GB1602145A - Process for hydrogenating olefinic compounds - Google Patents

Process for hydrogenating olefinic compounds Download PDF

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GB1602145A
GB1602145A GB23598/78A GB2359878A GB1602145A GB 1602145 A GB1602145 A GB 1602145A GB 23598/78 A GB23598/78 A GB 23598/78A GB 2359878 A GB2359878 A GB 2359878A GB 1602145 A GB1602145 A GB 1602145A
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Description

(54) PROCESS FOR HYDROGENATING OLEFINIC COMPOUNDS (71) We, ANIC S.P.A., an Italian company, of Via M. Stabile, 216, Palermo, Italy, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a process for hydrogenating olefinic compounds.
A number of different processes for hydrogenating unsaturated aliphatic compounds have been described. In these processes, there are used either (a) stoichiometrical reagents (e.g. alkyl aluminium hydrides and diimides), or (b) heterogeneous catalysts (such as Ni on kieselguhr) or homogeneous catalysts based on derivatives of transition metals.
Homogeneous catalysts have the advantage of being active under comparatively low hydrogen pressures and temperatures. In addition, low levels of catalysts are employed. In particular case of the hydrogenation of polymeric substrates, the mild reaction conditions reduce the tendency for degradation of the polymer as a side reaction to take place, and the low levels of catalyst make the purification of the end products easier. More particularly, from the year 1963, there have been used homogeneous catalysts deriving from the combination of compounds of transition metals, preferably with organic ligands, with (c) aluminium alkyls, more particularly aluminium trialkyls, (d) Grignard compounds, or (e) lithium alkyls.
The systems (c) and (e) have been used for the hydrogenation of diolefin polymer such as polybutadiene, polyisoprene and soloprenes, in order to obtain novel polymeric materials. It is particularly interesting to be afforded the possibility of obtaining saturated thermoelastomers by hydrogenation of unsaturated copolymers such as styrene/butadiene/styrene in such a way that the unsaturated elastomeric polybutadiene units are replaced by saturated elastomeric co-ethylene-butene-l units.
The application is nonlimiting since it is possible, by hydrogenation, to prepare, as a general rule, polymers having properties which are radically different from those of the starting polymer, and also polymers which cannot be obtained otherwise.
According to the present invention, there is provided a process for hydrogenating an olefinic compound, in which the hydrogenation is conducted in the presence of a catalyst system comprising (a) a hydride derivative of aluminium having the formula AIH,.xB, AlHY2 . xB, AlHY2 . xB or (IIAlNR)n wherein x is 1, 2 or 3, Y is a halogen atom, n is a number in the range from 4 to 40, R is an aliphatic, cycloaliphatic, or aromatic radical, and B is a Lewis base, and (b) a compound of a transition metal.
Preferably, the compound of the transition metal is Co (acetvlacetonate)2, Co(2-ethylhexanoate) 2, Ni (acetylacetonate) Ni (2-ethylhexanoate)2, Ti (cyclopenta dienyl)2CI2, Ti(alcoholate)4, Fe(acetylacetonate)3, Be(acetylacetonate)2, VO(alco holate),, V(dialkylamide)4, an uncomplexed halide of a transition metal, or a complex of a transition metal with a Lewis base. In the latter case, the Lewis base is, for example, an amine or phosphine.
The olefinic compound which is hydrogenated according to the invention is preferably an alpha olefin, an olefin with an internal bond and which is optionally substituted, a cyclo-olefin, an aryl olefin, a conjugated diolefin, a non-conjugated diolefin, a multi-olefin capable of being selectively hydrogenated, an unsaturated olefin oligomer, an unsaturated polymeric compound, or a homopolymer or copolymer derived from a conjugated or non-conjugated olefin.
The catalyst systems used according to the invention are active irrespective of possible variations in the order of addition of the olefinic compound and/or the components of the catalyst system. They maintain their efficiency unaltered relative to the hydrogenation reaction, no further additions of catalyst being required. The olefinic compound may be fed batchwise to the reaction mixture, and different olefinic compounds, either in admixture or separate from each other, may be used. It is possible, moreover, to control and to improve the selectivity of the reaction by the addition of appropriate agents which tone down the catalyst activity, such as amines, alcohols and others.
Generally speaking, the activity of binary hydrogenation catalyst systems varies as the molar ratio of the two components of the catalyst is varied, such as is the case with, for example, systems based on aluminium trialkyls when the ratio R*: 1Me (Me = transition metal and R* = alkyl group bound to the aluminium) is varied.
