CS258552B1 - A method for producing oligomeric highly unsaturated cyclic hydrocarbons - Google Patents

Abstract

A method for producing highly unsaturated cyclic hydrocarbons of the general formula (C3H4)n, where n is 3 to 10, by catalyzed co-oligomerization of propadiene and propyne in an organic solvent with the exception of tertiary amines and solvents containing active hydrogen at a temperature of 20 to 150 °C, at a pressure of 0.1 to 20 MPa, at a molar ratio of the amount of catalyst to the total amount of monomers of 0.001 to 1.0, while excluding the presence of more than an equimolar amount of oxygen and water to nickel, consisting in using a zero-valent nickel complex of the Ni(ligand)4 or Ni(ligand)3 type as a catalyst, where the ligands can be monodentate or bidentate unsaturated hydrocarbons, or organic phosphines or phosphites, or using a two-component catalytic system of a zero-valent nickel complex with hydrocarbon ligands - organic phosphine or phosphite, or using of a three-component catalytic system, a compound of divalent nickel - organic phosphine or phosphite - reducing agent, wherein propadiene and propyne contained in the residual pyrolysis C3 fraction are used for the co-oligomerization so that they are selectively reacted from this mixture. A mixture of highly unsaturated cyclic hydrocarbons of the general formula (C3H4)n, where n is 3 to 10, prepared by the method according to the subject of the invention is suitable as a starting raw material for the production of drying oil substitutes.

Description

The invention relates to a process for the production of oligomeric highly unsaturated cyclic hydrocarbons of the general formula where n is 3 to 10, by catalyzed co-oligomerization of propadiene and propyne contained in the residual pyrolysis fraction.

It is known that the pure hydrocarbons propadiene and propyne can be co-oligomerized to form highly unsaturated cyclic hydrocarbons of the general formulas (CjH^)^ and (C^H^)^ (J. Amer. Chem. Soc. 81,

250 (1959)) under catalysis by nickel compounds with weak acids having a dissociation constant of less than 9.10 ^-10 (British Pat. No. 802,350) or by nickel carbonyl phosphite complexes of the general formula Ni(CO) _m ^p (° ^R 3>4-ni' Where ^{R 9e and} -'-Kyl or aryl am takes the values 1, 2 or 3 (US Pat.

943 116) .

The current methods for preparing oligomeric highly unsaturated cyclic hydrocarbons of the general formula (C^H^), where n is 3 to 10, by the co-oligomerization of propadiene with propyne start from a mixture of pure monomers. This fact is a disadvantage, since the isolation of pure propadiene and propyne or their mixture significantly increases the production costs.

This disadvantage is eliminated by the method according to the invention, which allows the use of propadiene and propyne contained in the residual pyrolysis C1 fraction directly as raw material, by selectively reacting these monomers.

The residual pyrolysis fraction in the sense of the invention is understood to mean a mixture of hydrocarbons containing three carbon atoms in the molecule, which is obtained as a distillation residue after the isolation of propene in its production by pyrolysis of crude oil. This residual pyrolysis Cj fraction usually contains as main components propane (25 to 50%), propene (5 to 25%), propadiene (10 to 20%), propyne (10 to 40%) and a small amount of butane and butenes. Of this mixture of hydrocarbons, only propadiene and propyne react, the other components were not found to be involved in the reaction.

It has been found that the preparation of oligomeric highly unsaturated hydrocarbons of the general formula (C-jHPn, where n is 3 to 10, catalyzed by the co-oligomerization of propadiene and propyne contained in the residual pyrolysis fraction can be carried out selectively in a suitable solvent, which is an organic solvent with the exception of tertiary amines and solvents containing active hydrogen, preferably in an aromatic solvent or cyclic ether, particularly preferably in a crude mixture of products.

It is possible to use a batch or flow-through arrangement, preferably a stirred isothermal reactor bubbled with the residual pyrolysis fraction.

The preparation of highly unsaturated cyclic hydrocarbons of the general formula (υ ₃ Η^) _η , where n is up to 10, by catalyzed co-oligomerization of propadiene and propyne contained in the residual pyrolysis Cj fraction can be carried out at a pressure of 0.1 to 20 MPa, preferably at autogenous pressure in a batch configuration or atmospheric pressure when using a stirred isothermal reactor bubbled with the residual pyrolysis fraction. The reaction can be carried out at temperatures of 20 to 150 °C, preferably at 40 to 110 °C.

It has further been found that the reaction proceeds at molar ratios of the amount of catalyst to the total amount of monomers from 0.001 to 1.0, preferably from 0.001 to 0.05, the essential condition being the absence of more than equimolar amounts of oxygen and water to nickel during the preparation.

As a catalyst, it is possible to use a nickel complex in a zero oxidation state of the type NiL^ or NiLj, where it denotes four monodentate or two bidentate or one bidentate and two monodentate ligands and denotes three monodentate or one bidentate and one monodentate ligand, the ligands being unsaturated hydrocarbons or alkyl or arylphosphines or alkyl or arylphosphites or any combination of these ligands, or it is possible to use a two-component catalytic system, one component of which is a nickel complex in a zero oxidation state with hydrocarbon ligands and the second component is an organic alkyl or arylphosphine or alkyl or aryl3 phosphite, or it is possible to use a three-component catalytic system, one component of which is a divalent nickel compound subject to reduction to a nickel derivative in a zero oxidation state by the action of the reducing agent mentioned below, the second component is an organic alkyl or arylphosphine or alkyl or arylphosphite and the third component is a reducing agent capable of reducing a divalent nickel compound to a nickel derivative in the zero oxidation state, preferably an organoaluminum reducing agent containing at least one alkyl group on the aluminum atom.

