CS268883B1 - Process for the production of highly unsaturated cyclic hydrocarbons - Google Patents

Abstract

A method for producing highly unsaturated cyclic hydrocarbons of the general formula (CXH,) (n), where n is 3 to 10, by catalyzing the co-oligomerization of propadiene and promine in an organic solvent with the exception of amines and solvents containing active hydrogen at temperatures? 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 monomer of 0.001 to 1.0, excluding the presence of more than an equimolar amount of oxygen and water to nickel, under catalysis by a nickel compound selected from the group containing nickel compounds with weak acids having a dissociation constant lower than 9.10-x and further carbonyl phosphite or carbonyl phosphine complexes of nickel of the general formula Ni (CO) (m) (PA,) (4 - m), where A is alkyl or aryl, or alkoxyl or arosyl and m takes on the values 1,2 or 3, consisting in that propadiene and propyne contained in the residual pyrolysis C, fraction are used for the copolymerization in such a way that their selective reaction from this mixture occurs. A mixture of highly unsaturated cyclic hydrocarbons of the general formula (c,Pr) (n), where n is 3 to 10, prepared in the manner described, is suitable as a starting 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 jj is 3 to 10, by catalyzed copolymerization of propadiene and propyne contained in the residual pyrolysis C^ fraction.

It is known that the pure hydrocarbons propadiene and propyne can be co-oligomerized to highly unsaturated cyclic hydrocarbons of the formula (CjH^)^ and (C^H^)^ (J. Amer.

Cnem. 3oc. 81, 4250 (1959) under catalysis by nickel compounds with weak acids having a dissociation constant of less than 9·10 ^- ^θ (Brit. Pat. 802,350) or by nickel carbonylphosphite complexes of the general formula Ni(CO)^ P(OR)^)^^, where R is alkyl or aryl and m takes the values 1, 2 or 3 (U.S. Pat. 2,943,116).

The current process for preparing oligomeric highly unsaturated cyclic hydrocarbons of the total formula where n is 3^10, by the co-oligomerization of propadiene with propyne, starts from a mixture of pure monomers. This fact is a disadvantage, because the isolation of pure propadiene and propyne, or their mixtures, 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 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 butenes and butane. 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^H^)^ where n is 3 to 10, catalyzed by the co-oligomerization of propadiene and propyne contained in the residual pyrolysis .C^ 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 (CjH^)^, where n is 3 to 10, by catalyzed coalgomerization of propadiene and propyne contained in the residual pyrolysis 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 nickel compounds selected from the group containing nickel compounds with weak acids, having a dissociation constant of less than 9.10 ^-10 and further containing carbonylphosphite or carbonylphosphine complexes of nickel of the general formula NICO(PA-j)^^, where A is alkyl or aryl or alkoxyl or aroxyl and m takes the values 1, 2 or 3.

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 drying oil substitutes.

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

Example 1

7.7 g of dicarbonylbis-(triphenylphosphite)nickel were weighed into the autoclave under nitrogen and 50 ml of dry toluene were added. Then, after smoothing the solid carbon dioxide with acetone, 185 g of residual pyrolysis C$ fraction with a composition of 32% propadiene, 15% propyne and 53% propane and propene were distilled. The contents of the autoclave were left to react with stirring for 5 h at 100 °C. After distilling off the toluene, 47 g of a mixture of hydrocarbons with the general formula where n is 3 to 10 were obtained.

Example 2

8.2 g of bis(2,4-pentanedionato)nickel complex was weighed into the reaction vessel under nitrogen and 250 ml of dry toluene was added. Then, the residual pyrolysis Cj fraction with the same composition as in Example 1 was introduced into the resulting solution with stirring at a rate of 2 l/min. Within 20 minutes, the temperature of the reaction mixture was increased to 110 °C and the introduction of the fraction at this temperature was continued for another 20 h. After distilling off the toluene, 456 g of a mixture of hydrocarbons with the general formula (C^H^) _n were obtained, where n is 3 to 10.

Claims (1)

Process for the production of highly unsaturated cyclic hydrocarbons of the general formula where n is 3 to 10, by catalyzed co-oligomerization of propylene and propyne in solution in 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 in a batch or flow-through arrangement at a temperature of 20 to 150 °C, preferably at 40 to 110 °C, at a pressure of 0.1 to 20 MPa, preferably at atmospheric pressure in a flow-through arrangement, at a molar ratio of the amount of catalyst to the total amount of monomers of 0.001 to 1.0, preferably 0.001 to 0.05, while excluding the presence of more than an equimolar amount of oxygen and water to nickel and under catalysis by a nickel compound selected from the group consisting of nickel compounds with weak acids having a dissociation constant lower than 9.10 ^-10 and further carbonylphosphite or carbonylphosphine complexes of nickel of the general formula Nl(CO) _m (PAj) _/( _ _m , where A is alkyl or aryl or alkoxyl or aroxyl and m takes on the values 1, 2 or 3, characterized in that propadiene and propyne contained in the residual pyrolysis fraction containing 25 to 50% propane, 5 to 25% propene, 10 to 20% propadiene and 10 to 40% propyne are used for the co-oligomerization so that they are selectively reacted from this mixture.