Similarly, the catalyst systems used according to the present invention display a variation of their activity when the ratio H* : Me is varied (H* = hydride hydrogen bound to aluminium and Me = transition metal). However, the latter systems have the advantage that they attain their maximum activity for a ratio H* : Me which is less than the ratio H* : Me for the maximum activity of the systems based on aluminium alkyls. For example, by using Co compounds in the hydrogenation of monoolefins and diolefins, the systems used according to the present invention attain their maximum activity for a H* : Co ratio of 7 : 1 or less while for a similar reaction using aluminium alkyls the maximum activity has been reported as being attained for a R* : Co ratio of 18 :1 (W. R. Kroll, J. Catalysis, 15, 281, (1969)). Moreover, it has been reported (J. C. Falk, J. Polymer Sci., A 19, 2617, (1971)) that the systems AlR,/Co are active in the hydrogenation of unsaturated polymeric substrates with a R* : Co ratio of 9.75 :1, and in such a case the systems used according to this invention, based on hydrides, have proven to be active for a H* : Co ratio of 4 : 1 or more. This is indicative of an economic advantage obtainable with the catalyst system used according to this invention, inasmuch as the hydride hydrogens are completely exploited for the formation of the active catalyst, whereas, for systems based on aluminium alkyls, only a part of the Al-C bonds is exploited to this purpose and the remaining bonds are left unused.
Another advantage of the catalyst system used in this invention over the systems based on aluminium alkyls is that, while the latter display their maximum activity for a single value of the R* : Me ratio, the activity rapidly decreasing both above and below such value (see the above cited reference), for a few catalyst systems used m this invention, the activity remains at very high levels, which are near the maximum or at the very maximum, within a very wide range of values of the H* : Me ratio.
For example, this range is 6 to 30 for the (HA1N-iso C,H,)6 plus Co(2-ethylz hexanoate)2 system.
The catalyst systems used according to this invention have a still further advantage.
It is known that, as a rule as the degree of substitution of the double bond of the olefinic compound to be hydrogenated is increased, a decrease of the hydrogenation rate is experienced. Thus, for example, the hyrdogenation of isoprene with systems based on aluminium alkyls requires higher temperatures and, above all, higher hydrogen pressures than those which are required for hydrogenating simpler olefinic compounds such as alpha-olefins (Yoshio Tajima, E. Kunicka, J. Catalysis, 11, 83, (1968)).
Conversely, the catalyst systems used in this invention result in a virtually quantitative hydrogenation of isoprene to isopentane under the same mild conditions of temperature and pressure as are required for the hydrogenation of simpler olefinic compounds, and oligomerisation as a side reaction does not take place.
By varying the molecular structure of the derivative of aluminium hydride and/or the reaction conditions, it is possible to attain selective hydrogenation of olefinic compounds having unsaturations of different natures.
Lastly, in contrast to aluminium alkyls which are pyroforic, a few of the hydride derivatives used in this invention, and more particularly the poly(N-hydrocarbyl iminoalanes), are not pyroforic and, when in contact with air and moisture, they are decomposed by moderate reactions. In addition, the poly(N-hydrocarbylminoalanes) are stable at high temperatures (for example (HAlN-iso C,H,), decomposes at about 2500 C) and have a virtually unlimited storage life.
The reaction is preferably carried out in inert solvents such as aromatic or aliphatic hydrocarbonaceous solvents or ethereal solvents, at temperatures of from - 500C to 200"C, more preferably from 200C to 700C, and under a pressure of from 0.1 to 100 atmospheres absolute, preferably from 1 to 3 atmospheres absolute, with an atomic ratio of the hydride hydrogen to the transition metal higher than two.
EXAMPLES 1-11.
By adopting the quantities and the reaction conditions of TABLE 1, to a stirred solution of the olefins in toluene there are added, in the order given Co (acetylacetonate)2(toluene solution 0.06 M) and the derivative of aluminium hydride (generally in solution in toluene 0.2 M to 0.5 M of Al). The solution is then introduced in a stainless steel autoclave of the volume of 200 mls which has been evacuated of air. Then the autoclave is thermostatically heated to the desired temperature and pressurized with hydrogen. Stirring is carried out magnetically under the conditions which are prescribed and for the indicated period of time. As a rule, the complete conversion is achieved within a time which is definitely shorter than that which is adopted: especially in the case of the olefins, the hydrogenation step is completed within 10-15 minutes. At the end of the hydrogenation, the autoclave pressure is released and the products which have been obtained in solution are analyzed by gas chromatography.
TABLE I - HYDROGENATION OF OLEFINS WITH ALUMINIUM HYDRIDES-Co (ACETYLACETONATE)2 SYSTEMS.
