CS258551B1 - Process for the production of highly unsaturated cyclic hydrocarbon oligomers - Google Patents

Abstract

A method for producing highly unsaturated cyclic hydrocarbons of the general formula (c3H4)n' where n is 3 to 10, catalyzed co-oligomerization of propadiene with propyne in an organic solvent with the exception of tertiary amines and solvents containing active hydrogen at a temperature of 20 to 150 °C, under 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 as catalysts either complexes of zero-valent nickel of the type Ni(ligand)4 or Ni(ligand)3, where the ligands can be monodentate or bidentate unsaturated hydrocarbons or organic phosphines or phosphites, or using a two-component catalytic system: a complex of zero-valent nickel with hydrocarbon ligands - organic phosphine or phosphite, or using of a three-component catalytic system: a divalent nickel compound - an organic phosphine or phosphite - a reducing agent capable of reducing a divalent nickel compound to a zero-valent nickel derivative. A mixture of highly unsaturated cyclic hydrocarbons of the general formula <c3H4>n' where £ 3e 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 present invention relates to oligomeric highly unsaturated hydrocarbons of the empirical formula (C ₃ H _{4) n,} where n is 3-10, with the co-oligomerisation propadiene propyne catalyzed by nickel compounds.

It is known that co-oligomerization of propadiene with propyne in a 2: 1 molar ratio catalysed by nickel compounds provides a mixture of isomeric highly unsaturated cyclic hydrocarbons of the formulas (C ₈ H ₄ ) ₃ and (C ₃ H ₄ > ₄₎ and structural types of methyldimethylene cyclohexenes and methyltrimethylene cyclooctenes (J. Amer. Chem. Soc. 81, 4250 (1959)). As catalysts it is possible to use nickel compounds are weak acids having a dissociation constant of less than 9.10 ^- 1θ (Brit. Pat. 802,350), for example, nickel cyanide or 2,4-pentanedione, nickel or karbonylfosfitové nickel complexes of formula Ni _(CO) P (oR) _{3 4} _ _m, wherein R is alkyl or aryl am assumes the value 1, 2 or 3 (US Pat. 2,943,116).

The latter carbonyl phosphite complexes of nickel are usually prepared by reacting highly toxic tetracarbonyl nickel with phosphites (J. Chem. Soc. 1954, 1940). Another disadvantage of the two groups of catalysts used hitherto is the low yield of the products, which does not exceed 50%, but is usually about 20%.

It has now been found that highly unsaturated cyclic hydrocarbons molecular formulas (C ₃ H _{4> n} where n is 3-10, can be prepared in yields of up to 100% of the co-oligomerisation of propadiene with propyne catalyzed known complexes of nickel in the zero oxidation type Nil ₄ or NiL ₃ , where L ₄ denotes four monodentate or two bidentate or one bidentate and two monodentate ligands and L ₃ denotes three monodentate or one bidentate and one monodentate ligand, either unsaturated hydrocarbons or alkyl or arylphosphines or alkyl or arylphosphites or any combination thereof of these ligands.

The co-oligomerization can also be catalyzed by a two-component catalyst system, one component of which is a zero-oxidation nickel complex with hydrocarbon ligands such as bis (1,5-cyclooctadiene) nickel and the other component an organic alkyl- or arylphosphine or alkyl- or arylphosphite. a system comprising one component of a divalent nickel compound subjected to a reduction to a nickel derivative in a zero oxidation step by the following reducing agent, a second component being an organic alkyl or arylphosphine or an alkyl or arylphosphite and a third component a reducing agent capable of reducing the nickel salt step, preferably an organoaluminum reducing agent containing at least one alkyl group per aluminum atom.

The co-oligomerization of propadiene with propyne can be carried out in a suitable solvent while maintaining a constant temperature. Suitable solvents are organic solvents, with the exception of tertiary amines and solvents containing active hydrogen, preferably aromatic solvents and cyclic ethers, particularly preferably a crude mixture of co-oligomerization products.

It has been found that the reaction can be carried out at a pressure of 0.1 to 20 MPa, in a batch arrangement preferably at autogenous pressure, in a flow arrangement preferably at atmospheric pressure.

It has further been found that with the above catalysts, the co-oligomerization of propadiene with propyne can be carried out at a temperature of 20 to 150 ° C, preferably at 40 to 110 ° C, wherein mixtures with a large excess of one monomer provide predominantly known homooligomers of the monomer.

