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    • 专利摘要:
    A process for isomerization of alpha -olefin dimers which comprises dimerizing a lower alpha -olefin with a Ziegler type catalyst comprising a nickel compound and an organo-aluminum compound, and then continuing the reaction with addition of at least one compound, prior to deactivation of said catalyst, which is selected from the group consisting of the following organo-halogen compounds of the formulae (I), (II), (III) and (IV), <IMAGE> (I) <IMAGE> (II) <IMAGE> (III) <IMAGE> (IV) wherein X1 to X11 are the same or different and are each a halogen or hydrogen atom or an alkyl group having 1 to 20 carbon atoms and at least one of them in each formula is a halogen atom, R is a hydrocarbon group having 1 to 20 carbon atoms, R1, R2 and R3 are the same or different and are each a hydrogen or halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R5 and R6 are the same or different and are each an alkyl having 1 to 20 carbon atoms or, taken together, may form a cycloalkyl group, and n is an integer of 0 to 5.
    公开号:SU906361A3
    申请号:SU782652603
    申请日:1978-08-10
    公开日:1982-02-15
    发明作者:Сато Хироси；Тодзима Хидето；Ясуи Сеймей
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    I
    The invention relates to the isomerization of olefins, and specifically to a method for the isomerization of olefinic dimers, including the dimerization of such lower cb-olefins as ethylene, propylene 5 or butene-1 using Ziegler catalysts, including a nickel compound and an organoaluminum compound as main components, and the subsequent Continuing the reaction with 10 additions of the active organo-halide before deactivating said catalyst.
    Lower l-olefins, such as ethylene, propylene, 6utene-1, are 15 convenient starting compounds for the preparation of high molecular weight polymers that play an important role in the petrochemical industry. In addition, the dimers of these ct-olefins 20 can be used to obtain pure chemicals. For example, a propylene dimer, 2-methylpentene can be converted to isoprene by cracking using alumino-silicate.
    go catalyst; 2,3-Dimethylboutenes can be dehydrated to obtain 2,3-Diethylbutadiene, which can be used as a material for synthetic rubbers and pyromellitic anhydride, and 2-methylpentenes and 2,3-dimethylbutenes can be turned into agents that increase the octane number by their hydrogenation; 2, 3-Dimethylbutan-2 may be used as a raw material for the production of agricultural chemicals.
    However, in order to use olefins for these purposes, it is not enough to simply dimerize the olefins, and the double bond in the resulting dimer needs to be shifted to the desired position.
    There are four known methods for the dimerization of olefins; cation isomerization using proton acids as catalyst 1. T 3-isomerization using a combination of Lewis acid and proton acids lj; anion isomerization using an alkali metal or an alkali metal alcohol 2 as a catalyst and isomerization by adding hydrides and removing them by using a transition metal 3 as a catalyst. However, these methods have the following disadvantages: attempts to increase the yield of isomerization at water the occurrence of such side reactions as the formation of high polymers during intermolecular interaction, moreover, the materials from which the equipment is made are undesirable. acid corrosion. The anionic isomerization process is uneconomical since it requires relatively expensive solvents to react, for example, special aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide. The isomerization process due to the addition of 3J hydrides occurs under mild conditions with a small amount of side reactions, however, the catalyst for the jT-allylic nickel complex is synthesized by a complex procedure, and it is difficult to work with this complex, since it decomposes in air. The closest to the invention in technical essence and the achieved result is the method of isomerization of propylene dimers, including the dimerization of propylene on a complex catalyst containing nickel compounds, an organoaluminum compound to produce a reaction mass. According to a known method, a Ziegler catalyst consisting of nickel acetylacetonate, ethyl aluminum sesquichloride and trialkylphosphine is used as the catalytic system. In the first stage, dimerization of propylene is carried out at a temperature of from -10 to 28 ° C in the presence of a complex catalyst dissolved in an organic solvent. Then, the dimerization product after separation of unreacted propylene is directed to isomerization, which is carried out at a temperature of from -30 ° C to 38 ° C for 0.6-2 hours. 9 4 The purpose of the invention is to simplify the process technology. This goal is achieved by the fact that according to the method of isomerization of propylene dimers, which consists in dimerizing propylene in the presence of a complex catalyst containing nickel compounds, an organo-aluminum compound to produce a reaction mass, an organo-compound selected from the group containing: tert-butyl bromide or tert-butyl chloride, benzyl bromide or chloride, allyl bromide or bromide, propargyl bromide or chloride, with a molar ratio of organic halide to an organo-aluminum compound of 0.5-50: 1. and temperature 0-80 ° C. The essence of the proposed method consists in the following. After dimerization has been completed, an organohalide is added to the reaction mass, while the cymerization catalyst retains its activity, allowing isomerization to take place immediately. If an organic halide is added after deactivating a dimerization catalyst, for example, by treating a large amount of alcohol or water, isomerization does not occur. The amount of said organohalogen compound can vary within fairly wide limits (0.5–50 mol per 1 mol of the organoaluminum compound in the c-olefin dimerization catalyst system). Isomerization can be carried out both in a solvent and without it. Usually, one inert solvent is used for dimerization and isomerization (for example, benzene, toluene, n-hexane, n-heptane, chlorobenzene). Since the initial C-olefins do not have undesirable effects on the isomerization reaction, the latter can be carried out as if unreacted CL-olefins are not removed from the dimerization system, as well after removing the main amount of unreacted x-olefins from the dimerization system, which reduces the pressure inside the reactor, Isomer .ZATSYYY can be carried out both continuous, and cyclic
    5EO
    in a way. The isomerization temperature should be chosen in the range from O to 80 ° C. The time required for isomerization is chosen arbitrarily depending on the desired percentage of isomerization.