Reaction conditions Hydrog. products Atomic Ex. Co(AcAc)2 ratio Hyd.pr. Temp. Time Convers. Yield No. Solvent Alane mmols H*/Co(1) olefine mmols atm C hrs % Kind % 1 Toluene AlH3.N(CH3)3 0.1 6 Vinylcyclohexene 2 30 1 100 Ethylcyclohexane 96 (20) (10) Ethylcyclohexene 4 2 Toluene AlH3.N(CH3)3 0.1 6 Isoprene (10) 2 30 1 98 Isopentane 94 (20) 2-methyl-butene-2 4 3 Toluene (HAlN-t.C4H9)4 0.1 6 Octene-1 (20) 2 30 1 100 Octane 100 (20) 4 Toluene (HAln-t.C4H9)4 0.1 6 cyclohexene (20) 4 30 1 90 cyclohexane 90 (20) 5 Toluene (HAlN.t.C4H9)4 0.1 6 2-methyl-butene-2 3 80 0.5 100 Isopentane 100 (20) (20) (HAlN-i.C3H7)6 6 Toluene 0.1 6 octene-1 (20) 2 30 1 100 Octane 100 (20) 7 Toluene (HAlN-i.C3H7)6 0.1 6 cyclohexene (20) 0.5 30 1 85 Cyclohexane 85 (20) 8 Toluene (HAlN-i.C3H7)6 0.1 6 cyclohexene (20) 2 30 1 100 Cyclohexane 100 (20) 9 Toluene (HAlN-i.C3H7)6 0.1 6 2-methyl-butene-2 2 30 1 99 isopentane 99 (20) (20) 10 Toluene (HAlN-n.C3H7)8 0.1 6 Octene-1 (20) 2 30 1 100 octane 100 (20) 11 Toluene (HAlN-n.C3H7)8 0.1 6 2-methyl-butene-2 2 30 1 88 isopentane 88 (20) (20) (1) H* hydride hydrogen.
EXAMPLES 12-29.
By using the quantities and the reaction conditions set forth in TABLE 2, a solution of the olefine is supplemented, in the order given, by Co(2-ethylhexanoate)2 dissolved in toluene (0.06M) and the derivative of aluminium hydride (generally in solution in toluene at 0.2M--0.5M of Al).
The solution is introduced in a stainless-steel 200-ml autoclave which has been evacuated of air. Then the autoclave is thermostatically heated to the desired temperature and pressurized with hydrogen. Magnetic stirring is maintained for a definite time interval and the complete conversion is generally obtianed within a time which is definitely shorter than the one which has been adopted: especially in the case of the alpha-olefines the hydrogenation step is completed within 5-15 minutes.
On completion of the hydrogenation step, the autoclave pressure is released and the products which have been obtained in solution are analyzed by gas chromatography.
TABLE 2 - HYDROGENATION OF OLEFINS WITH ALUMINIUM HYDRIDES - Co(2-ETHYLHEXANOATE)2 CATALYST SYSTEMS.
Reaction conditions Hydrog. products Co(2-ethyl- Atomic Ex. hexano)2 ratio Hyd.pr. Temp. Time Convers. Yield No. Solvent Alane mmols H*/Co(1) Olefine mmols atm. C hrs % Kind % 12 Toluene AlH3.N (CH3)3 0.1 6 Vinylcyclohexene 2 30 1 100 Ethylcyclohexane 97 (20) (10) Ethylcyclohexene 3 13 Toluene AlH3.N (CH3)3 0.1 6 Isoprene (10) 2 30 1 100 Isopentane 100 (20) 14 Toluene AlHCl2.O(C2H5)2 0.1 6 Vinylcyclohexene 2 30 1 99 Ethylcyclohexane 93 (20) (10) Ethylcyclohexene 6 15 Toluene AlHCl2.O(C2H5)2 0.05 6 Isoprene (10) 2 30 1 95 isopentane 95 (20) 16 Toluene (HAlN-t.C4H9)4 0.1 6 Octene-1 (20) 2 30 1 100 Octane 100 (20) 17 Toluene (HAlN-t.C4H9)4 0.1 6 Cyclohexene (20) 2 30 1 100 Cyclohexane 100 (20) 18 Toluene (HAlN-t.C4H9)4 0.1 6 Vinylcyclohexene 1.5 30 1 100 Ethylcyclohexane 7 (20) (20) Ethylcyclohexene 93 19 Toluene (HAlN-i.(C3H7)6 0.1 6 Octene-1 (100) 2 30 1 100 Octane 100 (20) 20 Diethyl- (HAlN-i.C3H7)6 0.1 6 Octene-1 (20) 2 30 0.25 100 Octane 100 ene (20) TABLE 2 CONTINUED
Reaction conditions Hydrog. products Co(2-ethyl- Atomic Ex. hexano)2 ratio Hyd.pr. Temp. Time Convers. Yield No. Solvent Alane mmols H*/Co Olefine mmols atm. C hrs % Kind % 21 Toluene (HAlN-i.C3H7)6 0.1 6 Cyclohexene (20) 2 30 0.5 100 Cyclohexane 100 (20) 22 Toluene (HAlN-i.C3H7)6 0.1 6 2-methyl-butene-2 2 30 1 100 Isopentane 100 (20) (20) 23 Heptane (HAlN-i.C3H7)6 0.1 6 Vinylcyclohexene 2 30 1 100 Ethylcyclohexane 97 (20) (10) Ethylcyclohexene 3 24 Tetra- (HAlN-i.C3H7)6 0.1 6 Vinylcyclohexene 2 30 1 100 Ethylcyclohexane 26 hydro- (10) furan (20) Ethylcyclohexene 74 25 Toluene (HAlN-i.C3H7)6 0.15 6 Isoprene (100) 2 30 2 100 Isopentane 81.5 (15) 2-methyl-butene-2 18.5 26 Toluene (HAlN-n.C3H7)8 0.1 6 Octene-1 (20) 2 30 1 100 Octane 100 (20) 27 Toluene (HAlN-n.C3H7)8 0.1 6 Cyclohexene (20) 2 30 1 100 Cyclohexane 100 (20) 28 Toluene (HAlN-n.C3H7)8 0.1 6 2-methyl-butene-2 2 30 1 100 Isopentane 100 (20) (20) 29 Toluene (HAlN-n.C3H7)8 0.1 6 Isoprene (10) 2 30 1 100 Isopentane 90 (20) 2-methyl-butene-2 10 EXAMPLES 30-32.
