US3442971A - Process for production of olefines by dimerization,co-dimerization,polymerization and co-polymerization of olefines - Google Patents

Process for production of olefines by dimerization,co-dimerization,polymerization and co-polymerization of olefines Download PDF

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US3442971A
US3442971A US526079A US3442971DA US3442971A US 3442971 A US3442971 A US 3442971A US 526079 A US526079 A US 526079A US 3442971D A US3442971D A US 3442971DA US 3442971 A US3442971 A US 3442971A
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olefines
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hexene
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Olav-Torgeir Onsager
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Sentralinstitutt for Industriell Forskning
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • beryllium, aluminium, gallium and indium compounds of the types BeR AIR;, and InR in which at least one of the ligands, R, represents an organic hydrocarbon residue of hydrogen, are able to convert lower olefines to dimerized, trimerized and higher products with high alpha-olefine content, and that the presence of finely powdered metallic cobalt, nickel or platinum increases the selectivity of the systems favouring the formation of more low-molecular (dimerized) products.
  • finely powdered metallic nickel in the form of Raney nickel additions or metallic nickel reduced from nickel compounds by conversion with a certain amount of the organic main group metal component at higher temperature has been used.
  • a characteristic feature of the said processes, in which transitional metal additions are used as co-catalyst, is that these exist in finely powdered metallic form with the formation of a heterogenous phase in the catalytic mixtures.
  • organic ligands preferably such containing one or more carbon/carbon double or triple bonds
  • Compounds which contain such types of bonds are termed 1r-organic transition metal compounds.
  • Common to the types of organic nickel compounds indicated above is that these contain 1r-b0nd6d organic ligands. Since other nickel organic compounds containing the same type of bond satisfying the necessary stability requirements exist in addition to the above-mentioned types of vr-organic nickel compounds, active catalyst components will also be found among these compounds.
  • the advantage of the process according to the invention is that use is made of a soluble catalyst having such high activity that the reactions can take place at substantially lower temperature, pressure and catalyst concentration than those described as favourable in formerly known oligomerization processes of the Ziegler type.
  • the composition of the reaction products differs at essential points from the above mentioned types of processes by the fact that there are formed dimerized and trimerized mono-olefines with very high content of betaand gamma-olefines.
  • the formation of the active catalyst system is very simple. It occurs automatically at the mixing of the two types of catalyst components, advantageously in the form of solutions in an inert organic solvent, such as benzene, xylene, heptane or higher parafins, in argon or nitrogen atmosphere.
  • the concentration of the main group metal compound, as well as the rela tive proportion of the two types of compound, can be varied within wide limits. It has been found favourable to the process to use main group metal concentrations within the range 0.001-0.100 mole/liter, and a nickelmain group metal molar ratio in the range 1:1-0.01:1.
  • the process according to the invention can be performed at pressures from fractions of an atmosphere up to very large pressures, limited only by the apparatus construction. It is, however, advantageous, out of regard for temperature control, that the reactions take place at pressures not exceeding atm.
  • the reducing effect which lies in the main group metal-carbon bonds BeC, AlC, Ga-C and In-C may lead to a reduction of the nickel compounds, if the temperature during the conversion is too high.
  • the reaction temperature should therefore be kept below the temperature range in which a substantial part of the nickel compound in the course of the conversion is destroyed by reduction to preferably not exceeding 100 C.
  • the highest reaction temperatures can be selected in the processes which make metallic nickel,.
  • the process can be carried out either discontinuously, for example, by placing the catalyst components together with a solvent, if necessary, in a thermostat-regulated reaction vessel, passing the monomer or the monomer mixture for some time, e.g. 1-5 hours, into the catalyst mixture, and then extracting the reaction product by the usual working methods, or continuously, for example by passing the monomer or the monomer mixture through the catalyst mixture, with subsequent continuous isolation of the reaction product from the outflowing gas mixture. Unreacted monomer and solvent, if any, and catalyst are separated from the reaction product during the isolation of the latter and are suitably recirculated to the reaction vessel.
  • solvent can be omitted with advantage.
  • mixtures of their isomeric compounds may also be used as raw material for the processes, due to the isomerization activity of the catalyst systems.
  • One or more of the above-mentioned types of nickel compounds are placed in a thermostat-regulated glass reaction flask, equipped with a magnetic stirrer, reflux condenser and dropping funnel with pressure-equalizing means. On the top of the reflux condenser there was a possibility of connection to vacuum, highly purified nitrogen and highly purified starting-monomer for the syntheses.
