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    • 专利摘要:
    PURPOSE:To prepare lower alpha-olefin dimers having controlled isomer contents by dimerizing lower alpha-olefins using highly active Ni-type Ziegler catalyst which contains halogenated phenols as an activating agent.
    公开号:SU904514A3
    申请号:SU782630800
    申请日:1978-06-29
    公开日:1982-02-07
    发明作者:Сато Хироси；Ногути Таканобу；Ясуи Сеймеи
    申请人:Сумитомо Кемикал Компани Лимитед (Инофирма)；
    IPC主号:
    专利说明:

    ; The invention relates to a process for the dimerization of lower oi-olefins, for example ethylene and propylene, in the presence of a Ziegler-type catalyst based on nickel compounds.  Lower olefin dimers have the most diverse industrial applications.  So, for example, from propylene dimer, 2-methylpentene, by cracking in the presence of a silica-alumina catalyst, isoprene-methylpentene-T is obtained, which is: monomer, upon receipt of polymethylpentene, which is transparent, has excellent electrical characteristics and gives good characteristics.  : stereoregular polymerization.  2.3 Dimethylbutene can be dehydrated to 2.3 dimethylbutadiene, using jayeMoro as the starting mother. ala for synthetic rubber,.  2,3-Dimethyl-2-butene is an important starting material for the production of drugs used in agriculture and medicines.  3-methylbutene-1, which is a codimer of ethylene and propylene, is also used as a starting material in the preparation of drugs or preparations used in agriculture.  The known method of dimerization of propylene in the presence of a catalyst containing, as components, a complex nickel compound with n allyl, an organoaluminum halide, and an organic phosphine.  The result is a propylene dimer with a high yield of 6x10 g / h per gram of nickel o (meaning gram of propylene dimer per gram of nickel per hour).  The process for the preparation of isomers can be easily controlled by the rm.  The disadvantage of this method is that the complex compound of nickel with n-allyl must be synthesized separately, and this synthesis causes considerable difficulties.  In addition, this complex is very unstable in the air, and therefore working with it causes inconvenience.  A known method of dimerization of lower cl, α-olefins using a catalyst containing a compound of nickel, an organoaluminium halide and an organic phosphine 2.  However, when using aluminum organic halides as catalyst components, the halogen atom is bonded to aluminum, which, when combined with hydrogen, forms hydrogen halide, which causes equipment corrosion. In addition, it is impossible to completely separate the hydrogen halide that forms by distillation.  As a result, undesirable product contamination occurs.  Although the product yield and isomer distribution can to a certain extent be controlled by changing the number of halogen atoms in organoaluminum halides, however, such a change requires an additional reaction, which is not easy to accomplish during the process.  A known method of dimerization of lower-o-olefins, for example, propylene using a catalyst containing divalent nickel compounds, for example nickel bisacetylacetonate and an activating agent selected from the group containing aluminum alkylalkoxide and aluminum trialkyl.  The process is carried out at a molar ratio of the activating agent: 77 of a gel bisacetylacetonate, equal to 0.12: 1, a temperature of 40-200 ° C, and a pressure required for carrying out dimerization in the liquid or partially condensed phase.  The main products of the process are linear dimers (up to 7) L5j.  I - However, the activity of the specified catalyst is very low with respect to the dimerization reaction of propylene.  For example, the dimer yield is 1,. 8 g / h per 1 g of nickel.  In addition, carrying out the process in the presence of the specified catalyst does not allow adjustment of the isomer distribution in the dimer.  The aim of the invention is to increase the productivity and selectivity of the process by controlling the distribution of the isomer in the dimer. The goal is achieved by dimerizing lower 9 7b-olefins using a catalyst containing a divalent nickel compound, a salt, or a complex nickel compound, trialkyl aluminum, and using a catalyst additionally contains a1cium compound of trivalent phosphorus of the formula P R. R or (R;, N), PR or (Ro) f, P, in which R, R may be the same or different and each means alkyl Su-Cg, lower alkenyl, cyclohexyl, phenyl, tolyl, p-methoxyphenyl, benzyl and p is an integer (1-3), and chlorinated phenol selected from the group containing 2,3-, 2, -, 2,5-, 2,6-, 3 ,, 3,5-Dichlorophenol, 2 , 4,6-, 2,4,5-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol and tetrachlorohydroquinone, with a molar ratio of trialkylaluminium (B) to nickel compound (A) equal to 2-500, compounds - trivalent phosphorus (s) to the compound of nickel - 0.1-50 and chlorinated phenol (D) to the trialkylaluminum - 0.2 -20.  It is preferable to conduct the process at a molar ratio of chlorinated phenol to trialkyl aluminum of 0.5-10, preferably at D / B 2-10 and most preferably at D / B 2-5.  The concentration of catalyst in the process is usually about 10 mol (based on the nickel component) per reaction mixture, but its value may vary depending on the desired reaction rate.  