These Examples show that variations of the order of addition of the substrate and/or of the catalyst components do not impair the performance of the catalyst system.
EXAMPLE 30.
To a stirred solution of Co(2-ethyl hexanoate), 0.1 millimol in 17 ml of toluene are added in the order given (HAlN-isoC,H,)6 (0.6 milligramatoms of Al, corresponding to 3 mls of a toluene solution 0.2M of Al) and isoprene (10 millimols).
The mixture is introduced in a stainless steel 200-ml autoclave evacuated of air.
Then the autoclave is thermostatically heated to the temperature of 30"C and pressurized with 2 atm of hydrogen. Magnetic stirring is maintained under such conditions during one hour .On completion of the hydrogenation step pressure in the autoclave is released and the gas chromatographic analysis of the solution shows that isoprene has been hydrogenated to isopentane to 100%.
EXAMPLE 31.
To a stirred solution of (HAlNisoC,H7)s (0.6 milligramatoms of Al) in toluene (18 mls) are added, in the order given, Co(2-ethylhexanoate) (0.1 millimol, corresponding to 2 mls of a 0.05M solution in toluene) and isoprene (10 millimols).
The mixture is introduced in a 200-ml stainless steel autoclave evacuated of air. Then the autoclave is thermostatically brought to a temperature of 30"C and pressurized with hydrogen at 2 atm. Magnetic stirring is maintained under these conditions for one hour. Lastly, the autoclave presure is released and the gas chromatographic analysis of the solution shows that the isoprene has been hydrogenated to 100% (isopentane: 86%, 2-methyl-butene-2 14%).
EXAMPLE 32.
To a stirring solution of isoprene (10 millimols) in toluene (17 mls) are added, in the order given, (HA1N-isoC,H,), (0.6 milligramatoms of Al corresponding to 3 mls of a toluene solution 0.2M of Al) and Co(2-ethylhexanoate) (0.1 millimols, corresponding to 2 mls of a 0.05M solution in toluene). The solution is introduced in a 200-ml stainless steel autoclave which has been evacuated of air. Then the temperature is thermostatically brought to 30"C and the autoclave is pressurized with hydrogen to 2 attain. Magnetic stirring is maintained under these conditions during one hour. Lastly, the autoclave pressure is released and the gas chromatographic analysis of the solution indicates that isoprene has been hydrogenated to 100% (isopentane 70% and 2-methyl-butene-2 30%).
EXAMPLE 33.
This example shows that it is possible to feed the substrate in batches and without any supplemental addition of the catalyst. It is possible to feed in different substrates, both simultaneously and sequentially. The results show that, in fact, the catalyst retains its activity unaltered in time and, moreover, they confirm that satisfactory results can be achieved with low amounts of catalyst. To a stirred solution of octene-1 (20 millimols) in toluene (15 mls) are added, in the order given, Co(2-ethylhexanoate), (0.1 millimol corresponding to 2 mls of a 0.05M solution in toluene) and (HAIN-isoC3H7)6 (0.6 milligramatoms of Al, corresponding to 3 mls of a 0.2M solution in toluene of Al). The solution is introduced in a 200-ml stainless steel autoclave which has been evacuated of air. Then the temperature is thermostatically brought to 300C and the autoclave is pressurized to 2 atm with hydrogen. Magnetic stirring is maintained for 15 mins. and the pressure drop indicates that the hydrogenation reaction has been completed. Portions of octene-1 (20 millimols each) have been added and lastly, portions of cyclohexene (20 millimols) dissolved in toluene(12 mls) have been added at the time intervals indicated below, the pressure being brought again to 2 atm of hydrogen each time.
TIME INTERVAL ADDITION No. SUBSTRATE initial octene-l 15 mins 2nd octene-l 20 mins 3rd octene-1 30 mins 4th octene-1 60 mins 5th cyclohexene Upon the addition of cyclohexene the reaction mixture has been maintained 2 hours under the conditions indicated above. Then the pressure has been finally released and the reaction products have been analyzed by gas chromatography. The conversion of octene-1 and of cyclohexene into octane and cyclohexane, respectively, was quantitative.