  • the apparatus was evacuated for 1 hour, then filled with nitrogen. In the course of the nitrogen flushing the desired quantity of abs. solvent was added to the reaction flask.
  • a main group metal compound of the above-mentioned type or mixtures of these are, if necessary diluted with solvent, then added to the dropping funnel in a nitrogen atmosphere.
  • the whole apparatus is then carefully evacuated three times and after each time filled with the starting-monomer at atmospheric pressure.
  • the two catalyst components each saturated with the starting-monomer, are mixed under agitation in the reaction flask.
  • the inflow velocity of the starting-monomer required to maintain constant pressure in the reaction flask (1 atm.) was measured with a capillary flow meter as a function of reaction time.
  • the bath temperature was kept constant within the limits i0.05 C. by means of a water-circulation thermostat. After a certain reaction time the conversion was stopped and the reaction mixture was gas-chromatographically analyzed.
  • the reactions were carried out in a non-magnetic, acidresistant steel autoclave having a volume of 200 ml.
  • the autoclave was connected with a glass container which could be evacuated.
  • the connection between the two vessels could be closed by means of a high pressure valve.
  • the autoclave and glass container were evacuated to less than 0.5 mm. Hg in 30 min.
  • the valve between the two vessels was closed and the glass container filled with highly purified nitrogen.
  • the catalyst components and the solvent were then poured into the glass container in a nitrogen atmosphere.
  • C -olefines (of which 20% heXene-3-cis and trans, 55% hexene-Z-trans, 14% hexene-2-cis and 11% 3-methyl-pentene-2-cis and trans). 5% higher than C olefines.
  • C -olefines (of which 0.9% 4-methylpentene-1, 2.8% 4-methylpentene-2-cis, 23.1% 4-methyl-pentene-2-trans, 3.6% Z-methylpentene-l, 42.5% 2-methyl-pentene-2, 4.4% hexene-3-cis and trans, 13.6% hexene-Z-trans, 4.7% hexene-2-cis and 4.4% 2,3- dimethylbutene-Z). 5% higher than C -olefines.
  • Composition of product 2% C -olefines (of which, 72.7% butene-2-trans, 27.3% butene-2-cis). 28% C -olefines (of which, 1.0% Z-methyIbutene-l, 5.5% 2-methylbutene-2, 72.4% pentene-Z-trans, 21.1% pentene-Z-cis). 65% C -olefines (of which, 1.5% 4-methylpentene-1, 7.3% 4-methylpentene-2-cis, 52.4% 4-methylpentene-2- trans, 4.8% heXene-3-cis and trans, 17.5% hexene-2-trans, 12.7% 2-methylpentene-2 and 3.8% hexene-Z-cis). 5% C -olefines.
  • Composition of product 82.1% C -olefines (of which 1.8% butene-l, 70.0% butene-Z-trans, 28.2% butene-Z- cis). 14.9% C -olefines (of which 6.7% hexene-3-cis and trans, 3.1% 2-ethylbutene-1, 18.3% hexene-Z-trans, 20.1% 3-methylpentene-2-trans, 6.7% hexene-2-cis and 45.1% 3- methylpentene-Z-cis). 3% higher than C -oleflnes.
  • composition of product 97% C -olefines (of which 9.2% butene-l, 62.5% butene-Z-trans, 28.3% butane-2- cis). 3% higher than C -olefines,
  • Composition of product 91% C -olefines (of which 2.4% butene-l, 69% butene-Z-trans, 28.6% butene-Z-cis), 8% C -olefines (of which 29.2% hexene-3-+ 2-ethylbutene-l, 20.2% hexene-2-trans, 18.0% 3-methylpentene-2- trans, 32.6% 3-methylpentene-2-cis). 1% higher than C olefines.
  • Composition of product 46.6% C -olefines (of which 2% butene-l, 69.5% butene-2-trans and 28.5% :butene-Z- cis), 48.4% C -olefines (of which 4.0% hexene-3-cis and trans, 7.0% 2-ethylbutene-1, 9.0% hexene-Z-trans, 26.0% 3-methylpentene-2-trans, 4.0% hexene-Z-cis, 50% 3-methyl-pentene-Z-cis). 5% higher than C -olefiines.
  • Composition of product 72% C -olefines (of which 7.5% butene-l, 67.3% butene-Z-trans, 25.2% butene-2- cis), 26% C -olefines (of which 12.2% hexene-3-cis and trans, 25.1% hexene-2-trans, 15.5% 3-methylpentene-2- trans, 7.4% hexene-Z-cis, 39.8% 3-methylpentene-2-cis). 2% higher than C -olefines.
