DE2347224B2 - Calcium acid cis-epoxysuccinate and process for its preparation - Google Patents

Description

SP is. Alternatively, one can use an aqueous solution of acid, molybdic acid or the heteropolyacids of

fiv Either maleic acid or maleic anhydride and tungsten or molybdenum and the salts of these

fR ^. either calcium hydroxide or calcium carbonate acids, e.g. sodium tungstate, potassium tungsten!

3§§f ■ use whose pH value to a value of 2 to 4, sodium molybdate, phosphotungstic acid, phosphorus

Ift preferably 2.5 to 3.5, has been adjusted (and 5 molybdic acid or silicon tungstic acid. Of these

Preferably 2.5 b ,, (and 5 molybdic acid or silicon tungstic acid. Of these compounds, hereinafter referred to as an acidic calcium maleate solution, are sodium tungstate and potassium). The pH value is most preferred in this case wolframat. p by the molar ratio of maleic acid or the The catalyst is used in an amount of 2 · ΙΟ " ³

Maleic anhydride to the calcium compound loading to 10 10 ^"3 g-atoms, preferably 3 x 10 ~ ^a to jtiromt. A molar ratio of maleic acid or 10 · 7 ΙΟ- ³ g-atoms calculated as tungsten or Molyb-maleic anhydride to the calcium compound of 2 dan, per mole of hydrogen peroxide, (the pH being about 3) is most preferred- If the amount of catalyst used is less, test if the pH is higher than 4 or lower than 2 · 10 ~ ³ g- Atom, if the yield of acidic is kept than 2, a calcium cis-epoxysuccinate results in both cases that in the former case calcium cis should be used of more than 10 × 10 ^-3 g-atoms, re-epoxysuccinate (the normal salt) and in the latter case there is the danger that, if the catalyst is used, cis-epoxysuccinic acid is formed will. sator in an amount of more than 1 0 · 10 ^-3 g-atoms

Hydrogen peroxide is used in an amount of 1.5, a hydrolysis of the acid calcium cisfeis 2 moles per mole of the acidic calcium maleate an epoxysuccinate can occur, set. To the extent that the water used according to the invention becomes a reaction temperature

Itoffperoxyd amount less than 2 moles per mole of 50 to 70 ⁰ C, preferably 55 to 65 ° C, entered, decreases the amount of unreacted acid hold. If the reaction temperature is lower than calcium maleate in the liquid reaction product, 5O ⁰ C, a sharp drop of the Reakwas however, results is not a disadvantage, since the non-converted 25 tion speed. On the other hand, the acidic calcium maleate Reakletzte recycled and re-tion temperature exceeds 70 ⁰ C, can be carried Hydroterwendet. However, if the used lysis of the acidic calcium cis-epoxysuccinate calcium hydrogen peroxide amount is less than 1.5 moles per tartrate in a non-negligible amount of moles of the acidic calcium maleate, that is formed. Thus, the temperature range outside of the inventive amount of the remaining acidic calcium maleate 30 according to the temperature range -10 high, that the solubility of the acidic calcium cis- conditions is undesirable for practical reasons, epoxysuccinate is increased, which has the consequence, If the specified conditions are observed shows that a clear drop in the crystal yield per se a reaction time of 1 to 6 hours. Needless to say, acid calcium cis-epoxysuccinate causes the reaction time to be shortened at higher temperature. On the other hand, if a peroxide is used in an amount of more than 2 moles of the reaction temperature that is too low, set. If the hydrogen peroxide is used in excess of a relatively longer reaction time within the connection, the yield of the acidic given range increases. Calcium cis-epoxysuccinate, based on the water- That according to the method according to the invention

substance peroxide, from. Therefore, it is most preferred that the acidic calcium cis-epoxysuccinate is held in Hydrogen peroxide isolated in an amount essentially as follows. Crystallized according to the invention 2 moles per mole of the acidic calcium maleate borrowed the acidic calcium cis-epoxysuccinate from the liquid (i.e. essentially 1 mole of hydrogen peroxide per reaction product to the extent that the reaction g equivalent of the acidic calcium maleate). expires, out. The acidic calcium cis-Das which crystallized out Hydrogen peroxide is in the form of an aqueous 45 epoxysuccinate is separated and used added solution. In general, conventional solid-liquid separation processes, e.g. to do this, a 30 to 60 percent by weight solution. by filtration or centrifugation, 'isolated. Uie Gaseous hydrogen peroxide can also be used after the crystals have been separated from the liquid be turned. Liquid remaining in the reaction product (the liquid in the