EXAMPLE 34.
This example shows that the addition of amines lowers the catalyst activity without, however, suppressing it Due to the variations of the reaction velocity, it is thus possible, in the case of polyolefines, to adjust the selectivity of the hydrogenation.
To a stirred solution of Co(2-ethylhexanoate)2 (0.1 millimol) in toluene (17 mls) are added, in the order given (HAIN-isoC3H7)6 (0.6 milligramatom of Al corresponding to 3 mls of a toluene solution of 0.2M of Al), iso C,H7NH2 (0.7 millimol) and vinylcyclohexene (10 millimols). The solution is introduced into a 200-ml stainless steel autoclave which has been evacuated of the air. Then the autoclave is thermostatically heated to 30"C and presurized with hydrogen at 2 atm. Magnetic stirring is provided under presure for one hour. Lastly, the autoclave pressure is released and the solution analyzed by gas chromatography. The result is that vinylcyclohexene has been hydrogenated to 100% (ethylcyclohexene: 77% - ethylcyclohexene : 23%).
EXAMPLE 35.
This example shows that the addition of alcohols lowers the catalyst activity but does not suppress same and, in the case of polyolefines, it can adjust the selectivity of the hydrogenation. To a stirred solution of Co(2-ethylhexanoate)2 in toluene (17 mls) are added, in the order given, (HAIN-isoC,H7)G (0.6 milligramatoms of Al corresponding to 3 mls of a solution in toluene, 0.2M of Al), C2HsOH (0.7 millimol) and vinylcyclnhexene (10 millimols). The solution is introduced in a 200-ml stainless steel autoclave which has been evacuated of air. Then the autoclave is thermosatically heated to 30"C and pressurized with hydrogen to 2 atm. Magnetic stirring is provided under pressure for one hour. On completion of this step the autoclave pressure is released and the solution is analyzed by gas chromatography.
The result is that the vinylcyclohexene has been hydrogenated to 100% (ethylcyclohexene 98.5% -- ethylcyclohexane 1.5%).
EXAMPLE 36.
To a stirred solution of 2-methylbutene-2 (30 millimols) in toluene (17 mls) are added in the order given Co(laurate)2 (0.1 mIllimols) and (HAIN-isoCsH7)6 (0.6 milligramatoms of Al corresponding to 3 mls of a toluene solution 0.2M of Al).
The solution thus obtained is introduced in a 200-ml stainless steel autoclave evacuated of air. The autoclave is pressurized to 2 atm of hydrogen and thermostatically heated to 30"C. Magnetic stirring is provided during one hour. At last, the autoclave pressure is released and the solution is analyzed by gas chromatography. The result is that 2-methyl-butene-2 has been hydrogenated to 82% to isopentane.
EXAMPLES 37 48 (FIGURE 1).
The data plotted in FIGURE 1 shows that the AlH, . N(CH3)3-Co(2-ethyl- hexanoate ) 2 system shows a maximum activity in correspondence with H*/Co = 7 (H* is the hydride hydrogen) in the hydrogenation of isoprene. The tests have been conducted according to the following procedure.
To a solution of Co (2-ethylhexanoate)2 are added, in the order given, AlH2.
N(CH,), (solution in toluene 0.1M) in variable quantities, and isoprene (10 millimols). The initial quantity of toluene is such that, at the end, the volume of the solution is 20 mls. The solution is introduced in an evacuated 200-ml stainless steel autoclave. The autoclave is then thermostatically heated to 30"C and pressurized to 2 atm of hydrogen. Magnetic stirring is provided under these conditions for 30 mins.
Finally, the autoclave pressure is released and the solution of the obtained products is gas chromatographically analyzed, the results being those plotted in FIGURE 1. The plots of FIGURE 1 show the trends of the percentage yield of isopentane and of the percentage of unreacted isoprene in the reaction of hydrogenation of isoprene, as a function of the hydride hydrogen to cobalt ratio. The abscissae are the values of the atomic ratio of hydride hydrogen to cobalt, and the ordinates are the percentage values. The plot No. 1 relates to the percentage yield of isopentane as produced, and the plot No. 2 is the percentage of unreacted isoprene.
EXAMPLES 49-59 (FIGURE 2).
The plots of FIGURE 2 confirm that the AlH3. N( CH,) ,-Co (2-ethyl- hexanoate)2 system attains its maximum activity for H*/Co = 7 also in the hydrogenation of monoolefines (hexene-1). Apart from the different nature of the substrate and its quantities (20 millimols of hexene-1) and the reaction time (15 mins.), the quantity and the nature of the solvent and the components of the catalyst, as well as the other reaction conditions, are the same as for FIGURE 1.
On the plot of FIGURE 2 the curve No. 1 shows the tendt of the percentage yield of nor. hexane in the reaction of hydrogenation of hexene-1 as a function of the value of the ratio of the hydride hydrogen to cobalt. The abscissae report values of the hydride hydrogen to cobalt, and the ordinates are the percentage yield values.
