DE1193934B - Process for the catalytic oligomerization of olefins or acetylenic hydrocarbons - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

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File number:
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C07c

German class: 12 ο - 19/01

1193 934
C15890IVb / 12o
3rd December 1957
June 3, 1965

Unsaturated compounds can be converted into polymeric compounds by various processes. Depending on the type of connection used and the measures taken, you can get low Polymers, e.g. B. dimers and trimers or high polymers obtained. In many procedures, too Polymers of various degrees of polymerization obtained next to one another. Some connections will stimulated by the action of heat or light without additional measures to polymerize, others require the use of polymerization initiators Systems. Such systems are e.g. B. radical formers, such as peroxides or azo compounds, which are also used in combination with redox components, cationic agents such as Boron fluoride and aluminum chloride, or anionic pathogens such as sodium amide.

Organometallic compounds such as aluminum alkyls and the alkyls of the alkali metals, alone or in combination with compounds of transition metals groups IV to VII of the Periodic Table are used. Finally are also combinations of compounds of the transition metals with reducing agents as initiating polymerization known.

Polymer compounds, which are produced by various processes, often have only low, however, there are often technologically valuable differences in their properties.

There has now been a process for the catalytic oligomerization of olefins or acetylenic hydrocarbons found at elevated temperatures and normal or elevated pressure, which thereby is characterized in that the oligomerization in the presence of water-soluble compounds of the Performs platinum metals as a catalyst.

The peculiar effect of these compounds of platinum metals seems to be due to the deforming effect to be based, which the atoms or ions of the platinum metals on C-C double or triple bonds exercise.

Particularly suitable platinum metal compounds are those of palladium and rhodium. Since the The effect of these compounds is of a catalytic nature, only small amounts of them are required. To When the reaction is complete, they can be separated from the polymers and recovered by known methods will.

Thermal oligomerization in the presence of platinum metal compounds alone produces predominantly Low molecular weight products in addition to low levels of high molecular weight substances.

Process for catalytic oligomerization
of olefins or acetylene hydrocarbons

Applicant:

Consortium for the electrochemical industry

G. m. B. H., Munich 25, Zielstattstr. 20th

Named as inventor:

Dr. Jürgen Smidt, Munich-Solln;

Dr. Walter Hafner, Furth, Post Deisenhofen;

Dr. Josef Sedlmeier, Munich

When the polymerization temperature is selected, temperatures of up to about 100 ° C. are generally used preferred. The pressure to be applied depends on the volatility of the respective unsaturated compound and their solubility in the polymerization medium. It is useful at high concentrations unsaturated compounds to work, unless special circumstances, such as. B. the discharge of Heat of polymerization, greater dilution required do.

The polymerization can be carried out in solution, emulsion, suspension or in the gas phase will.

With the method it is possible to achieve high conversions with short residence times, in many cases selective sales can be achieved.

example 1

2 g of palladium chloride are ^{dissolved in 2 cm 3 of} concentrated hydrochloric acid ^{with heating, 60 cm 3 of} glacial acetic acid are added and placed in a 500 cm ³ shaking autoclave with a glass insert. After injecting 55 atmospheres of ethylene, the mixture is heated to 90 ° C. for 10 hours. The pressure in the cooled autoclave is still about 25 atm. The gas which escapes when the pressure is released is passed through a trap cooled with acetone and solid carbonic acid, in which the butylene isomer mixture formed collects. To expel the gases dissolved in the glacial acetic acid, the mixture is finally heated briefly to 80 to 90 ° C. The product is distilled for purification. Yield: 12 to 15 g of butylene.

Example 2

2 g of palladium chloride are dissolved with 0.75 g of sodium nitrite in a little water with gentle heating.

509 578/425

The red-brown solution is evaporated at 6O ⁰ C in vacuum to dryness, and the residue is taken up in 25 ml methyl ethyl ketone. This solution is shaken as in Example 1 in a 500 cm ³ autoclave with a glass insert for 9 hours at 570 to 90 ° C. under an ethylene pressure of 52 atmospheres. The butylene yield is 5 g, while from the solution it is still about 0.5 g of a high molecular weight product can be obtained.

IO

Example 3

3 ml of a 1 molar aqueous solution of palladium chloride are filled with acetone to 50 ml, saturated at -60 ⁰ C with acetylene and stirred for 5 hours at 80 ° C in a glass lined autoclave. When the warm autoclave is relieved, an exhaust gas is obtained which, in addition to acetylene, contains 12 percent by volume butadiene and 3 percent by volume vinylacetylene. In addition to divinylacetylene and higher polymers, further amounts of these products are dissolved in the reaction mixture and can be separated off by known methods.

Example 4

2.5 g of palladium chloride are dissolved in 3 ml of hydrochloric acid and made up to 50 ml with glacial acetic acid. This solution is shaken for 3 hours at 8O ⁰ C under a pressure of 26 at propylene in an enamelled autoclave. The reaction solution is diluted with water and the polymerization products, mainly dimers, are extracted with benzene.

Example 5

2.2 g platinum (TV) -chlorwasserstorrsäure are dissolved in 50 ml of propionic acid and at 12O ⁰ C under a pressure of 80 at ethylene for 8 hours in a 0.5-1 autoclave shaken. About 15% of the ethylene is polymerized into a mixture of liquid hydrocarbons.