  • Composition of product 92% C -olefines (of which 1.5% 4-methylpentene-1, 4.8% 4 methylpentene 2 cis, 23.0% 4-methyl-pentene-2-trans, 9.31% Z-methyIpentene-l and hexene-l, 4.7% hexene-3-cis and trans, 13.1% hexene- 2-trans, 37.1% 2-methyl-pentene-2, 3.9% hexene-Z-cis and 2.6% 2,3-dimethylbutene-2). 8% higher than C olefines.
  • composition of product 60% C -olefines (of which 7.0% butene-l, 65.5% butene-Z-trans, 27.5% butene-Z- cis), 30% C -olefines (of which 1.5 3-methylpentene-1,
  • Composition of product 63% C -olefines (of which 0.8% 4 methylpentene 1, 4.2% 4-methylpentene-2-cis, 24.1% methylpentene-Z-trans, 0.5% Z-methyl-pentene-l and hexene-l, 8.8% hexene-3-cis and trans, 24.6% hexene-Z-trans, 25.3% Z-methylpentene-Z, 6.7% hexene-Z-cis, 5.0% 2.3-dimethylbutene-2). 27% higher than C -olefines.
  • the catalyst is a catalytic mixture of one or more cyclobutadiene nickel diahalides and one or more compounds selected from the group consisting of and Me(R) (Y) in which R is selected from the group consisting of hydrocarbon radicals and hydrogen, Y is an acid radical, a is a number from 1 to 2, b is a number from 1 to 3, and Me is selected from the group consisting of Al, Ga and In.
  • the catalyst is a catalytic mixture of one or more cyclobutadiene nickel dihalides and one or more compounds selected from the group consisting of Be(R) (Y) and Me(R) (Y) in which R is selected from the group consisting of alkyl and aryl, Y is selected from the group consisting of halogen and alkoxy, a is a number from 1 to 2, b is a number from 1 to 3, and Me is selected from the group consisting of Al, Ga and In.
  • the improvement according to which the catalyst is a catalytic mixture of one or more cyclobutadiene-nickel-dihalides and one or more aluminumalkylhalides.
  • aluminium-alkylhalides are used as addition compounds with electron-donor components.
  • the improvement according to which the catalyst is a catalytic mixture of cyclobutadiene-nickel-dihalides, and an aluminium-alkylhalide.
  • aluminium-alkylhalide is used as an addition compound with triphenyl phosphine.
  • the improvement according to which the catalyst is a catalytic mixture of a cyclobutadiene nickel-compound selected from the group consisting of tetramethylcyclobutadiene-nickeldichloride, and tetraphenylcyclobutadiene-nickeldichloride, and a main group metal compound selected from the group consisting of aluminium-monoethyl-dichloride, aluminiummonoethyl-dibromide, aluminium-diphenyl-monochloride, dialuminium triethylmonoethoxy dichloride and beryliumdiethyl.

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Description

United States Patent Int. c1. (50% 3/10 US. Cl. 260683.15 20 Claims ABSTRACT OF THE DISCLOSURE Monoolefins are oligomerized using a catalyst mixture comprising a cyclobutadiene nickel dihalide and a compound such as ethylaluminum dichloride or diethylberyllium to give a product with a high content of betaand gamma-olefins. The use of ethylene and/or propylene as the feed with tetramethylcyclobutadiene-nickel-dichloride or tetraphenylcyclobutadiene-nickel-dichloride as a catalyst component is illustrated.
By the development of cracking processes in the modern petroleum industry the low-molecular alpha-olefines, such as ethane, propene and butene, have become easily available raw materials on a large industrial scale.
Besides the direct utilization in the production of highmolecular compounds in the plastic industry, the refining processes of these raw materials to products in the range C -C play an important part in industrial, organic chemistry.
It is known that beryllium, aluminium, gallium and indium compounds of the types BeR AIR;, and InR in which at least one of the ligands, R, represents an organic hydrocarbon residue of hydrogen, are able to convert lower olefines to dimerized, trimerized and higher products with high alpha-olefine content, and that the presence of finely powdered metallic cobalt, nickel or platinum increases the selectivity of the systems favouring the formation of more low-molecular (dimerized) products. In particular, finely powdered metallic nickel in the form of Raney nickel additions or metallic nickel reduced from nickel compounds by conversion with a certain amount of the organic main group metal component at higher temperature, has been used. In order to prevent the metallic nickel component from being inactivated during an early phase of the synthesis, processes have been developed in which acetylene or hydrocarbons with acetylene bonds are added during the conversions. In the polymerization of ethane with aluminium-trialkyl and metallic nickel as catalyst, the minimum amount of acetylene which is added is reported to lie in the range 0.21% of the total quantity of converted ethene (German Patent No. 1,001,981).