EXAMPLES 60-69 (FIGURE 3).
The results of FIGURE 3 show that, in the hydrogenation of isoprene the (HAlN-iiCCH- ) -Co (2-ethyihexanoate)2 system attains its maximum activity for H*/Co = 6 (H* being the hydride hydrogen) .For ratios of H*/Co smaller than 6, the activity, though being decreased somewhat, still remains at very high levels.
Apart from the different derivative of aluminium hydride, the quantities and the nature of the solvent, of the Co compound, of the substrate, as well as the reaction conditions, are those of FIGURE 1. In the plots of FIGURE 3 are shown the trends of the percentage yield of isopentane and the percentage of unreacted isoprene in the hydrogenation reaction of isoprene as a function of the atomic ratio of hydride hydrogen to cobalt. The abscissae report the values of the atomic ratio of the hydride hydrogen to cobalt, and the ordinates the percentage values of the yield of isopentane (curve No. 1) and of unreacted isoprene (curve No. 2).
EXAMPLES 70-78 (FIGURE 4).
The results of FIGURE 4 confirm that also in the hydrogenation of hexene-l, the (HAlN-isoC3H7)-Co(2-ethyihexanoate), exhibits its top activity for H*/Co of ab
TABLE 3 - HYDROGENATION OF OLEFINS WITH ALUMINIUM HYDRIDES-Ni (ACETYLACETONATE)2 CATALYST SYSTEMS.
Reaction conditions Hydrogenation products Atomic Hydr.
Ex. Solvent Ni(AcAc)2 ratio Olefine press. Temp. Time Conver- Yield No. mls Alane millimols H*/Ni(1) millimols atm. C hrs. sion % Kind % 79 Toluene AlH3.N(CH)3 0.1 6 Vinylcyclohexene 2 30 1 100 Ethylcyclohexane 81 (20) (10) Ethylcyclohexene 19 80 Toluene AlH3.N(CH)3 0.1 6 Isoprene (10) 2 30 1 100 Isopentane 65.5 (20) 2-methyl-butene-2 34.5 81 Toluene AlHCl2.O(C2H5)@ 0.1 6 Vinylcyclohexene 2 30 1 36 Ethylcyclohexane 2 (20) (10) 34 Ethylcyclohexene 82 Toluene (HAlN-i.C3H7)6 0.1 6 Octene-1 (20) 2 30 1 97.5 n-octane 97.5 (20) 83 Toluene (HAlN-i.C3H7)6 0.1 6 Vinylcyclohexene 2 30 1 100 Ethylcyclohexane 25.5 (20) (10) Ethylcyclohexene 74.5 (1) H* is hydride hydrogen EXAMPLES 84-88 (TABLE 4).
By adopting the quantities and the conditions as tabulated, to a toluene solution of the titanium compound there ar added, in the order given, the derivative of aluminium hydride (generally solutions of 0.1M to 0.5M of Al) and the olefine concerned. The solution is introduced in a 200-ml stainless steel autoclave which had been previously evacuated of air, and is aged for one hour at 800C. Then the autoclave is thermostatically heated to the desired temperature and pressurized with hydrogen.
Magnetic stirring is applied under the tabluated conditions and for the tabulated time interval. On completion of this step, the pressure in the autoclave is released and the products which have been obtained in solution are analyzed by gas chromatography.
TABLE 4 - HYDROGENATION OF OLEFINS WITH CATALYST SYSTEMS BASED ON ALUMINIUM HYDRIDES AND TITANIUM COMPOUNDS
Reaction conditions Hydrogenation products Titanium Atomic Hydr. Conver Ex. Solvent Compound ratio press. Temp. Time sion Kind Yield No. mls Alane (mls) (1) H*/Ti (2) Olefine mls. atm C hrs % 84 Toluene AlH3.N(CH3)3 Cp2TiCl2 12 Isoprene (10) 3 70 1 100 Isopentane 93 (20) (0.1) 2-methyl-butene-2 7 85 Toluene (HAlN-i.C3H7)6 Cp2TiCl2 12 Cyclohexene (20) 3 70 1 100 Cyclohexane 100 (20) (0.1) 86 Toluene (HAlN-i.C3H7)6 Cp2TiCl2 12 2-methyl-butene-2 3 70 1 65 Isopentane 65 (20) (0.1) (20) 87 Toluene (HAlN-i.C3H7)6 Cp2TiCl2 12 Isoprene (10) 3 70 1 100 Isopentane 41 (20) (0.1 2-methyl-butene-2 59 88 Toluene (HAlN-i.C3H7)@ Cp2TiCl2 6 Cyclohexene (20) 3 70 1 94 Cyclohexane 94 (20) (0.1) EXAMPLES 89 and 90 (TABLE 5).