The molar ratio of catalyst components is also an important factor in controlling the catalytic activity of the catalyst and controlling the distribution of the isomers formed.  Although the catalytic activity and distribution of the resulting isomers in a complex manner depends on all catalyst components and reaction conditions, in general, the catalytic activity increases with an increase in the molar ratio B / A and D / B.  However, as the C / A molar ratio increases, it decreases.  The molar ratios are chosen depending on which product they want to get.  The catalyst components phosphorus-containing compound, component C, has the greatest effect on the distribution of the dimer isomers formed.  The distribution of the resulting isomers of propylene dimers changes with an increase in the basicity of phosphorus-containing compounds from the distribution enriched in methylpentanes to the distribution enriched in dimethylbutenes, while other conditions also have an effect, but more subtle.  The desired selectivity is achieved by selecting the phosphorus-containing compound in accordance with the products that are to be obtained.  In addition, in accordance with the invention, by selecting a D / B molar ratio in the range of 1-20, preferably 2-10, most preferably 2-5, olefin isomers can be selectively obtained from lower oL-olefins in one step through isomerization The dimers (final olefins) of these cC-olefins. For example, in the dimerization of propylene, the amount of 2,3-dimethyl butene-2 formed in relation to the total amount of dimers is 50% or more, and under special conditions it reaches 80% or more.  And further, the amount of 2,3-Dimethyl-butene-2 in relation to 2,3-Dimethylbutenes is 50% or more, and under special conditions it reaches 95% and more.  If the entire amount of 2,3-dimethylbutene-2 is formed through the isomerization of 2,3-Dimeti butene-1, then dimerization and isomerization proceed simultaneously. Lower oL-olefins dimerize to form ultimately dimers of olefins with an unsaturated C — C bond at the end of the chain.  For example, propylene is dimerized to form olefins, such as 2,3 Dimethyl-1-butene, which is a valuable intermediate for the synthesis of chemicals.  The resulting olefins can be. -translated by isomerization into their isomers.  For example, 2,3 dimethylbutan-2, which is a valuable semi-product for the synthesis of chemicals used in agriculture and the like, can be obtained by isomerization of 2,3 dimethylbuthene-1.  In addition, the isomers of dimers can be obtained with high selectivity in a single stage using a special a way prepared catalyst.  This means that lower CL olefins can be directly converted into isomers of olefin dimers.  For example, propylene is converted to a single stage with a high selectivity not only in 2,3-Dimethyl-butane-1, but also in 2,3 Dimethyl-2-butene, which is an isomer of the first.  In the preparation of the catalyst in accordance with the proposed method, the order of mixing the components is not essential, but it is desirable that component D - chlorinated phenol and component B - trialkyl aluminum are always mixed with each other in the presence of component A - a nickel compound.  It is necessary to avoid that components D and B are mixed with each other in the absence of component A.  The following order of mixing is most preferred: components A, B and C are mixed in any order, after which the resulting mixture is mixed with component D.  Components A, C and D are mixed in any order, after which the resulting mixture is mixed with component B or mixture A and B mixed with mixture C and D, or mixture A and D mixed with mixture B and C, or simultaneously mixed. all four components A, B, C D.  In all cases, dimers are obtained in high yield.  The proposed method can be used to preliminarily prepare a catalyst solution in an inert solvent, which uses aromatic hydrocarbons (e.g. benzene, toluene, and xylene), aliphatic che hydrocarbons, e.g. hexane, heptane, and cyclohexane and halogenated aromatic hydrocarbons, e.g. chlorobenzene, and o-, m- and p-dichlorobenzene, which is then used in carrying out the reaction.  The catalyst can also be prepared. and in the reactor in the presence of an inert solvent, and then immediately carried out the reaction. In particular, to obtain a catalyst of a high degree of homogeneity, stability and activity. it is desirable to mix its components in the presence of a1-olefin, for example, ethylene or propylene.  In some cases, highly stable catalysts are obtained by mixing components in the presence of very small amounts of conjugated dienes containing 4-6 carbon atoms, for example, butadiene, isoprene or 1.3 pentadien.  The presence of large amounts of dienes with sped double bonds in the reaction system somewhat reduces the yield of dimers of lower o-olefins, and therefore, their preferred amount should be 1-100 moles per mole based on the nickel compound.  The dimerization reaction is usually wire in an inert solvent, but in some cases it can also be carried out in the absence of a solvent in an environment of liquefied lower end, for example, liquid ethylene or propylene.  The reaction is usually carried out at a temperature of -50-100 ° C and a pressure which is automatically set at a given temperature.  