Drawbacks of the known oligomerization processes of the Ziegler type, besides the additions of the types of organic compounds described above are, that these processes use very high catalyst concentrations of the main group metal compound, up to 20% of the reaction mixture. Also, due to the high temperatures and pressures which are required during the syntheses, up to 250 C./200 atm. (German Patent No. 964,642, US. Patent No. 2,695,327), vary inflammable and explosive mixtures are produced.
A characteristic feature of the said processes, in which transitional metal additions are used as co-catalyst, is that these exist in finely powdered metallic form with the formation of a heterogenous phase in the catalytic mixtures.
3,442,971 Patented May 6, 1969 Surprisingly we have now found that cyclodienenickel-dihalides, which in combination with metal-organic compounds of the metals in 2nd and 3rd main group in the periodic table are not reduced to metallic nickel, and which in mixtures with the main group metal compounds mentioned above represented very active catalyst systems for dimerization, co-dimerization, polymerization and co-polymerization of alpha-olefines from the range C -C at such mild conditions as, for example, 20 C./1 atm., under formation of mono-olefines in the range C -C with high content of betaand gammaolefines.
As the main group metal component there can be used one or more compounds of the types Be(R),(Y) )b( )3-b, )b( )3-b and )b( )3-b and/01' their adition compounds with electrondonor compounds such as ethers, phosphines etc., in which R=hydrocarbon radical, preferably alkyl and/ or hydrogen, Y=acid radical, such as halogen and alkoxy-groups, a=l2 and b=13.
From the literature it is known that organic ligands, preferably such containing one or more carbon/carbon double or triple bonds, can be attached to a transition metal by electronic interactions between the p-electrons of the ligand and the d-electrons of the transition metals or free d-electron orbitals (1r-bonds). Compounds which contain such types of bonds are termed 1r-organic transition metal compounds. Common to the types of organic nickel compounds indicated above is that these contain 1r-b0nd6d organic ligands. Since other nickel organic compounds containing the same type of bond satisfying the necessary stability requirements exist in addition to the above-mentioned types of vr-organic nickel compounds, active catalyst components will also be found among these compounds.
The advantage of the process according to the invention is that use is made of a soluble catalyst having such high activity that the reactions can take place at substantially lower temperature, pressure and catalyst concentration than those described as favourable in formerly known oligomerization processes of the Ziegler type. Besides, the composition of the reaction products differs at essential points from the above mentioned types of processes by the fact that there are formed dimerized and trimerized mono-olefines with very high content of betaand gamma-olefines. The formation of the active catalyst system is very simple. It occurs automatically at the mixing of the two types of catalyst components, advantageously in the form of solutions in an inert organic solvent, such as benzene, xylene, heptane or higher parafins, in argon or nitrogen atmosphere. The concentration of the main group metal compound, as well as the rela tive proportion of the two types of compound, can be varied within wide limits. It has been found favourable to the process to use main group metal concentrations within the range 0.001-0.100 mole/liter, and a nickelmain group metal molar ratio in the range 1:1-0.01:1.
The process according to the invention can be performed at pressures from fractions of an atmosphere up to very large pressures, limited only by the apparatus construction. It is, however, advantageous, out of regard for temperature control, that the reactions take place at pressures not exceeding atm. The reducing effect which lies in the main group metal-carbon bonds BeC, AlC, Ga-C and In-C may lead to a reduction of the nickel compounds, if the temperature during the conversion is too high. The reaction temperature should therefore be kept below the temperature range in which a substantial part of the nickel compound in the course of the conversion is destroyed by reduction to preferably not exceeding 100 C. The highest reaction temperatures can be selected in the processes which make metallic nickel,.
use of the most stable cyclobutadiene nickel compounds in combination with the least reduction-active main group metal compounds as catalysts.
