of the calcium hydroxide dispersion to the mixture of PA and BDP suggests that salts with ionic bonding are formed.

By adding the slurry to the reactor, the temperature of the reaction mixture must not exceed 100 ° C, otherwise the reaction water is converted into steam and a large volume increase would result in part of the product leaking out of the reactor. Upon completion of the neutralization, the product is cooled to a temperature of about 10 ° C above the melting point and worked up to a suitable final form.

The invention is illustrated by the following non-limiting examples.

Example 1

Kg 1000 kg acidic phosphorylation product of diacylglycerols from hydrogenated tallow containing 80% by weight % of a mixture of phosphatidic and bis (diacylglycerol) phosphoric acids in a ratio of PA: BDP of ~ 10.3, 2 wt. % unreacted diacylglycerols, 2 wt. of free fatty acids and the remainder to 100% (w / w) of triacylglycerol are continuously metered in with stirring with a suspension of 110 kg of calcium hydroxide in 200 kg of triacylglycerol from hydrogenated rapeseed oil, melting at 38 ° C. The original acid product temperature of 80 ° C increased to 95 ° C during the 65 ° C hydroxide slurry addition and was maintained at this level for 1 hour after the addition of the total amount of suspension. The mixture was then cooled to 75 ° C and flocculated on a cooled roller. The product produced was neutral, homogeneous and contained 3.3 wt. % phosphorus and 4.2 wt. of calcium.

Example 2

According to the procedure of Example 1, 1000 kg of a phosphorylation product of diacylglycerol from partially hydrogenated rapeseed oil with a melting point of 36 ° C containing 40% by weight of water was neutralized. % of a mixture of PA and BDP with a molar ratio of 15: 1, 1 wt.%, unreacted diacylglycerols, wt. % of free fatty acids and 57 wt. triacylglycerol, by suspension of 80 kg of calcium hydroxide in 200 kg of triacylglycerol from the above hydrogenated rapeseed oil.

The temperature of the acidic product at the beginning of the neutralization was 70 ° C and gradually increased to 93-84 ° C during dosing, the reaction mixture was cooled to 45 ° C and filled into polyethylene film lined cartons, 2.0 wt. % phosphorus and 0.3 wt. of calcium.

To compare our procedure with neutralization as an example.

. temperature of the calcium hydroxide slurry 93 ° C. After stirring for 2 hours at a temperature after passing through a tempering homogenizer where it solidified to a homogeneous product containing other conditions, the following

Example 3

Kg 1 kg of phosphorylation product of the same composition as in Example 1 but with a PA: BDP 2: 1 molar ratio at 80 ° C was dosed with a suspension of 90 g of calcium hydroxide in 180 g of triacylglccerol from hydrogenated rapeseed oil. The suspension temperature was 70 ° C. During dosing of the suspension into the acidic product, the temperature did not rise, but gradually decreased to 77 ° C. Even after stirring for 2 hours under constant heating to 95 ° C, the reaction of the mixture was clearly acidic and after stopping the stirrer to the bottom of the glass reactor, unreacted calcium hydroxide particles sedimented. The clear top content contained 3.0 wt. % phosphorus and only 0.6 wt. of calcium.

The calcium salts of these phospholipids can be used as biologically active substances in the food and agriculture industries and as a special additive in the plastics industry.

Claims (1)

Process for producing calcium salts of acidic phospholipids, characterized in that to the phosphorylation product of C 10 -C 24 diacylglycerols of fatty acids in the chain containing 40 to 80 wt. % of phosphatidic and bis (diacylglycerol) phosphoric acids in a molar ratio of 3: 1 to 20: 1 heated to 60 to 90 ° C are added 20 to 60 wt. suppression of calcium hydroxide in the C 10 -C 24 triglycerides of the fatty acids of the chain at 50-80 ° C, the temperature of the reaction mixture not exceeding 100 ° C, then the mixture is stirred at 70-95 ° C until neutral.