Its value is usually 0-30 kg / cm. However, in some cases, the required pressure is maintained by means of a compressor.  The lower o-olefins used in the present invention contain 1.5 carbon atoms.  These can be, for example, ethylene, propylene, butene-1, isobutylene and pentene-1.  As the nickel compound, organic nickel salts are used, for example, nickel naphthenate, octate, formate, acetate, benzoate, nickel oxalate, etc. d. , nickel salts of inorganic acids, for example, chloride, bromide, iodide, fluoride, nitrate, nickel sulfonate, etc. d.  and nickel complex compounds, such as, for example, nickel diacetylacetonate, nickel distitylacetoacetonate, nickel dimethylglyoxime, and the like. d.  As trialkyl aluminum can be trimethyl aluminum, triethyl aluminum, tri-n-propyl luminium, tri-isobutyl aluminum, tri-n-pentyl. aluminum, tri-n-hexylaluminum tricic / Lubexylaluminum, etc. d. The final product of the dimerization reaction is isolated from the reaction mixture by conventional methods, namely, termination of the reaction and removal from the reaction mixture by rectification.  After rectification, the product is isolated by gas chromatography.  The composition of the isomers in the product is determined by studying infrared spectra, nuclear magnetic resonance spectra and mass spectrometry analysis.  Example 1  A 200 ml ampoule of the foam bottle was flushed with nitrogen to remove air from it, after which 20 ml of dry chlorobenzene, 0.75 ml of a solution of 0.15 mmol of nickel naphthenate in toluene, 1.5 ml of a solution of 0.15 mmol of triphenylphosphine G toluene and 0.5 kn of isoprene in the sequence indicated.  Then 1.5 ml of a solution of 1.5 mmol of triethylaluminum in toluene are added to it and the mixture is stirred at room temperature for 5 minutes.  After that, 80 ml of a solution of 2.25 mmol 2, 6-trichlorophenol in chlorobenzene is added to the ampoule and its contents are stirred for 10 minutes.  The catalyst solution thus obtained is loaded into a 300 ml autoclave that has been previously purged with nitrogen to remove air from it.  The autoclave is sealed and propylene is introduced into it in such a quantity that the pressure in the autoclave is 5 kg / cm.  The reaction proceeds at 20 ° C for one and a half hours.  Pressure is maintained by feeding.  chi into the propylene autoclave.  At the initial stage of the reaction, a large amount of heat is released, and therefore the autoclave is cooled with ice.  After completion of the reaction, unreacted propylene is blown away and methanol is added to the autoclave to stop the reaction, after which the catalyst is washed out with water.  The product is distilled to give 55 g of propylene dimer.  The catalyst efficiency is (, 2 x 10 g propylene dimer / g nickel / h.  According to the results of gas chromatography analysis, the propylene dimer has the following composition,%: 2-methylpentene 1 and 2-methylpentene-2 k2; -methylpentene-1 and 4-methylpentene-2 18; hexenes 21; 2,3 Dimethylpentene-1 and 2,3-Dimethylpentene-2 20.  Example 2  A 200 ml Schlenk ampoule is purged with nitrogen to remove air from it, after which 20 ml of dry chlorobenzene, 0.75 1 of a solution of 0.15 mmol of nickel naphthenate in toluene, 1.5 ml of a solution of 0.15 mmol of triisopropylphosphine in toluene and 0.5 ml isoprene in this order.  Then 1.5 ml of a solution of 1.5 mmol of triethylaluminum in toluene are added to it and the mixture is stirred at room temperature for 5 minutes.  Then, 80 ml of a solution of 2.25 mmol of pentachlorophenol in chlorobenzene is added to the ampoule and its contents are stirred for 10 at room temperature.  The catalyst solution thus obtained is charged into a 300 ml Nerve steel autoclave, from which air has been previously removed by purging with nitrogen.  After the autoclave is sealed, it is loaded with propylene in such an amount that the pressure in the autoquale is 5 kg / cm and the reaction is carried out for -1.5 hours.  The pressure in the autoclave is maintained by passing it into propylene.  Subsequent processing and analysis are carried out as in Example 1.  The result is 90 g of propylene dimer.  The catalyst activity was 6.8 X 10 g, propylene dimer (g nickel) h.  The distribution of isomers in the propylene dimer obtained is the following,%: 2-methylpentene-1 and 2-methylpentene-2 11; -methylpentene-1 and -methylpentene16; hexenes 5; 2.3 Dimethyl-1-butene and 2.3 Dimethyl-2-butene.  Example 3  The experiment was carried out according to Example 2, but instead of peitachlorophenol, 5 mmol of 2,4,6-trichlorophenol was used.  As a result, 3 g dimers of propylene are obtained with the following distribution of isomers in it,%: 2-methylpentene-1 and 2-methylpentene-2 13; -methylpentene-1 and 4-methylpentene-2 18; hexes 11; 2,3 dimethylbutan-1 3 and 2-3-dimethylbutan-2 16.  The catalyst activity is 2.57 X 10-g / g nickel / h.  Example: A 200 ml Schlenk ampoule is purged with nitrogen to remove air from it, after which 20 ml of dry chlorobenzene, 0.375 ml of a solution of 0.075 mmol of nickel naphthenate in toluene, 0.73 ml of a solution of 0.075 mmol of triisopropylphosphine in toluene and 0.5 are introduced into it. ml of isoprene in that order.  