The process can be carried out either discontinuously, for example, by placing the catalyst components together with a solvent, if necessary, in a thermostat-regulated reaction vessel, passing the monomer or the monomer mixture for some time, e.g. 1-5 hours, into the catalyst mixture, and then extracting the reaction product by the usual working methods, or continuously, for example by passing the monomer or the monomer mixture through the catalyst mixture, with subsequent continuous isolation of the reaction product from the outflowing gas mixture. Unreacted monomer and solvent, if any, and catalyst are separated from the reaction product during the isolation of the latter and are suitably recirculated to the reaction vessel. By the process according to the invention, in which the monomer is a liquid, solvent can be omitted with advantage. In addition to the alpha-olefines, mixtures of their isomeric compounds may also be used as raw material for the processes, due to the isomerization activity of the catalyst systems.
APPARATUS AND TECHNIQUE For the examples 1-9 the following apparatus and work technique were used:
One or more of the above-mentioned types of nickel compounds are placed in a thermostat-regulated glass reaction flask, equipped with a magnetic stirrer, reflux condenser and dropping funnel with pressure-equalizing means. On the top of the reflux condenser there was a possibility of connection to vacuum, highly purified nitrogen and highly purified starting-monomer for the syntheses. The apparatus was evacuated for 1 hour, then filled with nitrogen. In the course of the nitrogen flushing the desired quantity of abs. solvent was added to the reaction flask. A main group metal compound of the above-mentioned type or mixtures of these are, if necessary diluted with solvent, then added to the dropping funnel in a nitrogen atmosphere. The whole apparatus is then carefully evacuated three times and after each time filled with the starting-monomer at atmospheric pressure. At reaction time zero the two catalyst components, each saturated with the starting-monomer, are mixed under agitation in the reaction flask. The inflow velocity of the starting-monomer required to maintain constant pressure in the reaction flask (1 atm.) was measured with a capillary flow meter as a function of reaction time. The bath temperature was kept constant within the limits i0.05 C. by means of a water-circulation thermostat. After a certain reaction time the conversion was stopped and the reaction mixture was gas-chromatographically analyzed.
For the Examples -13 the following apparatus and technique were used:
The reactions were carried out in a non-magnetic, acidresistant steel autoclave having a volume of 200 ml. The autoclave was connected with a glass container which could be evacuated. The connection between the two vessels could be closed by means of a high pressure valve. Before the experiment the autoclave and glass container were evacuated to less than 0.5 mm. Hg in 30 min. The valve between the two vessels was closed and the glass container filled with highly purified nitrogen. The catalyst components and the solvent were then poured into the glass container in a nitrogen atmosphere.
By opening the valve between the two vessels the catalyst solution was sucked into the evacuated autoclave. The connection to the vacuum pump was out 01f in advance. The autoclave was then filled with monomer to the indicated pressure, which was kept constant during the whole reaction period. The autoclave was fitted with a magnetic stirrer and placed in a water bath with the stated temperatures i0.1 C. The reaction mixtures were gaschromatographically analyzed.
EXAMPLE 1 Temperature: 28 C. Pressure: 1 atm. Solvent: 44 g. benzene. Catalyst: 35.7 mg. tetramethylcyclobutadienenickel-dichloride, 127 mg. aluminium-monoethyl-dichloride. Monomer: ethene, Reaction time: 60 min. Reaction product formed: 15 g. Composition of product: 78% C -olefines (of which 1.3% butene-l, 72.6% butene 2-trans and 26.1% butene-2-cis).
17% C -olefines (of which 20% heXene-3-cis and trans, 55% hexene-Z-trans, 14% hexene-2-cis and 11% 3-methyl-pentene-2-cis and trans). 5% higher than C olefines.
EXAMPLE 2 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene. Catalyst: 119 mg. tetramethylcyclobutadienenickel-dichloride, 127 mg. aluminium-monoethyl-dichloride. Monomer: propene. Reaction time: 60 min. Reaction product formed: 20 g.
Composition of product: C -olefines (of which 0.9% 4-methylpentene-1, 2.8% 4-methylpentene-2-cis, 23.1% 4-methyl-pentene-2-trans, 3.6% Z-methylpentene-l, 42.5% 2-methyl-pentene-2, 4.4% hexene-3-cis and trans, 13.6% hexene-Z-trans, 4.7% hexene-2-cis and 4.4% 2,3- dimethylbutene-Z). 5% higher than C -olefines.
EXAMPLE 3 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene. Catalyst: 35.7 mg. tetramethylcyclobutadienenickel-dichloride, 127 mg. aluminium-monoethyl-dichloride. Monomer: ethene/propene=% (gas volume at 20 C./1 atm.). Reaction time: 30 min. Reaction product formed: 9 g.