The mixture of highly unsaturated cyclic hydrocarbons prepared by the method according to the invention is suitable as a starting material for the production of substitutes for high-viscosity oils.

The following examples describe in more detail the method of carrying out the invention without limiting or defining the scope of its validity.

Example 1

6 g of bis(1,5-cyclooctadiene)nickel was weighed into the reaction vessel under nitrogen and 250 ml of toluene was added. The resulting solution was saturated with residual pyrolysis fraction with a composition of 14% propadiene, 15% propyne, 71% propane and propene at a flow rate of 2 l/min, while stirring for 10 minutes.

Then the temperature of the reaction mixture was increased to 60 °C and the introduction of the Cj fraction was continued for 10.5 hours. After distilling off the toluene, 475 g of a mixture of highly unsaturated cyclic hydrocarbons of the general formula (C3H4) were obtained, where n is 3 to 10.

Example 2

15.6 g of tetrakis(triphenylphosphine)nickel was weighed into the reaction flask under nitrogen, 150 ml of the mixture of products from Example 1 was added, and the residual pyrolysis fraction with a composition of 15% propadiene, 40% propyne, 44% propane and propene was added to the resulting solution for 10 minutes with stirring.

After this time, the temperature of the reaction mixture was increased to 100 to 105 °C and the fraction was added to the solution for another 8 h. A total of 211 g of the fraction was added to the reaction during this time. The total weight of the obtained mixture of highly unsaturated cyclic hydrocarbons of the general formula (C ₃ H ₄ ) _n , where n is 3 to 10, was 186 g.

Example 3

6.7 g of bis(1,5-cyclooctadiene)nickel was weighed into the reaction vessel under nitrogen, 250 ml of toluene and 9.9 g of tributylphosphine were added. The resulting solution was saturated with the residual pyrolysis fraction with the same composition as in example 1 at a flow rate of 2 l/min for 10 minutes, while stirring. Then the temperature of the reaction mixture was increased to 90 °C and the fraction was continued for 8 h. After distilling off the toluene, 326 g of a mixture of hydrocarbons with the general formula where n is 3 to 10 were obtained.

Example 4

2 g of bis(2,4-pentanedionate)nickel complex were weighed into the reaction flask under nitrogen,

6.1 g of triphenylphosphine and 75 ml of toluene were added. The reaction mixture was saturated with the residual pyrolysis Cj fraction with the same composition as in Example 1 for 10 minutes with stirring at a flow rate of 530 ml/min. Then 0.9 g of triethylaluminum was added, the temperature of the reaction mixture was increased to 100 °C and the fraction was added to it at the above-mentioned rate for another 4 hours with stirring. After distilling off the toluene, 47.7 g of a mixture of hydrocarbons with the general formula (C ₃ H ₄ ) _n , where n is 3 to 10, were obtained.

Claims (1)

A process for the preparation of oligomeric unsaturated cyclic hydrocarbons of the formula * ^C 3 ^H 4 * n ' ^wherein - ^{2e 3 and} % ¹⁰ ' catalyzed by co-oligomerization of propadiene and propyne in solution in an organic solvent except tertiary amines and active hydrogen containing solvents preferably in aromatic or cyclic solvents of ether, particularly preferably in the crude product mixture at a temperature of 20 to 150 ° C, preferably 40 to 110 ° C, at a pressure of 0.1 to 20 MPa, preferably at atmospheric pressure in a flow configuration, at a molar ratio of catalyst to total monomers 0.001 to 1.0, preferably 0.001 to 0.05, excluding the presence of greater than equimolar amounts of oxygen and water to nickel, characterized in that a nickel complex in the zero oxidation stage of the NiL ^ or NiL ^ type is used as the catalyst, where L ^ is four monodentate or two bidentate or one bidentate and two monodentate ligands and L 1 denote three monodentate or one monodentate and one bidentate ligand, either unsaturated hydrocarbons or alkyl or arylphosphines or alkyl or arylphosphites, or any combination of these ligands, or a two-component catalyst system, one component of which is a zero-oxidation nickel complex with a hydrocarbon ligand and a second component of an organic alkyl or arylphosphine or an alkyl or arylphosphite, or a three-component catalyst system is used, one component of which is a divalent nickel compound subjected to the following reducing agent by reduction to a zero-oxidation nickel derivative; or an alkyl or aryl phosphite and a third component a reducing agent capable of reducing the divalent nickel compound to a nickel derivative in the zero oxidation stage, preferably an organoaluminum reducing agent, wherein the cooligo measurement propadiene and propyne contained in the residual pyrolysis Cj fraction containing 25 to 50% propane, 5 to 25% propene, 10 to 20% propadiene and 10 to 40% propyne are used to selectively react from the mixture.