Then, 1.5 ml of a solution of 1.5 mmol of triethylaluminum in toluene is added to it and the mixture is stirred at room temperature for 5 minutes.  After that, 80 ml of a solution of 4.5 mmol of 2,4,6-trichlorophenol in chlorobenzene are added to the ampoule, and its contents are stirred at room temperature for 10 minutes.  The catalyst solution thus obtained is loaded into a 300 ml stainless steel autoclave with a capacity of 300 ml, which is previously purged from air with nitrogen.  After sealing the autoclave, propylene is introduced into it in such an amount that the pressure in the autoclave is 5 kg / cm and the reaction is carried out at 20 ° C for 1.5 hours.  The pressure in the autoclave is maintained by feeding it with propylene.  Subsequent processing and analysis are carried out as in Example 1.  As a result, 31 g of propylene dimer was obtained with the following distribution of isomers in it: 2-methylpentene-1 and 2-methylpentene-2 17. , 6; 4-methylpentene-1 and -methylpentene-2 15, hexenes 8; 2,3-DIMETHILBYTEN-l 6,6 and-2,3-DIMETHYLBUTEN-2 51.  Catalyst activity, b9 10 g / g nickel / h.  Example 5 The test was carried out as in Example 1, but instead of 2, 6-trichlorophenol, 1.125 mmol was used.  tetrachloro-p-hydroquinone.  The result is 30 g of propylene dimer with the following distribution of isomers,%: 2-methylpentene-1 and 2-methylpentene-2 25; -methylpentene-1 and A-methylpentene-2 35; hexenes 23; 2.3 Dimethylbutan-1 1b and 2,3-Dimethylbutan-2 0.5.  Catalyst activity 2.27 x 10 g / g nickel / h.  Example 6  The experiment was carried out as in Example 1, but instead of 2, |, 6-trichlorophenol, 4.5 mmol of pentachlorophenol was used.  The result is 25 g of propylene dimer with the following distribution of isomers,%: 2-mytilpentene-1 and 2-methylpentene-2 20; “-Methylpentene A-methylpentene-2 37; hexenes 20; 2,3 limethylbutan-1 19 and 2,3-dimethylbut. en-2 4.  Catalyst activity 1.89 X 10 g / g nickel / h.  PRI me R 7.  A 200 ml Schlenk ampoule is purged with nitrogen to remove air from it, after which 20 ml of dry chlorobenzene, 0.15 ml of nickel bis-acetylacetonate, 1.5 ml of a solution of 0.15 mmol of triisopropylphosphine in toluene and 0.5 ml are introduced into it. isoprene in the sequence indicated.  Then 1.5 m solution of 1.5 mmol of triethyl aluminum in toluene is added to it and the mixture is stirred at room temperature for 5 minutes.  After that, 80 ml of a solution of pentachlorophenol in chlorobenzene in various quantities are added to the ampoule and its contents are stirred at room temperature for 10 minutes.  Each of the catalysts obtained is loaded into a stainless steel autoclave with a capacity of 300 ml, from which air has been removed by purging with nitrogen.  After sealing the autoclave, propylene is introduced into it in such an amount that its pressure is 5 kg / cm and the reaction is carried out at 1.5 hours.  The pressure is maintained by supplying propylene to the autoclave.  Subsequent processing and analysis are carried out as in Example 1.  The results of the experiments are given in table. one.  Example 8  The autoclave from the non-steel was purged with nitrogen to remove air from it, after which 20 ml of chlorobenzene, 1.5 ml of a solution of 0.15 mmol of nickel naphthenate 13 toluene and 1.5 ml of a solution of 0.15 mmol of triisopropylphosphine in toluene were charged into it They are listed and propylene gas is passed through the mixture.  Thereafter, 1.5 ml of a solution of 1.5 mmol of aluminum triethyl in toluene and 80 ml of a solution of 2.25 mmol of pentachlorophenol in chlorobenzene are added to the autoclave, in order of their enumeration.  After sealing the autoclave, it is loaded with propylene in such an amount that the pressure in the autoclave is 5 mg / cm and the reaction is carried out at 0 ° C for 1.5 hours.  The pressure is maintained at the feed rate of the propylene autoclave.  After completion of the reaction, further processing and analysis are carried out as in the example. 60 g of propylene dimer of the following composition are obtained: 2-methylpentene-1 and; 2-methylpentene-2 1 -methylpentene-1 and | -methylpentene-2 23.9; hexenes 13.3; 2,3-dimethyl-butene-1 29.9 and 2,3-dimethyl-butene-2, 8 Catalyst activity 4, nickel / h.  I Example 9.  The experiment was carried out according to Example 2, but instead of 0.15 mmol.  triisopropylphosphine used the same amount of compounds of trivalent phosphorus.  . The results of the experiments are given in table.  2  PRI me R 10.  The experiments were carried out as in Example 2, but the temperature was maintained not at 20 ° C, but O or.  The results are presented in Table. H PRI me R 11.  Into a 100 ml ampoule with a volume of 100 ml, 0.6 mmol of nickel naphthenate (in the form of 3) is added. 0 ml of rastvor thief in monochlorobenzene), 1.2 mmol of triisopropylphosphine (in the form of a 1.0 ml solution in monochlorobenzene) and 0.5 ml of isoprene, in order of their enumeration.  After that, 6 mmol of triethylaluminium (in the form of 3.8 ml of solution in monochlorobenzene) are added and the mixture is stirred for 5 minutes.  Then 9 mmol of pentachlorophenol (in the form of a 20 ml solution in monochlorobenzene) are added while the ampoule is cooled with ice and its contents are stirred for 25 minutes.  