By adopting the tabulated quantities and conditions, to a toluene solution of the vanadium compound are added, in the order given, the derivative of aluminium hydride (generally as a toluene solution, 0.1M to 0.5M) and the olefine.
The solution is introduced in a 200-ml stainless steel autoclave which has been purged of air. Then the autoclave is thermostatically heated to the tabulated temperature and pressurized with hydrogen.
Magnetic stirring is applied under the tabulated conditions and for the tabulated time interval. On completion of this step, the pressure in the autoclave is released and the product as obtained in solution are analyzed by gas chromatography.
TABLE 5 - HYDROGENATION OF OLEFINS WITH CATALYST SYSTEMS BASED ON ALUMINIUM HYDRIDES AND VANADIUM COMPOUNDS
Reaction conditions Hydrogenation products Vanadium Atomic Hydr. Conver.
Ex. Solvent Compound ratio press. Temp. Time sion Yield No. mls Alane mls H*/V (1) Olefine mls atm C hrs % Kind % 89 Toluene AlH3.N(CH3)3 VO(O.n.C4H9)3 12 Octene-1 4 70 2 93 Octane 93 (20) (0.2) 90 Toluene AlH3.N(CH3)3 V[N(C2H5)2]4 12 Octene-1 3 30 21 65 Octane 51 (20) (0.1) (1) H* - hydride hydrogen EXAMPLE 91 (TABLE 6).
By adopting the tabulated quantities and conditions, to a toluene solution of the iron compound are added, in the order given, the aluminium hydride derivative (generally in a 0.1M-0.5M Al toluene solution) and the olefine concerned.
The solution is introduced into a 200-ml stainless stel autoclave which has been evacuated of air.
Then the autoclave is thermostatically heated to the tabulated temperature and pressurized with hydrogen.
Magnetic stirring is applied under the conditions which are tabulated and for the tabulated time interval.
On completion of this step, the autoclave pressure is released and the products obtained in solution are analyzed by gas chromatography.
TABLE 6 - HYDROGENATION OF OLEFINES WITH CATALYST SYSTEMS BASED ON ALUMINIUM HYDRIDES AND Fe (ACETYLACETONATE)3.
Reaction conditions Atomic Hydr. Hydrogenation products Ex. Solvent Fe(AcAc)3 ratio press. Temp. Time Conver No. mls Alane mls H*/Fe (1) Olefine mls atm. C hrs sion % Kind Yield 91 Toluene AlH3.N(CH3)3 0.5 9 Octene-1 (20) 4 30 1 93 Octane 93 (20) (1) H* is the hydride hydrogen.
EXAMPLE 92.
To a stirred solution of CoCl2 (0.1 millimol) in toluene (17 mls) is added a solution of (HAlN-isoC3H7)6 (0.6 milligramatoms of Al) in toluene (3 mls). A reaction is noted which brings about a slow conversion of CoCl2 into a soluble compound. After 15 mins. isoprene (10 millimols) is added and the reaction mixture is introduced in a 200-ml stainless steel autoclave which has previously been evacuated of air. The autoclave is thermostatically heated to 30 C and pressurized to 2 atm. of hydrogen. Magnetic stirring is continued during one hour. On completion of this step the autoclave is vented and the solution is gas chromatograpically analyzed. The result is that isoprene has quantitatively hydrogenated to isopentane (yield 73%), 2-methyl-butene-2 (yield 22.5%) and 3-methyl-butene (yield 4.5%).
EXAMPLE 93.
A sample (1.55 gram) of a block copolymer of styrene-butadiene-styrene containing 81.5% of butadiene units (90% with 1,4 linking and 10% with 1.2 linking) is solubilized in cyclohexane (100 mls). The stirred solution is then supplemented, in the order given, by Co(2-ethylhexanoate)2 (0.1 mol corresponding to 0.78 ml of a 0.13M solution in cyclohexane) and by AlH,. N(CH,), (0.2 mol corresponding to 0.66 ml of a 0.3M solution of Al in toluene). The resultant solution is then charged in a 200-ml stainlees steel autoclave which had been evacuated by air and thermostatically heated to 50"C. The autoclave is pressurized to 5 atm. of hydrogen.
Magnetic stirring is applied under these conditions for one hour. Finally, the pressure is released and the product is recovered quantitatively by evaporating off the solvent from the reaction mixture which had previously been repeatedly washed with water to remove the catalyst impurities. The IR spectrum (a very weak band at 10.35 micron which can be attributed to traces of residual unsaturations and the 1NMR show that a block copolymer styrene- (ethylene-butene-1 ) -styrene has been obtained in agreement with the virtually quantitative hydrogenation (about 100%) of the starting polymer.
EXAMPLE 94.
The hydrogenation of a block copolymer styrene-butadiene-styrene has been carried out by using the same compounds and the same conditions of EXAMPLE 93 with the only exception of the aluminium hydride derivative which was now(HA1N- isoC,H7), and the ratio H*/Co which was adopted and the was 4 (H* is hydride hydrogen).