It has been found that the preparation of highly unsaturated cyclic hydrocarbons by co-oligomerization of propadiene with propyne can be carried out at a molar ratio of nickel to total monomers of from 0.001 to 1.0, preferably from 0.001 to 0.05. An essential condition for carrying out the co-oligomerization is the absence of greater than equimolar amounts of oxygen and water to nickel during preparation.

By varying the ratio of monomers and reaction conditions used, it is possible to vary the composition of the mixture of cooligomerization products which, in addition to the known homooligomers of propadiene, homooligomers of propyne and cooligomers of methyldimethylene cyclohexenes and methyltrimethylene cyclooctenes, contains further cyclic hydrocarbons of the formula (C ₃ H ₄ ) _n , some of which have the structure of alkenyldimethylbenzenes.

The highly unsaturated cyclic hydrocarbon mixture prepared by the process of the present invention is suitable as a starting material for the manufacture of drying oil substitutes.

The following examples illustrate embodiments of the invention without limiting or limiting it.

Example 1

3.8 g of tetrakis (triphenylphosphine) nickel 2 were weighed into the reaction vessel under nitrogen and then 200 ml of dry toluene, 14.4 g of propadiene and 7.2 g of propyne were successively distilled in a vacuum of the order of 10 Pa. The reaction vessel was sealed and then placed in a thermostat heated to 70 ° C where it was left under magnetic stirring for 22 h. After toluene was distilled off, 21.2 g of a product mixture containing 17% of the hydrocarbons of the formula (C ₃ H ₄ ) _{3 were obtained} . 25% of the hydrocarbons of the empirical formula (C ₃ H _{4> 4} 55% hydrocarbons of the empirical formula (C ₃ H ₄₎ g and 3% hydrocarbons molecular formulas (C3H4), where k is 6 to 10

Example 2

Analogous to Example 1, 3.8 g of bis 1,2-bis (diphenylphosphino) ethane nickel were catalysed from 13.5 g of propadiene and 4.5 g of propyne in 200 ml of xylene after reaction for 20 h at 120 ° C. 6 g of a mixture of products containing 70% of hydrocarbons of the empirical formula (C ₃ H _{4) 3,} 11% of hydrocarbons of the empirical formula (C ₃ H _4> 19 ₄ and 4 hydrocarbons of the empirical formula (C ₃ H ₄₎ j.

Example 3

17 g of tetrakis (triethylphosphite) nickel were weighed into the autoclave under nitrogen and then 100 ml of dry toluene was added and 50 g of propadiene and 50 g of propyne were distilled while cooling the solid carbon dioxide-acetone mixture. The mixture was then allowed to react with stirring at 110 ° C for 29 h. After distilling off the toluene, 44 g of a product mixture containing 20 g of ethyl acetate were obtained.

% Hydrocarbons of the empirical formula (C ₃ H _{4) 3,} and 8% of hydrocarbons of the empirical formula (C ₃ H _{4) 4} ·

He attaches

2.7 g of (1,5-cyclooctadiene) bis (tributylphosphine) nickel were weighed into the autoclave under a nitrogen atmosphere and then 20 ml of the product mixture of Example 3 was added. Next, 6.4 g of propadiene were distilled while cooling the solid carbon dioxide / acetone mixture. and 12.8 g propyne. The reaction mixture was allowed to react with stirring at 90 ° C for 22 h. After this time the contents of the autoclave weighed 28.3 g and contained 68% of hydrocarbons of the empirical formula (C ₃ H _{4> 3,} 15% of hydrocarbons of the empirical formula (C ₃ H _{4) 4,} 8% of hydrocarbons of the empirical formula (C ₃ H ₄₎ and 5 9% of the hydrocarbons of the formulas where k is 6 to 10.

Example5

5.6 g of bis (1,5-cyclooctadiene) nickel were weighed into the reaction vessel under a nitrogen atmosphere and then 300 ml of toluene was added. The resulting solution was simultaneously bubbled through propadiene at a flow rate of 240 ml / min and propyne also at a rate of 240 ml / min while stirring with a magnetic stirrer. The reaction mixture was heated to 60 ° C and monomers were introduced at this temperature for 10 hours. After toluene was distilled off, 354 g of a product mixture containing 18% of the hydrocarbons of the formula (C ₃ H ₄ ) ₃ , 22% of the hydrocarbons of the formula (C ₃ H) were obtained. _{4) 4,} 35% of hydrocarbons of the empirical formula (C ₃ H _{4) 5} to 25% hydrocarbons and molecular formulas (CJH ^^ wherein k is 6 to 10

Example 6

4.8 g of bis (1,5-cyclooctadiene) nickel were weighed into the autoclave under nitrogen, 75 ml of toluene and 9.6 g of triphenylphosphine were added. 20 g of propadiene and 40 g of propyne were then distilled while cooling with a mixture of solid carbon dioxide and acetone. The reaction mixture was allowed to react at 100 ° C for 20 h with stirring. After the toluene was distilled off, 53 g of a product mixture containing 48% of the total hydrocarbons of the formula (C ₃ H ₄ > ₃ , 7% of the total hydrocarbons of the formula ^3H 4 → ³³ * ³³ _{) were obtained} . ₄ ) _k , wherein k is 6 to 10.