The result is a catalyst solution.  After the stainless steel autoclave is pre-purged with nitrogen to remove air, 100 ml of dry monochlorobenzene and the prepared catalyst solution are loaded into it, then sealed, propylene is charged in such a quantity that the pressure is equal to kg / cm and the reaction is carried out at 20 ° C and stirring for 1.5 hours  The pressure is maintained by feeding propylene to the autoclave.  After completion of the reaction, further processing and analysis are carried out as in Example 1.  The result is 950 g of propylene dimer with a content of 2.3 dimethylbutan-1 - 90.5.  Catalyst activity 1,798 X 104 g / g nickel / h.  Example 12  The experiment was carried out according to Example 11, but using 18 mmol of pentachlorophenol.  The result is 1100 g of propylene dimer with the following distribution of isomers,%: 2, -dimethylbutan-1 2.5 and 2,3-Dimethylbuthene-2 In, 5.  Catalyst activity 2,082 X 10 g / g nickel / h.  Example 13 20 ml of dry chlorobenzene, 0.3 ml of a solution of 0.03 mmol of nickel naphthenate in toluene, 1.0 ml of a solution of 0.1 mmol of triisopropylphosphine in toluene and 0 are added to a Schlenk vial of 200 ml purged with nitrogen to remove air from it. , 5 ml of isoprene in order of their enumeration, after which c.  It is 3 ml of a solution of 1 mmol of triethyl aluminum in toluene and the mixture is stirred at room temperature for 5 minutes.  After that, 7b ml of a solution of 9 mmol of pentachlorophenol in chlorobenzene is added to the ampoule and its contents are stirred at room temperature for 5 minutes.  The resulting catalyst solution is loaded into a 300 ml stainless steel autoclave, which has been previously purged with nitrogen to remove 139 air from it.  After sealing the autoclave, it is loaded with propylene in such an amount that the pressure is 5 kg / cm and the reaction is carried out at about-20 ° C for 1.5 hours.  The pressure is maintained by introducing propylene into the autoclave.  At the initial stage of the reaction, a large amount of heat is observed, and therefore the autoclave is cooled with ice.  After the end of the reaction, unreacted propylene is blown off and methanol is added to the autoclave to stop the reaction.  The catalyst components are washed out with water.  The product is distilled at atmospheric pressure to give 150 ml of propylene dimer.  The catalyst activity is 5.68 X 10 g propylene dimer / g nickel l / h.  According to the results of gas chromatographic analysis, the dimer has the following composition,%: cis- and trans- -methylpentene-2; 2.3 Dimethylbutan-1, 0; 2 methylpentene-1 and hexene-1 2.0; trans -2-hexene 3; 2-methylpentene-2; cis-hexene-2 2.0 and 2,3-dimethylbuthenes The yield of 2.3 dimethylbutenes is equal to b5 and isomerization of 2.3 dimethylbouten to 2.3 dimethylbuthene-2 proceeds with a high degree, which means that the dimerization and. isomerization proceeds quantitatively in one stage.  Example T.  The experiment was carried out according to Example 13, but the amount of triisopropylphosphine was increased from 0.1 to 0.3 mmol. The yield of propylene dimer is 110 g, catalyst activity, X 10 g of dimer / g nickel / h.  Dimer has the following composition,%: cis- and trans- | -methylpentene-2 20; 2.3 dimethylbutan-1 3.0; 2-methylpentene-1 and hexene-1 1.0; trans-hexene-2; 2-methylpentene-2 11; cis-hexene-2.  1.0 and 2, -dimethylbutyl-2 60.  fi. .  Example 15 In the vial Schlenka volume.  200 ml were added 20 ml of dry chlorobenzene, 0.15 np of a solution of 0.015 mmol of nickel naphthenate in toluene, 0.15 ml of a solution of 0.015 mmol of triisopropylphosphine in toluene and 0.5 ml of isoprene in the order listed above, after which it was added 1.3 ml of a solution of 1.5 mmol of triethylaluminum in toluene and stir its contents at room temperature for 5 minutes.  Then 78 ml of the solution, 5 mmol of pentachlorophenol in toluene are added to the ampoule and its contents are stirred at room temperature for 5 minutes.  The resulting solution was loaded into a 300 ml stainless steel autoclave, which was pre-purged with nitrogen to remove air from it.  After sealing the autoclave, propylene is loaded into it in such a quantity that the pressure is 5 kg / cm and the reaction is carried out for 1.5 hours.  The pressure is maintained by feeding propylene to the autoclave.  The reaction mixture is treated as in example 1.  The result is 60 g of propylene dimer. The catalyst activity is 5 x 10 g dimer / g nickel / h.  The resulting dimer had the following composition,%: cisi trans-1-methylpentene-2 30; 2,3-Dimethylpentene-1 2.0; 2-methylpentene-1 and hexene-1 A; trans-hexene-2 10; 2-methylpentene-2 18; cis-hexene-2 k and 2,3 dimethyl-butene-2 32.  Example 16  Experiments were carried out according to Example 13 (but instead of triisopropylphosphine, 0.1 mmol of each of the trialkylphosphines and aninophosphines were used.  The results of the experiments are given in table.  four.  Example 17  20 ml of dry toluene, 1.5 ml of a solution of 0.15 mmol of nickel naphthenate in toluene, 1.5 ml of a solution of 0.15 mmol of triisopropylphosphine in toluene and 0.5 ml of isoprene are added to the deaerated Schlenk ampoule with a capacity of 200 ml. after which a solution of 3.0 mmol of aluminum triethyl in toluene is added to it and the mixture is stirred for 5 minutes at room temperature.  