As already mentioned, the reaction takes place after 5 ° which is referred to below as residual liquid the process according to the invention in aqueous solution can be recycled and reused sung. As the initial concentration of acidic calcium will be.

maleate in the solution of the acidic calcium maleate, to For the gain of the acidic ^calciu ^ ^CI ^ P? ^xy

to which hydrogen peroxide has been added (in the following, succinate in better yield from the liquid is referred to as the reaction solution), the reaction product is then cooled a concentration of 20 to 35 Ge Calcium-cis-epoxysucc.nats in water increases a lot by weight. On the other hand, the initial ring is greater than the solubility of the only Ca in the concentration of hydrogen peroxide as a result of maleate and of the catalyst in water; ™ ^rC ? ^ Possible the above-mentioned mole ratio to be observed 60 ledigl.ch by e.nfaches ^Kuhle "^"^{ss' gen} necessarily 3.5 to 8.5 weight percent. Reaction product ^d »» ^^^ SST

As a catalyst, succnate can be precipitated in the case of the invention. Therefore, it is; Do not use any epoxidation catalyst to concentrate the liquid reaction product in accordance with the process. Use Lor, which is soluble in water. Due As a cooling temperature, a temperature st the η ednge the greater water solubility and better than the 65 Reakt.onstemperatur but not .n> edng ^e j activity, the comparison given below 0 ° C is suitable. ^Au »PfJ ^ fS ^ ESSi biitangen are preferred as catalysts in which, however, a temperature of 10 to 25 C ^ o fin ^ emaßen method is used: Tungsten If the cooling temperature is lower than 0 C

takes the purity of the acidic calcium cis-epoxysuccinate away. The crystals of acid calcium cisepoxysuccinate, which have crystallized from the cooled liquid reaction product are in isolated in the manner described above. The residual liquid can also be returned in a circle and be reused.

As already stated above, the residual liquids mentioned are recycled and reused if necessary. When returning and reusing dL · back liquid, it is used as received or, preferably, boiled to convert the dissolved calcium cisepoxysuccinate to calcium tartrate which precipitates and is separated off. The residual fluids mentioned are, before they are returned and reused, mixed with fresh maleic acid or maleic anhydride and calcium hydroxide or calcium carbonate or the acidic calcium maleate, which were consumed in the first reaction, and possibly also with fresh catalyst and fresh water. The residual liquid is then reused after further addition of hydrogen peroxide.

Thus it is according to the method according to the invention possible without the use of complicated and extensive procedures acidic calcium cis-epoxysuccinate with high purity in good yields, not with the catalyst or with calcium cisepoxysuccinate is contaminated to produce. Furthermore, it is possible according to the invention, after the separation and isolating the crystals of the acidic calcium cis-epoxysuccinate from the liquid reaction product return and reuse any residual liquid.

When the crystals of acid caloium cis-epoxysuccinate obtained in this way are placed in an organic Solvents such as ethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane or 1,2-diethoxyethane, be subjected to acidic decomposition

Table I.

cis-epoxysuccinic acid is obtained smoothly. Continue to be by the acid hydrolysis of the acidic calcium cis-epoxysuccinate calcium tartrate and tartaric acid educated. .

It is thus possible, in a technically advantageous manner Way cis-epoxysuccinic acid or tartaric acid or the salts of these acids according to the invention Process to produce the acidic calcium cis-epoxysuccinate.

The following examples are intended to explain the invention further without, however, restricting it.

example 1

According to the method of the present invention, calcium acid cis-epoxysuccinate was obtained in the following Prepared manner using those given in Columns A, B or C of Table I below Reaction conditions. Maleic anhydride and the catalyst were in the following Table I specified amounts dissolved in 150 g of water, whereupon calcium hydroxide in the specified in Table I. Amount was added to give an acidic calcium maleate solution. This solution became then an aqueous 35.2 percent strength by weight hydrogen peroxide solution was added dropwise. After completion after the dropping, the reaction solution was heated, whereupon the reaction was continued until essentially no more hydrogen peroxide could be detected. The obtained liquid reaction product was then cooled to allow crystallization of acid calcium cis-epoxysuccinate promote that separated and isolated and washed with a small amount of water and dried became. The conditions met in this case are summarized in Table I below.