At the end of the reaction the IR spectrum and the 1HNMR show that a block polymer styrene-(ethylene-butene-l )-styrene has been obtained, in agreement with the virtually quantitative hydrogenation (about 100%) of the butadiene units of the starting polymer.
EXAMPLE 95.
A sample (1.4 gram) of polybutadiene having a high contents of 1,4-cis unsaturations (about 99%) is solubilized in cyclohexane (100 mls). The stirred solution is then supplemented, in the order given, with Co(2-ethylhexanoate)2 (0.1 millimol corresponding to 0.78 ml of a 0.13M solution in cyclohexane) and with AIH,.
N(CH3), (0.167 millimol corresponding to 0.54 ml of 0.31M solution in toluene).
The resultant solution is then introduced into a 200-ml stainless steel autoclave which has been evacuated of air and thermostatically heated to 50"C. The autoclave is pressurized with hydrogen to 3 atm. Magnetic stirring is applied under these conditions for one hour. Finally, the pressure is released and the product is quantitatively recovered by evaporating off the solvent from the reaction mixture which had previously been washed many times with water so as to remove the catalyst impurities.
The 1HNMR indicates that a copolymer of ethylene and butadiene (1,4 trans) has been obtained which corresponds to the hydrogenation of the 88% of the unsaturations of the starting polymer with an inversion of the structure of the residual unsaturations.
EXAMPLE 96.
The hydrogenation of a sample of polybutadiene having a high contents of 1,4 cis unsaturations has been carried out by adopting the same compounds and the same conditions as in EXAMPLE 95, with the exception of the hydride derivative of aluminium which was (HA1N-isoC,H,),. The ratio H*/Co which has been used is 5.
(H* is the hydride hydrogen).
On completion of the step, the 1HNMR indicates that a copolymer of ethylene and butadiene (1,4 trans) has been obtained, which corresponds to the hydrogenation of the 86.7% of the unsaturations of the starting polymer, with an inversion of the structure of the residual unsaturations.

Claims (13)

WHAT WE CLAIM IS:
1. A process for hydrogenating an olefinic compound, in which the hydrogenation is conducted in the presence of a catalyst system comprising (a) a hydride derivative of aluminium having the formula AlH, . xB, AlHY2 . xB, AlH2Y . xB or --(HAINR)il wherein x is 1, 2, or 3, Y is a halogen atom, n is a number in the range from 4 to 4û, R is an aliphatic, cycloaliphatic cr aromatic radical and B is a Lewis base, and (b) a compound of a transition metal.
2. A process according to claim 1, wherein the hydrogenation is carried out in a solvent inert to the hydrogenation.
3. A process according to claim 2, wherein the hydrogenation is carried out in an aromatic or aliphatic hydrocarbonaceous solvent, an ethereal solvent or another inert solvent.
4. A process according to claim 1, 2 or 3, wherein the hydrogenation is carried out at a temperature of from -500C to +2000C.
5. A process according to claim 4, wherein the hydrogenation is carried out at a temperature in the range from +20"C to +400 C.
6. A process according to any preceding claim, wherein the hydrogenation is carried out at a pressure in the range from 0.1 to 100 atmospheres absolute.
7. A process according to claim 6, wherein the hydrogenation is carried out at a pressure in the range from 1 to 3 atmospheres absolute.
8. A process according to any preceding claim, wherein the hydrogenation is carried out with an atomic ratio of the hydrogen directly bound to the aluminium of derivative (a) to the transition metal of compound (b) equal to or greater than 2: 1.
9. A process according to any preceding claim, wherein the compound of the transition metal is Co(acetylacetonate)2, Co(2-ethylhexanoate),, (Ni(acetylacetonate)2, Ni (2-ethylhexanoate)2, Ti(cyclopentadienyl) 2C12 Ti(alcoholate)4, Fe(acetylacetonate),, Fe (acetylacetonate)2, VO(alcoholate),, V ( dialkylamide)4, an uncomplexed halide of a transition metal, or a complex of a transition metal with a Lewis base.
10. A process according to any preceding claim, wherein hydrogenation is carried out in the presence of an amine or alcohol as a "moderator" in order to obtain selective hydrogenation.
11. A process according to any preceding claim, wherein the olefinic compound is an alpha olefin, an olefin with an internal bond and which is optionally substituted, a cyclo-olefin, an aryl olefin, conjugated diolefin, a non-conjugated diolefin, a multiolefin capable of being selectively hydrogenated, an unsaturated olefin oligomer, an unsaturated polymeric compound, or a homopolymer or copolymer derived from a conjugated or non-conjugated olefin.
12. A process for the hydrogenation of an olefinic compound, substantially as described in any one of the foregoing Examples.
13. A hydrogenated compound whenever produced by a process according to any preceding claim.
GB23598/78A 1977-06-08 1978-05-26 Process for hydrogenating olefinic compounds Expired GB1602145A (en)

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