DE928645C - Process for the production of dialdehydes or their conversion products from diolefins - Google Patents

Description

Process for the production of dialdehydes or their conversion products from diolefins It is already known that compounds with two unconjugated olefinic double bonds on both double bonds carbon oxide and hydrogen can accumulate if they are under in the presence of cobalt or other catalysts Treated with carbon dioxide and hydrogen under suitable pressure and temperature conditions will. So far, however, either the yields of divalent derivatives have been here low or the primary reaction products not detectable.

The addition of carbon monoxide and hydrogen to diolefins takes place thus either only or predominantly only on one of the two double bonds. For this Basically, either the formation of dialdehyde completely or partially does not occur (cf. z. B. FIAT report IOOO, p. 3I), or the reaction conditions are so unfavorable that initially formed dialdehydes, which are known to be very sensitive substances react further to form resins (FIAT Rev., Vol. 36, I, pp. I68, I948).

It has been found that one can obtain either a comprehensive or a complete Formation of dialdehydes from diolefins also achieve undesirable secondary reactions these sensitive substances can be prevented if the water gas accumulation in Presence of diluents, polymerization inhibitors and stabilizers with cobalt compounds providing cobalt carbonyl hydrogen, possibly in the presence of metallic cobalt or iron.

Surprisingly, aromatic hydrocarbons are used as solvents for this, substituted aromatics and hydroaromatics are particularly suitable.

In contrast, aliphatic hydrocarbons perform in some Cases instead of resinifying to monomeric dialdehydes under otherwise identical conditions Dialdehydes.

An initial polymerization of the diolefins used can be by adding metallic cobalt or iron in the form of powder, rasps, shavings or prevent it in another sufficiently divided form. It was unforeseeable that, in contrast, the addition of nickel severely impair the formation of aldehydes can.

The most important condition that arises to obtain the primary Dialdehyde is required, consists in maintaining a sufficiently low level Reaction temperature. When used as a catalyst, for example, cobalt in finely divided form and reduced state is used for water gas attachment, then the reaction temperature lie below 1200, while above this temperature, e.g. B. at I40 bis I500, resinification occurs. If other catalysts are used for the water gas attachment, z. B. aqueous cobalt sulfate solutions, then the temperatures are generally slightly higher, for successful dialdehyde formation, for example at I40 to I50 °, while at much higher temperatures there is a risk that the olefins or the aldehydes formed show hydrogenating side reactions.

It has proven to be very advantageous for the mixture of substances used Add inhibitors which stabilize the dialdehydes formed. Therefor are z. B. aromatic oxy compounds, such as hydroquinone, are suitable.

While, according to the literature, diolefins in the oxo synthesis so far no dialdehydes or diols or at most 15 to 35,010 yield of these Compounds provided are achieved using the procedure of the invention Yields of dialdehydes or their desired derivatives of at least 50%, often also of 70% and more.

If the aldehydes are to be obtained as such, one submits the crude reaction products for the purpose of removing the dissolved metal and for cleavage any acetals that have formed are expediently treated with pressurized water. Do you want the aldehydes Hydrogenate immediately afterwards to diols, so the aforementioned pressurized water treatment can be combined in one operation with the hydrogenation.

Example I In a 2.3 l autoclave with a magnetic stirrer was provided, 500 ccm of a reaction mixture were charged, which consists of 200 ccm Dicyclopentadiene stabilized with 0.2 g hydroquinone, 300 cc benzene and 200 ccm of an aqueous solution containing 15 g cobalt per liter as cobalt sulphate and 30 g of magnesia (MgO) contained in the form of magnesium sulphate. About this mixture 3 g of Ferrum reductum were added. The autoclave was then closed and from a steel bottle of water gas, which for 1 part of carbon dioxide is 1.2 parts of hydrogen contained, initiated up to a pressure of 180 ast. After that, the stirrer was used switched on and the heating of the autoclave started. At one temperature from 1400 no further increase in pressure could be observed, rather it occurred a pressure drop.

Within 120 minutes, an - was present in the autoclave free gas space of 1.3 1 104 at water gas added, of which in the first 30 minutes about 50 at.

After the uptake of gas had ended, the autoclave was cooled, the reaction product was separated from the catalyst solution, mixed with 66 01o of its volume of water and heated to about 200 ° within the autoclave for 1 hour. Here were something existing acetals are split and the metal carbonyls in solution are precipitated. After the water had been separated off, the reaction product was distilled. After Abortion of the solvent was obtained at a pressure of 10 mm Hg between 165 and 175 ° the main fraction in the amount of 60 percent by weight of the dicyclopentadiene used.

