CS256690B1 - Process for preparing a homogeneous mixture of phosphatide and bis (diacylglycerol) phosphoric acids - Google Patents

Abstract

The present invention relates to a process for the preparation of homogeneous mixtures of phosphatidic acid salts of bis (diacylglycerol) phosphoric acids. The essence of the solution is phosphorylation in two stages, whereby a first phosphatidic product is prepared by reacting diacylglycerols with polyphosphoric acids prepared in situ from phosphoric acid and phosphorus pentoxide, and further phosphorus pentoxide is dispersed in the phosphate acid prepared in this way. a fine dispersion in which a further portion of diacylglycerol is allowed to be added at elevated temperature to form an acidic product which, after neutralization, provides a homogeneous product which does not dissolve after prolonged storage. The products made according to the solution can be used as non-toxic emulsifiers and viscosity reducers in the production of foodstuffs in agriculture as well as in other industries.

Description

The present invention relates to a process for the preparation of homogeneous mixtures of phosphatidic and bis (diacylglycerol) phosphoric acid salts, consisting of two-stage phosphoryl diacylglycerols, in a first step from a portion of diacylglycerols producing a phosphatidic acid-rich intermediate in which phosphorous pentoxide is dispersed and homogeneous the residue of diacylglycerols is gradually admitted and the mixture is stirred at elevated temperature until the unreacted diacylglycerol content of the product is less than 10% by weight.

A mixture of phosphatidic and bis (diacylglycerol) phosphoric acids is today produced by phosphorylating diacylglycerol fatty acids with phosphorus pentoxide dispersed in triacylglycerols, e.g. AO 173 720. The products produced contain a high proportion of triacylglycerols and, when made from unsaturated acid derivatives, e.g. rapeseed diacylglycerols, are susceptible to excretion of a portion of the phosphorylated component upon storage because phospholipids are only slightly soluble in triacylglycerols. More concentrated products with a lower content of triacylglycerols can be prepared according to U.S. Pat. AO 203 421 phosphoryl diacylglycerols by dispersing phosphorus pentoxide in a mixture of phosphatidic and bis (diacylglycerol) phosphoric acids obtained in previous phosphoryl diacylglycerols. The disadvantage of such a process, however, is the volatility of these acids, which cannot be stored for extended periods of time without the risk of undesirable by-products.

These disadvantages are overcome by the process for the preparation of a homogeneous mixture of phosphatidic and bis (diacylglycerol) phosphoric acids according to the invention, in which in the first step an intermediate with a high phosphatidic acid content of 10 to 40 wt. parts of the starting diacylglycerol with an agent prepared at a temperature of 40 to 100 ° C from 1 to 5 wt. % of 70 to 90 wt.% of trihydrogenphosphoric acid; and from 1 to 8 wt. 4 parts by weight of phosphorus pentoxide and an acidic semi-product with a high phosphatidic acid content are dispersed. parts of phosphorus pentoxide to form a homogeneous, low-viscous suspension, to which a further 50 to 90 wt. parts of diacylglycerol heated to 40 to 90 ° C. The mixture is then reacted at 60-120 ° C to an unreacted diacylglycerol content of 5% by weight in the reaction mixture.

The diacylglycerols used can be derivatives of both saturated and unsaturated fatty acids having 10 to 24 carbon atoms per molecule, e.g. acylglycerols prepared from low and high erucic acid rapeseed oil, sunflower oil, peanut oil, palm kernel fat, coconut fat, palm oil oils, cottonseed oil, tallow, lard, hydrogenated vegetable and livestock oils and fats and other fatty raw materials. Diacylglycerols prepared by glycerolysis of triacylglycerols containing 10 to 30 wt. % monoacylglycerols and 20 to 40 wt. unreacted triacylglycerols as well as diacylglycerols obtained by other routes, e.g., esterification of fatty acids with glycerol and partial enzymatic cleavage of triacylglycerols.

Preferred feedstocks are also moieties resulting from the molecular distillation of monoacylglycerols and containing up to 85 wt. diacylglycerols. A different kind of diacylglycerols may be used in the preparation of the acid product in the first stage than in the second stage phosphoryl; for example, in the manufacture of lard-consistency products, a saturated acid derivative such as diacylglycerol from hydrogenated tallow or hydrogenated vegetable oils is used in the first step and an unsaturated acid derivative such as diacylglycerol from rapeseed oil is allowed in the second step. The acid products produced can be neutralized in a conventional manner prior to finalization, for example with ammonia gas, sodium, potassium, calcium, triethanolamine and other bases.

As can be seen from the following non-limiting examples, the phosphorylated products produced according to the invention (Examples 1 to 2) are homogeneous and contain more active ingredients than the products prepared by conventional methods (Examples 3 and 4).