    Isomerization must be carried out in an atmosphere of inert gas, for example nitrogen or argon, therefore the ingress of large amounts of air or moisture in the isomerization process is undesirable. It is preferable that the organohalide compound that is added for isomerization is freed from air and moisture.
    In the examples given, the compositions of the cL-olefin dimers are analyzed by gas chromatography (on a six-meter column filled with sebaconitrile).
    Example 1. Air from a steel autoclave with a capacity of 300 ml equipped with an electromagnetic stirrer is displaced with nitrogen and 77 ml of dry chlorobenzene are loaded into this autoclave; 0.75 ml of toluene with 0.15 mmol of nickel naphthalenate dissolved in it and 0.3 ml of toluene with 0.16 mmol of triisopropylphosphine dissolved in it in the sequence indicated. Then in this mixture is dissolved
    sixteen
    a certain amount of propylene, strung it at. Thereafter, 1 ki ml of toluene with 1.5 mmol of ethyl aluminum sesquichloride dissolved in it is added to the resulting mixture, and the autoclave is sealed immediately thereafter. The reaction is carried out at 1.5 hours while maintaining the propylene pressure at 5 kg / cm. After the end of dimerization, part of the reaction solution is sampled.
    After the unreacted propylene was blown, 1.5 mmol of tert-butyl bromide dissolved in 3 ml of toluene was added to the reactor, after which the autoclave was sealed. Isomerization was carried out for 1 hour. During isomerization, the monomer showed a pressure of 1.5 kg / cm. After the isomerization is completed, the reaction solution is cooled to room temperature, and isopropanol is added to stop the reaction, after which the catalyst residue is washed with water. The product obtained is distilled at atmospheric pressure, and 92 g of propylene dimer are obtained. Compositions of samples taken before and after isomerization are analyzed using gas chromatography. The results are shown in table 1.

    Table 1
     After dimerization, the reaction is carried out at 80 ° C for 1 h without adding an organo-halide.

    2,3-D methylbutene-2
    X 100; 2, 3-dimethylbutenes 7 2-methylpentene-2 X 100. 2-methylpentenes The isomerization percentage of 2,3-dimethylbutene-1 to 2, 3-dimethylbutene-2 is 89.7 Example 2. Air from a 300 ml autoclave equipped with electromagnetic with a stirrer, displaced with nitrogen. B9 ml of dry chlorobenzene is charged into the autoclave; 0.75 ml of toluene with 0.15 mmol of naphthalene nickel dissolved in it; 0.3 ml of toluene with 0.15 mmol of triisopropylphosphine dissolved in it; 9 ml of toluene with 2.25 mmol of penta hlsrphenol and 0.5 ml of isoprene dissolved in them in the sequence indicated. After that, while stirring, 1.07 ml of toluene with 1.5 mmol of triethyl pyumini dissolved in them was added to the reactor, after which the mixture was stirred After dimerization, the reaction was carried out at 1 hour without adding organic halide.
    The percentage of isomerization of 2,3-dimethylbutene-1 to 2,2-dimethylbutene-2.