Composition of product: 2% C -olefines (of which, 72.7% butene-2-trans, 27.3% butene-2-cis). 28% C -olefines (of which, 1.0% Z-methyIbutene-l, 5.5% 2-methylbutene-2, 72.4% pentene-Z-trans, 21.1% pentene-Z-cis). 65% C -olefines (of which, 1.5% 4-methylpentene-1, 7.3% 4-methylpentene-2-cis, 52.4% 4-methylpentene-2- trans, 4.8% heXene-3-cis and trans, 17.5% hexene-2-trans, 12.7% 2-methylpentene-2 and 3.8% hexene-Z-cis). 5% C -olefines.
EXAMPLE 4 Temperature: 20 C. Pressure: 1 atm. Solvent: 37 g. benzene. Catalyst: 30 mg. tetramethylcyclobutadienenickel-dichloride, 180 mg. aluminium monoethyl dibromide. Monomer: ethene. Reaction time: 60 min. Reaction product formed: 2.3 g. Composition of product: 80% C -olefines (of which approx. butene-2-trans). 15% C olefines (of which 31% hexene-3-trans, 69% hexene- 2-trans). 5% higher than C -olefines.
EXAMPLE 5 Temperature: 20 C. Pressure: 1 atm. Solvent: 40 g. benzene. Catalyst: 30 mg. tetramethylcyclobutadienenickel-dichloride, mg. dialuminium-triethyl-monoethoxy-dichloride. Monomer: ethene. Reaction time: min. Reaction product formed: 7.5 g.
Composition of product: 82.1% C -olefines (of which 1.8% butene-l, 70.0% butene-Z-trans, 28.2% butene-Z- cis). 14.9% C -olefines (of which 6.7% hexene-3-cis and trans, 3.1% 2-ethylbutene-1, 18.3% hexene-Z-trans, 20.1% 3-methylpentene-2-trans, 6.7% hexene-2-cis and 45.1% 3- methylpentene-Z-cis). 3% higher than C -oleflnes.
EXAMPLE 6 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene. Catalyst: 35.7 mg. tetramethylcyclobutadienenickel-dichloride, 217 mg. aluminium-diphenyl-monochloride +131.2 mg. triphenylphosphine. Monomer: ethene. Reaction time: min. Reaction product formed 4.5 g.
Composition of product: 97% C -olefines (of which 9.2% butene-l, 62.5% butene-Z-trans, 28.3% butane-2- cis). 3% higher than C -olefines,
Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene. Catalyst: 119.0 mg. tetramethylcyclobutadienenickel-dichloride +l31.2 mg. triphenylphosphine, 34 mg. berylliumdiethyl (added in this order). Monomer: ethene. Reaction time: 30 min. Reaction product formed: g.
Composition of product: 91% C -olefines (of which 2.4% butene-l, 69% butene-Z-trans, 28.6% butene-Z-cis), 8% C -olefines (of which 29.2% hexene-3-+ 2-ethylbutene-l, 20.2% hexene-2-trans, 18.0% 3-methylpentene-2- trans, 32.6% 3-methylpentene-2-cis). 1% higher than C olefines.
EXAMPLE 8 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene. Catalyst: 75 mg. tetramethylcyclobutadiene-triphenylphosphine-nickel-dichloride, 127 mg. aluminiummonoethyl-dichloride. Monomer: ethene. Reaction time: 30 min. Reaction product formed: 4 g.
Composition of product: 46.6% C -olefines (of which 2% butene-l, 69.5% butene-2-trans and 28.5% :butene-Z- cis), 48.4% C -olefines (of which 4.0% hexene-3-cis and trans, 7.0% 2-ethylbutene-1, 9.0% hexene-Z-trans, 26.0% 3-methylpentene-2-trans, 4.0% hexene-Z-cis, 50% 3-methyl-pentene-Z-cis). 5% higher than C -olefiines.
EXAMPLE 9 Temperature: 20 C. Pressure: 1 atm. Solvent: 44 g. benzene. Catalyst: 43.8 mg. tetraphenylcyclobutadienenickel-dichloride, 127 mg. aluminium-monoethyl-dichloride. Monomer: ethene. Reaction time: 30 min. Reaction product formed: 5 g.