Then a ml of a solution of 9 mmol of pentachlorophenol in toluene is added to the vial and its contents are stirred at room temperature for 5 minutes.  The resulting catalyst solution is loaded into a 300 ml stainless steel autoclave, which is pre-purged with nitrogen. ohm to remove air from it.  After sealing the autoclave, propylene is loaded into it in such an amount that the pressure is 5 kg / cm and the reaction is carried out at 20 ° C.  for 1.5 hours  The pressure is maintained by feeding propylene to the autoclave.  The reaction mixture is treated as in example 13. The result is 110 g of propylene dimer, of the following composition,%: n-hexenes 5; Methylenemenes 27 and 2.3 dimethyl6utene 68, (of which 2.3 are dimethylbutan-1 and 2.3 dimethylbutin-2 6).  Catalyst activity on dimer 8.32 x 10 g / nickel / h, Example 18.  20 ml of dry chlorobenzene, 0.5 ml of a solution of 0.05 mmol of nickel naphthenate in toluene, 3 ml of a solution of 0.3 mmol of triisopropylphosphine in chlorobenzene, 0.5 ml of isoprene and 3 ml of a solution of 3 mmol of triethylaluminum in toluene, in the order of their enumeration.  The mixture is re; stir at room temperature for 5 minutes.  Then, 77 ml of a solution of pentachlorophenol in chlorobenzene is added to the vial and the contents are stirred at room temperature for 5 minutes.  The catalyst solution thus obtained is loaded into a 300 ml stainless steel autoclave, which is preliminarily flushed with nitrogen to remove air from it.  After sealing the autoclave, propylene is added to it in such a quantity that the pressure is 5 kg / cm and the reaction is carried out. for about 1.5 hours  The pressure is maintained by feeding propylene to the autoclave.  The reaction mixture is treated according to example 13.  The results are shown in Table.  five.  Example 19  The experiment was carried out according to Example 18, but instead of 9 mmol of pentachlorophenol, 9 mmol of each of the halogenated phenols was used.  The results are presented in Table.  6  Example 20  Into a 1 liter stainless steel autoclave purged with nitrogen to remove air from it, 40 ml of dry chlorobenzene, 1.5 ml of a solution of 0.255 mmol of nickel naphthenate in chlorobenzene, 4.5 ml of a solution of 0.45 mmol of triisopropylphosphine are added; in chlorobenzene, O, 5 ml of isoprene, and 4.5 ml of a solution (4.5 mmol) of triethylaluminium in chlorobenzene in the order listed.  The mixture is stirred at room temperature for 5 x.  Then, 210 ml of a solution of 13.5 mmol of pentachlorophenol chlorobenzene is added to the autoclave and its contents are mixed for 5 minutes.  After sealing the autoclave, 270 propylene is loaded into it, in tens of 27 g each, under pressure, at 20 ° C for 2 hours and stirred with an electromagnetic stirrer.  After completion of the reaction, the reaction mixture is then treated as in Example 13.  3 As a result, 2 б g of propylene dimer is obtained.  The dimer yield is 9b% based on the loaded propylene.  The dimer has the following composition: 2,3-dimethylbutene 73; methylpentene 24 and n-hexene 3.  2,3-Dimethylbutenes are composed of 97% 2, 3-Dimethyl-2-butene and -2, 3-3-Dimethyl-1-butene.  The degree of isomerization is 97, the catalyst activity on the dimer is 9.81 x 10 g / g nickel / h.  Example 21  Dimerization is carried out according to Example 11, but instead of propylene monomer, ethylene monomer is used and the process is carried out at a pressure of 1-2 kgf / cm for 30 minutes.  1.600 g of ethylene dimer are obtained.  Gas chromatography of the reaction product shows that the product contains 1.120 g of ntbutenes, and the rest is trimer oligrmers or higher polymers.  Catalyst activity 6,3b X nickel / h.  Example 22  Prov. However, the experiment of Example 20 was used, but instead of nickel naphthenate, 0.225 mmol of nickel compounds were used.  Results are given in t abl.  7  Example 23  The experiment was carried out according to Example 20, but instead of 4.5 mmol of triethyl aluminum be | eut 4.5 mmol of triisobutyl aluminum.  The result is 250 g (yield 92,61) propylene dimer.  Catalyst activity 9.46 X 10-g / g nickel / h.  Example 24  The experiments were carried out according to Example 9, but instead of the phosphorus-containing compounds listed in Table. 2 take the compounds listed in table. eight.  The results are shown in Table.  eight.  Example 25  Experiments are carried out as in Example 20, but the amount of nickel naphthenate is 0.009 mmol instead of 0.225 mmol, and the amount of triisopropylphosphine is 0.018 mmol instead of 0.45 mmol (molar ratio AI / Ni 500).  87 g (yield 29) of propylene dimer are obtained in the results.  Example 2b  Experiments were carried out according to example 20, but the amount of nickel naphthenate was 2.25 mmol instead of 0.225 mmol, and the amount of triisopropylphosphine was 2.25 mmol instead of 17 Q, kS mmol (molar ratio AI / NI 2).  Examples 27 and 28.  Experiments were carried out as in Example 20, but the amount of triisopropylphosphine is 0.0225 and 11.25 mmol instead of O, 3 mmo. The results are shown in Table.  E.  Examples 29 and 30.  Experiments were carried out according to Example 20, but the amount of pentachlorophenol is 0.9 and 90 mmol instead of 13.5 mmol.  