Example6

2.5 millimoles of platinum metal compound are dissolved in 50 ml of solvent and placed in a U-tube from Treated with acetylene 20 mm in diameter. The flow rate is 2 liters per hour. the Results can be seen from the table.

Example 7

The catalyst used is silica gel impregnated with 2.5 percent by weight platinum (IV) hydrochloric acid. 2.51 acetylene per hour are passed over 50 cm ^{3 of} this contact at HO ^{0 C.} 5% of the acetylene is converted to vinyl acetylene.

Example 8

3 g of palladium bromide are dissolved with 2.3 g of hydrobromic acid (40%) i ⁿ 75 ml of propionic acid and placed in a 0.5-1 shaken with glass insert. After about 50 atm of ethylene has been injected, the mixture is heated to 95 to 105 ° C. for 6 hours. When releasing the pressure in the autoclave and then distilling the solution, about 25 g of n-butylenes, 1.5 g of hexene isomers and about 0.5 g of bromination products are obtained.

Similarly, 0.98 g of lithium bromide and 2.9 ml of perchloric acid is obtained with a solution of 3 g of palladium (60%) in 75 ml of propionic acid by heating at 9O ⁰ C 16stündiges about 20 g butylene.

Example 9

Is heated in an O ^ -l shaken with glass panels 2 g of palladium chloride, 2 ml of concentrated hydrochloric acid and 60 ml of methyl ethyl ketone under an initial pressure of 50 ethylene at only 2 hours at 9O ⁰ C, then 4 hours at 100 ° C, as can be prepared from about 4 g of butylene are then isolated from the contents of the autoclave.

Example 10

1 g of rhodium oxide is dissolved in 2.3 ml of concentrated hydrochloric acid. Careful evaporation gives 1.2 g of RhCl ₃ H ₂ O therefrom. 0.5 g of this RhCl ₃ · xH ₂ O are dissolved in 60 ml of methanol and placed in a 0.5-1 shaking autoclave with a glass insert. After forcing in ethylene 50atü 6 hours at 6O ⁰ C is heated and then allowed to stand overnight at room temperature and then heated for a further 7 hours at 80 ° C. About 12 g of butylene are produced.

solvent React
functional Sales in% Di-
vinyl-
ace- Platinum metal
link tem-
pera-
door vinyl
ace style Dimethyl sulfoxide ⁰ C style 0.3 PdCl ₈ Ethyl alcohol 120 30.0 0.0 PdCl ₂ Propionic acid 80 0.5 0.2 LiPdQ ₃ Tetrahydrofuran 120 0.4 0.2 PtCl ₂ Nitrobenzene 60 2.4 0.3 PtCl ₄ Dioxane 120 0.7 0.3 PtCl ₄ water 100 1.5 1.8 H ₂ PtCl ₈ acetic acid 100 7.5 0.4 H ₂ PtCl ₆ Dimethyl sulfoxide 120 4.0 0.0 H ₂ PtCl ₈ Dimethyl sulfoxide 120 50.0 0.0 H ₂ PtCl ₈ water 150 38.0 0.1 H ₂ PtBr ₈ water 100 12.3 0.0 RhCl ₃ 100 0.8

60

Example 11

3 g of palladium bromide and 2.3 g of hydrogen bromide (40%) are dissolved in 60 ml of tetrahydrofuran and placed in a 0.5-1 shaking autoclave with a glass insert. After injecting 50 atmospheres of ethylene Heated to 100 ° C for 6 hours. About 17 g of butylene can then be isolated from the contents of the autoclave will.

Example 12

1.5 g of palladium bromide and 1.15 g of hydrogen bromide (40%) are dissolved in 80 ml of dioxane and poured into a Brought 0.5-1 shaking autoclave with glass insert. After injecting 60 atmospheres of ethylene, 6 hours 100 ° C heated. About 40 g of butylene can then be isolated from the contents of the autoclave.

Example 13

1.8 g of palladium chloride and 0.8 cm ^{3 of} hydrogen bromide (63%) are dissolved in 100 cm ^{3 of} glacial acetic acid and placed in a 0.5 l autoclave with a glass insert. After injecting 60 atmospheres of ethylene, the mixture is heated to 110 ° C. for 2 hours with shaking. Working up the contents of the autoclave gives about 22 g of butylene

and about 1 g higher polymers and halogenation products.

Claims (5)

Patent claims: 1. Process for the catalytic oligomerization of olefins or acetylene hydrocarbons elevated temperatures and normal or elevated pressure, characterized in that the oligomerization in the presence of Carries out water-soluble compounds of the platinum metals as a catalyst. 2. The method according to claim I _3, characterized in that the catalysts used are palladium compounds. 3. The method according to claim 1 and 2, characterized in that one works at a temperature range from 50 to 170 ⁰ C. 4. The method according to claim 1 to 3, characterized in that one at atmospheric pressure up to 30 atm. is working. 5. The method according to claim 1 to 4, characterized in that in solution, preferably in essentially non-aqueous solvents. Considered publications:
U.S. Patent No. 2,656,398.