Composition of product: 72% C -olefines (of which 7.5% butene-l, 67.3% butene-Z-trans, 25.2% butene-2- cis), 26% C -olefines (of which 12.2% hexene-3-cis and trans, 25.1% hexene-2-trans, 15.5% 3-methylpentene-2- trans, 7.4% hexene-Z-cis, 39.8% 3-methylpentene-2-cis). 2% higher than C -olefines.
EXAMPLE 10 Temperature: 25 C. Pressure: 5 atm. Solvent: 44 g. benzene. Catalyst: 29.8 mg. tetramethylcyclobutadienenickel-dichloride, 190 mg. aluminium-monoethyl-dichloride +1965 mg. triphenylphosphine. Monomer: propene. Reaction time: 60 min. Reaction product formed: 35 g.
Composition of product: 92% C -olefines (of which 1.5% 4-methylpentene-1, 4.8% 4 methylpentene 2 cis, 23.0% 4-methyl-pentene-2-trans, 9.31% Z-methyIpentene-l and hexene-l, 4.7% hexene-3-cis and trans, 13.1% hexene- 2-trans, 37.1% 2-methyl-pentene-2, 3.9% hexene-Z-cis and 2.6% 2,3-dimethylbutene-2). 8% higher than C olefines.
EXAMPLE 11 Temperature: 0 C. Pressure: 41 atm. Solvent: 44 g. benzene. Catalyst: 35.7 mg. tetramethylcyclobutadienenickel-dichloride, 127 mg. aluminium-monoethyl-dichloride. Monomer: ethene. Reaction time: 60 min. Reaction product formed: 70 g.
Composition of product: 60% C -olefines (of which 7.0% butene-l, 65.5% butene-Z-trans, 27.5% butene-Z- cis), 30% C -olefines (of which 1.5 3-methylpentene-1,
0.7% hexene-l, 12.0% hexene-3-cis and trans, 10.6% 2- ethylbutene-l, 22.0% heXene-2-trans, 13.6% 3-methylpentene-Z-trans, 8.0% hexene-Z-cis, 31.6% 3-methylpentene- 2-cis). 10% higher than C -olefines.
EXAMPLE 13 Temperature: C. Pressure: 5 atm. Solvent: 44 g. benzene. Catalyst: 59.5 mg. tetramethylcyclobutadienenickel-dichloride, 254 mg. aluminium-monoethyl-dichloride. Monomer: propene. Reaction time: 60 min. Reaction product formed: 7 g.
Composition of product: 63% C -olefines (of which 0.8% 4 methylpentene 1, 4.2% 4-methylpentene-2-cis, 24.1% methylpentene-Z-trans, 0.5% Z-methyl-pentene-l and hexene-l, 8.8% hexene-3-cis and trans, 24.6% hexene-Z-trans, 25.3% Z-methylpentene-Z, 6.7% hexene-Z-cis, 5.0% 2.3-dimethylbutene-2). 27% higher than C -olefines.
I claim:
1. In a process for the production of monoolefines in the range of C -C by the catalytic conversion of olefines in the range of C -C the improvement according to which the catalyst is a catalytic mixture of one or more cyclobutadiene nickel diahalides and one or more compounds selected from the group consisting of and Me(R) (Y) in which R is selected from the group consisting of hydrocarbon radicals and hydrogen, Y is an acid radical, a is a number from 1 to 2, b is a number from 1 to 3, and Me is selected from the group consisting of Al, Ga and In.
2. The improvement according to claim 1 wherein the cyclobutadiene nickel dihalides are employed as addition compounds with electron-donor components.
3. The improvement according to claim 1, wherein the compounds selected from the group consisting of and Me(R),,(Y) are employed as addition compounds with electron-donor components.
4. The improvement according to claim 1, wherein both the cyclobutadiene nickel dihalides and the compounds selected from the group consisting of and Me(R) (Y) are employed as addition compounds with electron-donor components.
5. In a process for the production of monoolefines in the range of C -C by the catalytic conversion of olefins in the range of C -C the improvement according to which the catalyst is a catalytic mixture of one or more cyclobutadiene nickel dihalides and one or more compounds selected from the group consisting of Be(R) (Y) and Me(R) (Y) in which R is selected from the group consisting of alkyl and aryl, Y is selected from the group consisting of halogen and alkoxy, a is a number from 1 to 2, b is a number from 1 to 3, and Me is selected from the group consisting of Al, Ga and In.
6. The improvement according to claim 5, wherein the cyclobutadiene nickel dihalides are used as addition compounds with electron-donor components.
7. The improvement according to claim 5, wherein the compounds selected from the group consisting of )a( )2-a and Me(R) (Y) are employed .as addition compounds with electron-donor components.