The impurities contained in the crystals of acid calcium cis-epoxysuccinate obtained in this way consisted essentially of calcium tartrate and a very small amount Water.

approach

Maleic anhydride
(Purity 100%) (g)
Calcium hydroxide
(Purity 99.7%) (g)
catalyst

Amount of catalyst (g)
Amount of aqueous hydrogen peroxide solution (g)
pH of the reaction solution
before the reaction (at 40 ° C)
Reaction temperature, ° C
Response time, hours
Cooling temperature, ⁰ CI hours

Purity of Acid Calcium Cis-Epoxysuccinate Crystals (g)
Yield of acidic calcium cis-epoxy succinate crystals (%)
Cis-epoxysuccinic acid residues in 3.4
the residual liquid
(calculated as acid calcium cisepoxysuccinate in g)

49.0 53.9 18.6 20.4 Phosphotungstic acid
[H ₃ (PWi ₂ O ₄₀ ) -3OH ₂ O]
0.513
48.3 Sodium molybdate
(Na ₂ MoO ₄ · 2H ₂ O)
1.161
48.3 2.83 3.42 70 x 1.5
15th
96.8 50 x 1.5, then
55 · 2.5
20th
99.1 70.8 70.0 3.4 6.0

58.8
22.3

Sodium _{Phosphomolybdate Na 3} (PMOj ₂ O ₄₀ ) - 10 H, O
0.414
48.3

3.15
60-3

25th
99.7

64.4
8.8

The analytical values obtained using the conditions given in column B of table I. Crystals of acid calcium cis-epoxysuccinate are summarized in Table II below.

Table II By S Measured 170.9 Theore value table 9.36 value I. 169.1 i
I. Neutralization equivalent 11.83 (g / g equivalents) 9.46 r Epoxy oxygen content / C 28.2 C. (Weight percent) \ H 3.1 11.85 I. Calcium content game 2 I. (Weight percent) 28.4 ι Elemental analysis 3.0 ! (Weight percent) fr

By dissolving 58.8 g maleic anhydride and 0.792 g sodium tungstate (dihydrate) in 150 g Water and adding 22.2 g of calcium hydroxide, an aqueous acidic calcium maleate solution was prepared. This aqueous solution had a pH of 3.0. While stirring this solution were at 60 ° C 48.6 g of a 35 weight percent aqueous Hydrogen peroxide solution was added dropwise over 15 minutes to start the reaction to put. The reaction was then carried out at 60 ° C for 3 hours including the dropping time, to completely implement the hydrogen peroxide. Thereupon it became the liquid reaction product cooled to 25 ° C to bring acidic calcium cisepoxysuccinate to crystallize, the dinn was filtered off, washed with a small amount of water and dried. That way 77.7 g of acid calcium cis-epoxysuccinate (dihydrate) were obtained with a purity of 99%.

95% by weight of the total residual liquid was under reduced pressure at 40 ° C concentrated, whereupon 48.1 g of maleic anhydride, 0.0792 g of sodium tungstate (dihydrate) and 18.2 g of calcium hydroxide were added so that the total weight of the charge was the same as that at the first reaction used. This solution had a pH of 2.3. This solution was given then dropwise 48.6 g of an aqueous 35 weight percent hydrogen peroxide solution, whereupon the Experiment was continued in the same manner as described above and using 75.7 g of acid Calcium cis-epoxysuccinate (dihydrate) was obtained in the form of crystals with a purity of 95%.

Example 3

The first reaction was repeated in the same way as described in the first half of Example 1, whereby the crystals of acid calcium-cis-

ao epoxysuccinate were isolated and whereupon the total amount of residual liquid by boiling was concentrated for 3 hours. The crystals that appeared on standing overnight at room temperature had failed, were with a minor

as amount of water washed and dried, whereby one 7.9 g of crystals were obtained. They consisted of calcium tartrate (tetrahydrate) with a purity of 99%.

To that remaining after the calcium tartrate crystals were obtained by the above treatment Liquid was added 47.6 g maleic anhydride, 19.1 g calcium hydroxide and water, so that the total weight the feed was the same as that used in the first reaction. In in this case no additional catalyst was added. The pH of this solution was 3.0. to 48.6 g of an aqueous 35% by weight solution were added to this solution Hydrogen peroxide solution and repeated the example in the same way as described above, 75.9 g of acid calcium cisepoxysuccinate in the form of crystals with a purity of 98% and 10.5 g calcium tartrate (Tetrahydrati crystals obtained with a purity of 99%.