Example 7

2 g of bis (2,4-pentanedione) nickel complex, 6 g of triphenylphosphine, 100 ml of dry toluene were added to the autoclave under nitrogen, and 27 g of propadiene and 17 g of propyne were distilled while cooling with solid carbon dioxide-acetone. Then, 0.9 g of triethyl aluminum was added and the mixture was allowed to react at 100 ° C for 20 h with stirring. After distilling off toluene to provide 26 g of a mixture of products containing 25% hydrocarbons of the empirical formula (C ₃ H _{4) 3,} 32 »hydrocarbons of the empirical formula (C ₃ H _{4) 4,} 18% of hydrocarbons of the empirical formula (C ₃ H _{4> 5} and 25 % of the hydrocarbons of the formulas (.delta.), where k is 6 to 10.

Claims (6)

A process for producing oligomeric highly unsaturated cyclic hydrocarbons of the formula (C ₃ H ₄ > _n , where n is 3 to 10), catalyzed the co-oligomerization of propadiene with propyne in solution in an organic solvent except tertiary amines and active hydrogen-containing solvents at 20 to 150 ° C, at a pressure of 0.1 to 20 MPa, at a molar ratio of catalyst to total monomer of 0.001 to 1.0, excluding the presence of greater than equimolar amounts of oxygen and water to nickel, characterized in that a nickel complex is used as catalyst in a zero oxidation stage of the type NiL ₄ or NiLj, where L ₄ denotes four monodentate or two bidentate or one bidentate and two monodentate ligands and L 4 denotes three monodentate or one bidentate and one monodentate ligand, the ligands being unsaturated hydrocarbons or alkyl or aryl phosphines or alkyl or arylphosphites or any other thereof or a two-component catalyst system, one component of which is a zero-oxidation nickel complex with hydrocarbon ligands and the other component of an organic alkyl or arylphosphine or alkyl or arylphosphite, or a three-component catalyst system, one component of which is a bivalent nickel compound by treating said nickel derivative in a zero oxidation step with said reducing agent, the second component being an organic alkyl or arylphosphine or an alkyl or arylphosphite and a third component reducing agent is an agent capable of reducing the divalent nickel compound to a nickel derivative in the zero oxidation step, preferably an organoaluminum reducing agent. 2. A process according to claim 1, wherein the batch is used and the reaction is carried out in an autoclave at 40 to 110 [deg.] C. under autogenous pressure at a molar ratio of catalyst to total monomers of 0.001 to 0.05 and a monomer ratio of 0 to 0. , 33 to 3.0. 3. A process according to claim 1, wherein a stirred isothermal reactor is bubbled through a mixture of propadiene with propyne at a ratio of from 0.33 to 3.0 at 40-110 [deg.] C at atmospheric pressure and a mole ratio of catalyst to total monomers. 0.001 to 0.05. 4. A process according to claim 2 or 3, characterized in that one of the following nickel complexes is used as the catalyst: bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, bis 1,2-bis (diphenylphosphino) ethane nickel, (1,5-cyclooctadiene) bis (tributylphosphine) nickel, tetrakis (triethylphosphite) nickel. 5. Process according to claim 2 or 3, characterized in that a two-component catalyst system is used, one component of which is bis (1,5-cyclooctadiene) nickel and the other component is an organic trialkyl or triarylphosphine or trialkyl or triarylphosphite, preferably triphenylphosphine, tributylphosphine. , triphenyl phosphite, triethyl phosphite, tris (2-biphenylyl) phosphite or tris (2-tolyl) phosphite. 6. Process according to claim 2 or 3, characterized in that a three component catalyst system is used, one component of which is a nickel salt, preferably a bis (2,4-pentanedione) nickel complex, the other component being an organic trialkyl or triarylphosphine or trialkyl or triarylphosphite. triphenylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphite, triethylphosphite, tris (2-biphenylyl) phosphite or tris (2-tolyl) phosphite, and the third component is an organoaluminum reducing agent, preferably triethylaluminum, triisobutyl aluminum, diethylethoxyaluminum or ethyl diethoxyoxyaluminum.