    Example 3. Air from a 300 ml autoclave equipped with an electromagnetic stirrer is forced out with nitrogen, and 69 ml of dry chlorobenzene is charged into the autoclave; 0.75 ml of toluene with 0.15 mmol dissolved in them 9
    naphthalenate nickel; 0.3 ml of toluene with dissolved in them 0.15 mmol of triisopropylphosphine and 0.5 ml of isoprene in the specified sequence. Thereafter, while stirring, 1.07 ml of tpoluol was added and dissolved at room temperature for 5 minutes. The autoclave is then hermetically closed and dimerization is carried out at 20 ° C for 5 hours, the propylene pressure being maintained at 5 kg / cm. After the end of dimerization, the largest amount of the reaction solution is removed for analysis. Unreacted propylene is blown, and 3 ml of toluene is added to the autoclave with 1.5 mmol of tert-butyl bromide dissolved in them. After that, the autoclave is hermetically closed and isomerization is carried out at a certain temperature for 1 hour. After completion of the isomerization, the reaction solution is treated as in Example 1, resulting in 89 g of propylene dimer. The composition of the isomers is studied using gas chromatography. The results are shown in Table. 2. Table 2
    1.5 mmol of triethylaluminum and 9 ml of toluene with 2.25 mmol of pentachlorophenol dissolved in them in the sequence indicated. After that, the autoclave is immediately hermetically closed. The dimerization is carried out for 1.5 hours, maintaining the propylene pressure at 5 kg / cm1. After the dimerization is completed, a small amount of the reaction solution is taken as a sample. After purging unreacted propylene to the semi-dimerization, the reaction is carried out at 20 ° C for 1 m, without adding an organohalogen compound. The percentage of isomerization of 2,3-dimethylbutene-1 to 2, 3-dimethylbutene-2.
    An example. The experiment was used instead of benzyl chloride as in Example 3, with the exception of organic halides, which are taken up in the isomerization stage in Table 1. t.
    Organohalohydrin compound 2.25 mmol 1.5 molar ratio
    Organoaluminum compound 1.5 g AOLE
    1.5 ml mmol benzyl chloride is added to the solution. The autoclave is then sealed and isomerized at 20 ° C for 1 hour. After the isomerization is complete, the reaction solution is treated as in Example 1, and 120 g of propylene dimer are obtained. The composition of the resulting isomers analyzed by gas chromatography. The results are shown in Table. 3
    Table 3
    Table
    Control experience after dimerization of propylene, the reaction is carried out
    at 80 ° C for 1 h without adding an organohalogen compound. The percentage of isomerization of 2,3-dimethylbutene-1 to 2,3-dimethylbutene-2. Example 5. The experiment was performed in the dimerization of propylene
    water according to example 3, except 25 OI.5 mmol of tri-p-butylphosphine. The fact that instead of triisopropylphosphine, the results are given in Table. 5. Before Isomerization After Isomerization Content Example 6. The experiment was carried out as in Example 3, except that 5 in the isomerization stage, T-butyl chloride was used instead of U-benzyl; Organo-aluminum compound T-butyl-chloride Organo-aluminum compound
    Tert.butyl chloride
    Organoaluminum compound
    I
    Table 5
    J4.5 mmol
     3.0 molar ratio 1.5 mmol 38.0 57.0 5.0 4.0 96.0 2,3-Dimethyl-2-butene in 2,3-Dimethyl-butenes. various amounts of tert-butyl chloride, which are listed in Table 6. Isomerization temperature of 20 ° C. Mmol Q mmol ratio 1.5 mmol 1.5 mmol 1.0 mol ratio 1.5 mmol
    The content of 2,3 dimethyl-butene-2 in 2,3-dimethyl-butene-1 Example 7-Air in a 300 ml autoclave equipped with an electromagnetic stirrer is forced out with nitrogen, 96 ml of dry chlorobenzene are loaded into the autoclave; O.ub ml of toluene with 0.15 mmol of nickel naphthalenate dissolved in them; 5 ml of chlorobenzene with 0.15 mmol of triphenylphosphine dissolved in them and 0.5 ml of isoprene in the indicated sequence. After that, while stirring, 1.07 ml of toluene was added with 1.5 mmol of aluminum triethyl and dissolved in them, and stirring was continued for 5 minutes. To the mixture were added 9 ml of chlorobenzene with 2.25 mmol of pentachlorophenol dissolved in them and stirring was continued for another 3 minutes. Then autoclave
    Before isomeric Percent isomerization
    Table 6
    2-methylpentene-2
    100
    2-methylpentene-1 + 2-methylpentene-2 is hermetically sealed and dimerization is carried out for 1.5 hours at a pressure of propylene 5 KG / CM-. After the end of dimerization, a small amount of the reaction solution is taken as a sample for investigation. Then, 1, 5 ml of toluene is added to the reaction mixture with 1.5 mmol of tert-butyl chloride dissolved in them, the autoclave is sealed and it is isomerized for 1 hour at. After completion of the reaction, the reaction solution is treated as in Example 1, resulting in 85 g of propylene dimer. C.) The stakes of dimers before and after the addition of tert chloride, butyl are shown in Table. 7. IT Table 7 15906 The percentage of isomerization of 2-methylpentene-1 to 2-methylenepentene-2 is 97.6 y ,. Example 8. The experiment was conducted according to the example of the city, with the exception of 20, 8
    26.0
    3.2 i p and mep 9. The experiment was carried out according to example 6, except that the amount of tert-butyl chloroCa as can be seen from the examples given isomerization is usually carried out at atmospheric pressure after purging unreacted propylene, but it can also be carried out after dimerization increasing pressure by adding an active organo-halogen compound without purging unreacted propylene. In the latter case, the pressure of the reaction is sometimes more than 5 kg / cm - at an appropriate reaction temperature in the range of 0-80 C.