The results are given in Table.  ten.  Example 31  The experiment was conducted according to example 19.  The results are shown in Table.  eleven.  Example 32  By analogy with example 13, the dimerization of propylene is carried out, except that the reaction temperature and the duration of the reaction are changed according to Table.  12.  The obtained results are summarized in table.  one. 2  EXAMPLE 33 — Experiments were conducted in Example 9, but instead of the compounds listed in Table. 2 uses phosphorus-containing compounds, which are listed in Table.  13.  The results are summarized in table.  13.  ; Process-can also be effective.  in the case of using phosphorus-containing compounds, the molecules of which include v-alkenyl and aralkyl groups.  When M: er 1 (comparative).  The experiment was conducted according to Example 8, but penta chlorophenyl (the activating agent) was not administered.  The yield of the propylene dimer was L 3 g, t. e.  catalyst activity.  low - 0,227 Yu g / g nickel / h.  PR, M and R 2 (comparative).  The experiment was carried out according to Example 2, but instead of 1.5 mmol of triethylaluminium, 1.5 mmol of ethyl aluminum dichloride were used and pentachlorophenol was not added.  The yield of the polymer dimer is 70 g, the catalyst activity is 10 g / g nickel / h.  The dimer has the following composition: 2,3-methylpentenium 2-methylpentene-2 1.5; 4-methylpentene-1 and -methylpentene-2 15.3; hexenes 28; 2, 3-dimethyl-1-butene and 2, 3-Dimethyl-2-7, 7.  The distribution of isomers in this example is very different from the distribution in example 2.  This means that the phosphorus-containing compound has an excellent effect in this case.   3 (comparative).  Example 20 ml of dry chlorobenzene, 0.3 ml of a solution of 0.03 mmol of nickel naphthenate in toluene, 0.3 ml of a solution of 0.3 mmol of triisopropylphosphine in toluene and 0.5 ml of isoprene in the order of listing.  Thereafter, 3.0 ml of a solution of 3.0 mmol of ethyl aluminum dichloride are added to the ampoule and the mixture is stirred at room temperature for 5 minutes.  The resulting catalyst solution is loaded into a 300 ml stainless steel autoclave previously purged with nitrogen to remove air and it.  After sealing the autoclave, propylene is loaded into it in such a quantity that the pressure is 5 g / cm and the reaction is carried out at 20 ° for 1.5 hours.  The pressure is maintained by feeding propylene to the autoclave.  The reaction mixture is treated according to example 12.  As a result, grams of propylene dimer are obtained.  The catalyst activity is 5.3x10 g of propylene dimer / g nickel / h.  Dimer has the following composition,%: cis- and trans-4-methylpentene-2 31; 2, 3-dimethylbutan-1 50; 2-methylpentene-1 and hexene-1 10; trans-hexene-2 6; 2-methylpentene-2; cis-hexene-2 2 and 2, H-dimethyl-2-butene-0.  Isomerization of 2, 3-dimethyl-butene-1 does not occur at all.  If we compare the results of this comparative example 3 with the results of example k, we see the effect on the course of the reaction of halogenated phenol.  As can be seen from the above examples, the catalyst used in the method has a high catalytic activity (for example, an activity of 10–10 or more g of propylene dimer / g nickel / h, which allows a significant increase in the productivity of the process.  In addition, it can be used to easily control the distribution of the resulting isomers.  The technology of the proposed method has the following advantages in comparison with the known methods: the nickel compound used is readily available; it can be obtained without resorting to complex methods of synthesis; besides, it is stable and easy to work with; The organoaluminum compound does not contain a halogen atom and, therefore, when working with it, halogenohydrogen does not form and the apparatus does not corrode; The combined phenols, which are an important activating component of the proposed catalysts, are stable; The activity of chlorine associated with the aromatic core is so low that they do not interact with other components of the catalyst, such as, for example, organoaluminum compounds.  . A large amount of chlorobenzene E (1) is effectively used as a solvent without having an undesirable influence on the course of the reaction.  Since there is no dissociation of halogen atoms with the formation of anions X, there are no problems associated with the corrosion of equipment.  In addition, since no hydrogen halides are formed, there is no danger of contamination of the final product.  The adjustment of the catalytic activity of the catalyst and the control of the distribution of the resulting isomers can be carried out by simple operations, for example, by changing the amount of chlorinated phenol.  Table 1
    Tri-n-butylphosphine Tri-n-octylphosphine TRI7P - tolyl 6 phosphine Tri-p-methoxy 8 phenylphosphine Tri-dimethylamino42, phosphine
    Table 2 13 35 4.0 Oe, 8 10 12.5 12 36, 5 15, 021232.08.32 U 10 21.321C, E4.97.95 Yu 26,424,513,73,19,084MO
    21
    Three-di-n-butylaminophosphin0, 1585
    160
    583 -8.0 i, 096 Tri-n-butyl, 5, 5 13 phosphin130 Ethyl di-tert. butylphosphine} kO 50 39
    90t51 +
    22 Continued table. 2
    17 31 2.0 b.