8. The improvement according to claim 5 wherein the cyclobutadiene nickel dihalides and the compounds selected from the group consisting of Be(R) (Y) and are used as addition compounds with electron-donor components.
9. In a process for the production of monoolefines in the range of C -C by the catalytic conversion of olefins in the range of C -C the improvement according to which the catalyst is a catalytic mixture of one or more cyclobutadiene-nickel-dihalides and one or more aluminumalkylhalides.
10. The improvement according to claim 9 wherein the cyclobutadiene-nickel-dihalides are used as addition compounds with electron-donor components.
11. The improvement according to claim 9 wherein the aluminium-alkylhalides are used as addition compounds with electron-donor components.
12. The process according to claim 9 wherein the cyclobutadiene-nickel-dihalides and the aluminium-alkylhalides are used as addition compounds with electron-donor components.
13. In a process for the production of monoolefines in the range of C -C by the catalytic conversion of ethene and propene at a temperature of up to 100 C. and at a pressure of up to 100 atmospheres, the improvement according to which the catalyst is a catalytic mixture of cyclobutadiene-nickel-dihalides, and an aluminium-alkylhalide.
14. The improvement according to claim 13 wherein the cyclobutadiene-nickel-dihalides are used as addition compounds with triphenyl phosphine.
15. The improvement according to claim 13 wherein the aluminium-alkylhalide is used as an addition compound with triphenyl phosphine.
16. The improvement according to claim 13 wherein the cyclobutadiene-nickel-dihalides and the aluminiumalkylhalide are used as addition compounds with triphenyl phosphine.
17. In a process for the production of mono-olefines in the range of C C by the catalytic conversion of ethene and propene at a temperature of up to 100 C. and at a pressure of up to 100 atmosphere, the improvement according to which the catalyst is a catalytic mixture of a cyclobutadiene nickel-compound selected from the group consisting of tetramethylcyclobutadiene-nickeldichloride, and tetraphenylcyclobutadiene-nickeldichloride, and a main group metal compound selected from the group consisting of aluminium-monoethyl-dichloride, aluminiummonoethyl-dibromide, aluminium-diphenyl-monochloride, dialuminium triethylmonoethoxy dichloride and beryliumdiethyl.
18. The'improvement according to claim 17, wherein the'cyclobutadiene nickel compound is used as an addition compound with triphenyl phosphine.
19. The improvement according to claim 17 wherein the main group metal compound is used as an addition compound with triphenyl phosphine.
20. The improvement according to claim 17 wherein the cyclobutadiene nickel compound and the main group metal compound are used as addition compounds with triphenyl phosphine.
References Cited UNITED STATES PATENTS 3,134,824 5/1964 Walker et al 260683.15 3,379,706 4/1968 Wilke 260683.15 X 2,969,408 1/1961 Nowlin et al. 3,321,546 5/1967 Roest et al.
FOREIGN PATENTS 651,596 2/1965 Belgium.
PAUL M. COUGHLAN, JR., Primary Examiner.
U.S. C1. X.R. 252431
US526079A 1965-02-12 1966-02-09 Process for production of olefines by dimerization,co-dimerization,polymerization and co-polymerization of olefines Expired - Lifetime US3442971A (en)

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US2969408A (en) * 1955-12-30 1961-01-24 Phillips Petroleum Co Process and catalyst for polymerization of olefins
US3134824A (en) * 1961-06-15 1964-05-26 Phillips Petroleum Co Ethylene polymerization with supported nickel biscyclopentadienyl catalyst
BE651596A (en) * 1963-08-10 1965-02-08
US3321546A (en) * 1962-11-30 1967-05-23 Shell Oil Co Olefin dimerization using aluminum alkyl halide-nickel complex catalyst

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US2969408A (en) * 1955-12-30 1961-01-24 Phillips Petroleum Co Process and catalyst for polymerization of olefins
US3134824A (en) * 1961-06-15 1964-05-26 Phillips Petroleum Co Ethylene polymerization with supported nickel biscyclopentadienyl catalyst
US3321546A (en) * 1962-11-30 1967-05-23 Shell Oil Co Olefin dimerization using aluminum alkyl halide-nickel complex catalyst
BE651596A (en) * 1963-08-10 1965-02-08
US3379706A (en) * 1963-08-10 1968-04-23 Studiengesellschaft M B H pi-allyl metal compounds and their use as polymerization, including oligomerization, catalysts

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