    Table 8
    56.5
    3.5
    ,five
    权利要求:
    Claims (3)
    [1]
    Invention Formula
    The method of isomerization of propylene dimers, comprising the dimerization of propylene on a complex catalyst containing nickel compounds, an organoaluminum compound to produce a reaction mass, characterized in that
    simplifying the process, the reaction mass is subjected to isomerization with the addition of an organohalide compound selected from the group 36116, which is isomerized after propylene dimerization is carried out at OC for 5 hours by adding tert-butyl bromide (1.5 mol). The results obtained are presented in Table. 8. yes, replace with the amount shown in table. 9. The results are presented in table 3. Table9
    1790636118
    py containing tert-butyl bromide or 1. Thomas. C.L, industrial and tert.butyl chloride, methyl or chlorine engineering chemistry. vol. C, benzyl hydroxide, methyl or chlorine. 25bA.
    Crystalline allyl, methyl or chlorine-,
    [2]
    2. Bank S. Journal of American propargyl, with a molar ratio of 5 i chemical Society, 19b5, vol. 87, organic halide connection to aluminum - P-
    Moorganic compound 0.5-50: 1
    [3]
    3. US patent No. 35 +558, and temperature. . cl. 260-239, publ. 1972.
    Sources of information, ju class. 2bO-683.15, published. 1972 (entered into consideration during the totip examination).
    k. U.S. Patent No. 3686352
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    同族专利:
    公开号 | 公开日
    IT1203195B|1989-02-15|
    CH636834A5|1983-06-30|
    JPS5711286B2|1982-03-03|
    GB2003174A|1979-03-07|
    BE869652A|1979-02-12|
    DE2835365C2|1987-04-09|
    DE2835365A1|1979-02-22|
    HU180956B|1983-05-30|
    FR2399990B1|1981-05-08|
    GB2003174B|1982-02-10|
    FR2399990A1|1979-03-09|
    NL7808398A|1979-02-13|
    DK352478A|1979-02-12|
    JPS5430101A|1979-03-06|
    IT7868868D0|1978-08-07|
    US4209653A|1980-06-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    IL27721A|1966-04-15|1971-03-24|Sentralinst For Ind Forskning|Process for dimerization,codimerization,polymerization and copolymerization of mono-olefins|
    US3454668A|1966-10-31|1969-07-08|Monsanto Co|Isomerization of 2,4,4-trimethyl-2-pentene to 2,5-dimethyl hexenes|
    DE1924628C3|1969-05-14|1973-11-15|Studiengesellschaft Kohle Mbh, 4330 Muelheim|Process for the catalytic isomerization of olefins|
    US3542896A|1969-08-22|1970-11-24|Sun Oil Co|Olefin isomerization process|
    US3686352A|1970-02-18|1972-08-22|Arthur H Neal|Dimerization process|
    US3903188A|1973-12-07|1975-09-02|Du Pont|Isomerization of dienes|
    US4155946A|1977-06-29|1979-05-22|Sumitomo Chemical Company, Limited|Process for dimerizing lower alpha-olefins|NL1015302C2|1999-05-28|2001-05-08|Sumitomo Chemical Co|Process for the production of 2,3-dimethylbutene-1 and 2,3-dimethylbutene-2.|
    US6355855B1|2000-02-29|2002-03-12|Hercules Incorporated|Process for the isomerization of 1-alkenes to internal alkenes and catalyst therefor|
    US8395007B2|2009-07-29|2013-03-12|The United States Of America As Represented By The Secretary Of The Navy|Diesel and jet fuels based on the oligomerization of butene|
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    US8350107B2|2009-07-29|2013-01-08|The United States Of America As Represented By The Secretary Of The Navy|Selective isomerization and oligomerization of olefin feedstocks for the production of turbine and diesel fuels|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP9667977A|JPS5711286B2|1977-08-11|1977-08-11|
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