This main fraction had the following key figures: Density ................ D20 = I, I22 refractive index ......... n20 = 1.5238 molecular weight ...... .. D = 210 iodine number ................ JZ = 19 neutralization number ...... NZ = 0.5 ester number X EZ = 39 hydroxyl number OHZ = 43 carbonyl number ... . COZ = 435 On the basis of this number, the reaction product had the composition shown in the table below: Weight mole fractions body percent weight JZ COZ OHZ EZ JZ COZ OHZ EZ 12.1 unsaturated monoaldehyde ...... 162 157 345 - - 19 41 - - 67.4 dialdehyde ..................... 192 0 584 - - 0 394 - - 7.5 diol .......................... 196 0 0 572 - 0 0 43 - 13.3 Ester (double dialdehyde) ...... 384 0 0 0 292 0 0 0 39 100.3 214 - - - - 19 435 43 39 on average EXAMPLE 2 The batch used according to Example 1 was separated from the catalyst solution by decanting after the uptake of gas had ended and again filled into the autoclave which had previously been charged with 50 cc of reduced nickel hydrogenation catalyst and 200 cc of water. At about 150 atmospheres of hydrogen pressure, the reaction mixture was treated at 160 to 2000 until the pressure remained constant.

When the hydrogenation was complete, the oily components became from the water and separated from the catalyst and then distilled. Was used for distillation an apparatus working with short distillation paths and a heatable receiver used.

After the benzene had been separated off, the following fractions were obtained: Bis 180 "at 2 mm Hg 20 weight percent monol with about 250 /, diol, from 180 to 2100 at 2 mm Hg 56 percent by weight diol, from 210 to 230 ° at 2 mm Hg 6 percent by weight Diol with about 20,010 ester, about 2,300 at 2 mm Hg 18 weight percent more resinous Residue consisting of esters, aldols, etc. The overall yield of diol was to approximately 65 percent by weight.

Example 3 With the aid of the apparatus used in Example I were 500 ccm dicyclopentadiene-benzene mixture, which is divided into 2 parts by volume of dicyclopentadiene 3 Part of the volume contained benzene and was stabilized with 0.1 o, IO /, hydroquinone, below Use of 100 cc of reduced cobalt-magnesia-kieselguhr catalyst among the Treated the reaction conditions used in Example I with water gas. The catalyst contained 10 parts magnesia and 200 parts kieselguhr per 100 parts of cobalt. Already at 1000 gas uptake occurred so that a temperature of 1100 was not exceeded needed to be. With a free gas space of 1.51 that remained in the autoclave was, twice as much water gas was injected that a pressure of I50 kglqcm was created. This pressure decreased twice within 30 minutes to 100 kg / qcm, so that a total of an amount of gas was absorbed that was below the pressure of 100 kglqcm water gas gas space of 1.5 1 corresponded. After this Cooling to 60 °, the gas was blown off and the reaction mixture with 200 ccm of water charged, which was pressed in by means of nitrogen. With stirring, the reaction mixture was then heated to a temperature of 180 "and 30 minutes at this temperature left.

After cooling, the reaction product was separated from the water and hydrogenated as in Example I.

The distillation carried out according to Example I gave the following Products: Up to I80 "at 2 mm Hg 20 weight percent monol with 20 oils diol, from I80 up to 2100 at 2 mm Hg 37 weight percent diol, from 210 to 2300 at 2 mm Hg 6 weight percent Diol with 20% ester, above 230 ° at 2 mm Hg 37 percent by weight ester, aldols, resins.

Claims (6)

PATENT CLAIMS: I. Process for the preparation of dialdehydes or their conversion products from diolefins by catalytic water gas attachment to both double bonds, characterized in that the water gas attachment in Presence of diluents, polymerization inhibitors and stabilizers with cobalt compounds providing cobalt carbonyl hydrogen, optionally in the presence of metallic cobalt or iron. 2. The method according to claim I, characterized in that as a diluent aromatic or hydroaromatic hydrocarbons are used. 3. The method according to claim I and 2, characterized in that at Use of non-metallic cobalt compounds that serve as a catalyst should, cobalt or ferrous metal in the form of powder, filings, turnings, sheet metal or added in another sufficiently widely divided form. -4. Method according to claim 1 to 3, characterized in that as Stabilizers organic or aromatic dioxy compounds, especially hydroquinone, to be used. 5. The method according to claim I to 3, characterized in that at Use of metallic cobalt or reduced cobalt compounds Catalysts the water gas accumulation between 100 and 120 "is made. 6. The method according to claim I to 5, characterized in that the Aldehydes with the help of water at 160 to 2000 at the same time of their metal content and their acetals content.