    20
    Table 3
    Table
    96 6,058 - 10 97, 923 10 3.0 97 95 5.30 -} {f
    23
    TRI- / DIETHL35 amino / -phosphine 90
    85 - The ratio of the amount of 2.3 dimethylbutenes /% /. The ratio of the amount of 2.3 Dimethylbutan-2 to. 2, Zdimetilbutenov. .
    90 "51
    2h
    Continued table. i
    18 4; o
    96 3.08 -W
    96
    95
    35 3.22
    ten
    17 5.0 2.3 Dimethylbutene-2 to the total number Table 5 the total number of T a b l and c a
    25
    ,
    116 k, 33 Q70
     90 9.2 1072 Phenylbisethylaminophosphine 0, 15 125 9, 10 Phenyldiphenyl Phosphinate 0, 15 110 8.327 10
    26
    Table 7
    26
    Table 8
    T a b l: i c a 9
    Table 10 18 6517 155827
    27
    9-, 0 21, i, 5
    28
    Table 11
    27.3
    5.2
    Table 12
    Table 3
    29
    | -RG ioprolil Octyl p-octip
    权利要求:
    Claims (3)
    [1]
    1. A method of dimerizing lower &agr; -olefins using a catalyst containing a divalent nickel compound — a salt, or a complex compound of nickel and aluminum trialkyl, characterized in that, in order to increase the productivity and selectivity of the process, a catalyst is used which additionally contains a trivalent phosphorus compound of the formula
    s) 2. 3 2P R R R or (R2N V. P or
    (RO) R | -, in which R, R and R may be the same or different and each means alkyl With /) - Cf, lower
    thirty
    90451 Continuation of the table of TZ
    alkenyl, cyclohexyl, phenyl, tollyl, p-methoxyphenyl, benzyl, where n is an integer (1-3). and chlorinated phenol,
    selected from the group containing 2,3 2,4-, 2,5-, 2,6-, З ,, 3,3-dichlorophenol, 2,4,6-, 2,4,5-trichlorophenol, 2,3 ,, 6-tetrachlorophenol, pentachlorophenol and tetrachlorohydroquinone, with a trialkylaluminium ratio of 2-500 to a nickel compound, 2 to 500 phosphorus compounds to a nickel compound, 0.1 to 50 and chlorinated phenol to a trialkylaluminum, 0.2 to 20.
    [2]
    2, the method according to claim 1, wherein the process is carried out at a molar ratio of chlorinated
    3190 51 32
    phenol to trialkylaluminum, equal. Sources of information,
    0,., Taken into account in the examination
    [3]
    3. The method according to claim 1, characterized in that the process wire t1, Japan Patent ff,
    with a molar ratio of chlorinated scl. 16 B 121, pub. 1971. Phenol to trialkyl aluminum, equal to 2, US Patent h 3513218, 37
    2-10 ..kl. 2bO-683.15, published. 1970.
    . The method according to claim 1, characterized by -.
    with the fact that the process is carried out, 3 "US Patent P 3 83268,
    at a molar ratio of chlorinated 10cl 260-683.15 publ. 19b9 (profenol to trial aluminum, equal to 2-5-totype).
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    同族专利:
    公开号 | 公开日
    JPS5412303A|1979-01-30|
    JPS577606B2|1982-02-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS5439004A|1977-08-29|1979-03-24|Sumitomo Chem Co Ltd|Preparation of 2,3-dimethylbutene-2|
    JPS59210032A|1983-05-14|1984-11-28|Nissan Chem Ind Ltd|Method for dimerization and codimerization of lower monoolefin|
    JPS59210033A|1983-05-14|1984-11-28|Nissan Chem Ind Ltd|Method for dimerization and codimerization of lower monoolefin|
    JP2550641B2|1988-02-29|1996-11-06|住友化学工業株式会社|Method for dimerizing lower α-olefins|
    DE102010006589A1|2010-02-02|2011-08-04|Linde Aktiengesellschaft, 80331|Process for the preparation of linear α-olefins|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP7818377A|JPS577606B2|1977-06-29|1977-06-29|
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