Claims (2)

Sodium tungstate, also at the same time from what claims: has the consequence that the disodium epoxysuccinate is also contaminated with this material, with 1. Calcium acid cis-epoxysuccinate. In addition, a loss of catalyst sets in. 2. Process for the preparation of acidic 5 To the disodium calcium cis-epoxysuccinate obtained in this way according to claim 1, da- epoxysuccinate is added to form the barium, characterized in that acidic calcium epoxysuccinate is added barium chloride, dissolved in hot maleate and hydrogen peroxide in aqueous water are added. Solution in the presence of a water-soluble epoxy- However, since the disodium epoxysuccinate with dation catalyst converts. io impurities is dirty is an impurity of the barium epoxysuccinate is also not avoid. According to the method according to the invention The invention relates to the acidic calcium cis-epoxy-containing acidic calcium cis-epoxysuccinate is, as succinate and a process for its preparation already indicated above, a new compound with the following properties:
Hydrogen peroxide. Acid calcium cis-epoxysuccinate is a substance that bummenformei: used as the starting material for the production of ice- Ca (C ₁ H ₃ O ₅ ) ;, (The crystals usually lie Epoxysuccinic acid and its salts or wine ao in the form of the dihydrate),
acid and its salts can be used. The _ . , cis-epoxysuccinic acid and its salts are valuable t-ormelgewicnt:
full starting materials for production crosslinked 302.21 (dihydrate: 338.24). polymerizates or for the production of organic acids. On the other hand, tartaric acid and 25 properties of the dihydrate
their salts are excellent as acidulants for
Beverages or used as industrial chemicals Appearance:
will. White crystals. So far, the normal _f ^ of the epoxysuccinates
Salts such as the disodium salt and the barium salt 30 transition points:
known of epoxysuccinic acid. At 165 ⁰ C the crystal luster disappears, and As a process for the production of epoxysuccinates it is released heat that even at 185 ° C a method is known so far which consists in developing, that by using maleic acid as, The starting material is the disodium salt of the epoxy amber- 35 drainage points: stinic acid and from the disodium salt of the At 194 and 198 ° C heat is absorbed, Epoxysuccinic acid is the barium salt of the epoxysuccinic acid and at the same time there is a loss of weight. stinic acid (compare e.g. that of GB .....
Payne and PH Williams in The Journal Solubility: of Organic Chemistry ”, Vol. 24, p. 54, 1959, loading 40 At 25 ⁰ C, 0.68 g of the material dissolves in 100 g of the described method). With this well-known water Maleic acid and hydrogen peroxide will drive in an aqueous solution in the presence of sodium- The invention is based on the surprising solid tungstate as a catalyst, after you adjust the pH, that you get the new sub-value according to the invention with an aqueous sodium hydroxide solution 45 punch, namely the acidic calcium cis-epoxysuccinate brought to 4 to 5.5, converted to the epoxy by epoxidation of acidic calcium maleate with dation to achieve the epoxysuccinate. This hydrogen peroxide can be obtained, the soluble epoxysuccinate are finally given to the training speed of the acidic calcium cisvone according to the invention Disodium epoxysuccinate an equivalent of sodium epoxysuccinate in water is much less than that hydroxide. Since the disodium obtained in this way - 5 ° of the acidic calciepoxysuccinate used as starting material is soluble in water, must be abummaleate. separation of this substance in the form of crystals, the object of the invention is therefore to reduce the acidic an extensive process can be used to create the calcium cis-epoxysuccinate and one consists in specifying the reaction product multiple process for its preparation in highly pure liquid under reduced pressure 55 form with good yields, without the at 40 ⁰ C concentrated on and acetone added. Further application of a complicated and extensive process is required in this procedure due to the fact that the procedure is carried out.
matter that the product obtained, disodium epoxy- The invention thus relates to the acidic calcium cis- succinate, is contaminated by any unreacted Na epoxysuccinate and a process to its Hertiiummaleate, hydrogen peroxide in 60 position, which is characterized in that one corresponds to an amount 1.2 times the stoichiometric acid calcium maleate and hydrogen peroxide in amount, ie 1.2 times the molar aqueous solution in the presence of a water-soluble amount of maleic acid, used. Thus the epoxidation catalyst is implemented.
Yield of disodium epoxysuccinate, based on the starting material in the invention Hydrogen peroxide, lower. Furthermore, when 65 acidic calcium maleate is used in accordance with the procedure, it falls the liquid reaction product is concentrated and can be a material that reacts with either calcium Concentrate for the precipitation of dinalrium epoxy hydroxide or calcium carbonate from either maleic succinate Poured in acetone, the catalyst, acid or maleic anhydride has been made