Example 1

500 kg of diacid glycerols from hydrogenated tallow heated to 70 [deg.] C. were charged into a homogenizer equipped with active stirrers and 50 kg of phosphoric phosphoric acid were sucked under vacuum. After 5 minutes of emulsification, 50 kg of phosphorus pentoxide powder were sucked in with stirring. Within 10 min, the temperature in the reactor spontaneously increased to -95 ° C and was maintained at this level for an additional 40 min. After this time, the unreacted diacylglycerol content was 3% by weight. After cooling to 70 ° C, an additional 320 kg of phosphorus pentoxide was sucked into the homogenizer and after 5 min stirring the suspension was transferred to the reactor. During this time, the temperature of the suspension rose to 80 ° C. 3500 kg of rapeseed diacylglycerol were then metered into the reactor at a rate of 100 kg per minute. The temperature spontaneously increased to 97 ° C due to reaction heat. After the entire amount of diacylglycerol was metered in, the reaction mixture was cooled to 80 ° C over 30 minutes and neutralized by introducing 120 kg of ammonia gas. The produced lard consistency product was formed into blocks. It was homogeneous even after one year of storage and contained 3.8 wt. org. % phosphorus bound and only 2 wt. unreacted diacylglycerol.

Example 2

According to the method of Example 1, 250 kg of 75% by weight of phosphoric phosphoric acid were emulsified in 2000 kg of diacylglycerol from hydrogenated vegetable oils, m.p. The temperature of the reaction mixture rose to 80 ° C and was maintained at this temperature for 90 min. After dispersing an additional 150 kg of phosphorus pentoxide, the temperature rose to 92 ° C; the slurry was then transferred to the reactor and mixed therein with the flowing diacylglycerol from the hydrogenated tallow melting at 60 ° C previously heated to 70 ° C. The temperature during inflow of diacylglycerol rose to 115 ° C and dropped to 95 ° C after dosing 4000 kg in 30 min. After cooling to 80 ° C, the thus prepared mixture of phosphatidic and bis (diacylglycerol) phosphoric acids was then neutralized with 400 kg of calcium hydroxide after addition of 50 kg of water. The product was flocculated on cooled rollers at 70 ° C; was homogeneous even after 6 months of storage and contained 3.7 wt. % organic phosphorus and 5 wt. diacylglycerols.

Example 3 •

000 kg of a mixture of diacylglycerols of the same composition as in Example 1, i.e. 1,000 kg of hydrogenated tallow diacylglycerol and 3,000 kg of rapeseed oil were stirred at 440C with 440 kg of phosphorus pentoxide powder for 4 hours. After this time, the reaction mixture was cooled to 75 ° C and neutralized with 120 kg of ammonia gas. After cooling, the product was placed on 2 layers; bottom - approx. was a very viscous brown liquid containing 12.6 12.6 wt. phosphorus, upper brown liquid - approx. - contained only 0,9% w / w; % phosphorus and 16 wt. unreacted diacylglycerols.

Example 4

000 kg of rapeseed diacylglycerol at 90 ° C was phosphorylated with a suspension of 440 kg of phosphorus pentoxide dispersed in 900 kg of hydrogenated rapeseed triacylglycerol melting point 38 ° C. During the addition of the suspension to the present diacylglycerol, the temperature rose to 107 ° C. After 4 hours of reaction, the mixture in the reactor was cooled to 75 ° C and neutralized with 120 kg of ammonia gas. The medium viscous liquid product settled over two days after storage for 10 days. The lower solid layer - about 12 wt. - contained 12,5% w / w; % phosphorus and an upper liquid layer of 2.4 wt. % phosphorus and 8 wt. unreacted diacylglycerol.

Claims (1)

Process for preparing homogeneous mixtures of phosphatidic and bis (diacylglycerol) phosphoric acids by phosphorylating diacylglycerols of fatty acids containing 8 to 24 carbon atoms in the chain-linked fatty acid, characterized in that in the first step 10 to 40 wt. parts of the starting diacylglycerol heated to 40 to 100 ° C, emulsifying 1 to 5 wt. 70 to 90 wt. of phosphoric acid and, with stirring, 1 to 8 wt. % of phosphorus pentoxide and at least 90 wt. of the present diacylglycerol is added to the product 4 to 12 wt. 60 to 90% by weight of phosphorus pentoxide are added to the suspension at 60-90 ° C. parts of diacylglycerol heated to 40 to 90 ° C, and the mixture is then reacted at 60 to 120 ° C to an unreacted diacylglycerol content in the reaction mixture of 5 wt.