• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Improved process for dimerizing lower alpha -olefins using a novel nickel-containing Ziegler catalyst system comprising… (A) an organic acid salt or complex of nickel,… (B) a trialkylaluminum,… (C) a trivalent phosphorus compound of the formula:… PR<1>R<2>R<3> (I)… P(NR<1>2)3 (II)… P(OR<1>)3 (III)… wherein R<1>, R<2>, R<3> are alkyl, cycloalkyl, aryl or aralkyl,… (D) a fluorinated isopropanol of the formula:… CFmH3-m-@@-CFnH3-n…… (IV)… wherein m and n are in 4 </= m+n </= 6, and optionally… (E) a catalyst co-activator: halogenated compounds of the formulae: …<CHEM>… wherein X is halogen, R<4>, R<5>, R<6> are alkyl, and n is 1 to 3, and further optionally,… (F) a compound selected from aliphatic alcohol and aliphatic carboxylic acid or ester thereof,… which gives the dimers with high selectivity of isomers and uniformity of catalyst without corrosion of apparatus.
    公开号:SU1690542A3
    申请号:SU874028774
    申请日:1987-01-05
    公开日:1991-11-07
    发明作者:Сато Хироси；Икими Киеси；Тодзима Хидето；Такахаси Микото
    申请人:Сумитомо Кемикал Компани, Лимитед (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for dimerizing lower α-olefins using a new nickel-containing catalyst such as a Ziegler catalyst.
    The aim of the invention is to simplify the process technology by using a catalytic system with high stability, which does not result in the formation of thin precipitates from catalysts and their deposition on the surface of heat exchangers, and therefore, there is no undesirable decrease in heat removal capacity of heat exchangers to cool the material in continuous process.
    The inventive method of the invention makes it possible to obtain dimers of lower cr-olefins with high selectivity.
    PRI me R 1 (by a known method). Air is removed from a 100 ml stainless steel autoclave, then nitrogen is let in instead. A solution of 0.045 mmol of nickel naphthenate in 0.45 ml of toluene, a solution of 0.045 mmol of tricylohexylphosphine in 0.45 ml of toluene and 3 , 6 mmol, 0.36 ml of isoprene in the above sequentially, and then a solution of 0.45 mmol of triethylaluminum in 0.42 mol of toluene is added to the mixture while cooling with ice, after which the mixture is stirred. A solution of 1.35 mmol of 1.15,3,3,3-hexafluoroeopropanol in 1.35 is then added to the mixture.
    Os
    Yu
    oh ate j
    YU

    Oj
    ml of toluene while cooling with ice and stirring, and then the mixture is stirred for another 15 minutes Dry toluene is added to the finished catalytic solution with a concentration of 3.9 mol Nl / l, and then propylene is introduced under a constant pressure of 4 mg / cm for 30 minutes at 20 ° C and the reaction is carried out with stirring.
    After the completion of such a reaction, the reaction mixture is analyzed by gas chromatography (n-pentene is used as an internal standard), and the mixture is sampled under pressure. The reaction mixture obtained after purging from unreacted propylene is transparent and no precipitate is formed on the walls of the autoclave.
    PRI me R 2 (by a known method). The reaction is carried out analogously to example 1, except that 0.675 mmol of HFIP is used.
    The results are summarized in table 1.
    EXAMPLE 3 Air is removed from a stainless steel autoclave and air is then replaced with nitrogen instead. A solution of nickel naphthenate (0.045 mmol) in 0.45 ml of toluene, a solution of 0.045 mmol of tri-cyclohexylphosphine in 0.45 ml of toluene and 1.8 mmol of isoprene (0.18 ml) are introduced into the autoclave in the indicated sequence, and then in a mixture a solution of 0.45 mmol of triethylaluminum in 0.42 ml of toluene is added under ice-cooling. A solution of 0.45 mmol of t-butyl chloride in 0.45 ml of toluene is added to the mixture while cooling with ice and stirring and the mixture is stirred for another 5 minutes, and then a solution of 1.35 mmol of HFIP in 1.35 ml of toluene is additionally added and the mixture is additionally mix for 15 minutes. Dry toluene (catalyst concentration 3.87–10 mol Nl / l) is added to the prepared catalytic solution, and then propylene is introduced under a constant pressure of 4, kg / cm2 and the reaction is carried out in a mixture with stirring for 30 minutes at 20 ° WITH.
    After completion of the reaction, the reaction mixture is analyzed as in Example 1.
    The results obtained are summarized in table 2.
    The reaction mixture is clear; no precipitate forms on the walls of the autoclave.
    Examples 4-b. Analogously to Example 3, except that the amount of t-butyl chloride is replaced by the amount indicated in Table 2, the reaction is carried out. No precipitate is formed on the walls of the autoclave.
    Examples 7-10. The reaction is carried out analogously to example 3, except that the amount of tert-butyl chloride is 0.09 mmol, and the amount of HFIP is replaced
    the number specified in table.3.
    The results are summarized in table 3. No precipitate is formed on the walls of the autoclave.
    Examples 11 and 12 (by the known
    way). Stainless steel autoclave
    steel remove air and then instead
    nitrogen is introduced. A solution is introduced into the autoclave.
    0.01 mol bis-triisopropylphosphine nickel. chloride in 0.5 ml of toluene and 0.8 mmol (0.08
    ml) isoprene, and then a solution of 0.2 mmol of aluminum triethyl in 0.5 ml of toluene is added to this mixture while cooling with ice, after which the mixture is stirred for 5 minutes. In this mixture further
    add the HFIP solution in the amount indicated in tab. 4, while cooling with ice and stirring, and the mixture is again stirred for an additional 15 minutes. 8.5 ml of dry toluene (catalyst concentration 9.92 10 mol Ni / l) is added to the resulting catalytic solution, and then propylene is introduced under a constant pressure of 4 kg / cm2 and the mixture is reacted at a mixture at 20 ° C
    for 30 min while stirring.
    After completion of the reaction, the reaction mixture is analyzed analogously to example 1.
    The results are summarized in table 4. No precipitate is formed on the walls of the autoclave.
    Example13. Analogously to Example 4, except that in this case, instead of 0.09 mol of tert-butyl chloride, 0.09 mmol of benzyl chloride is used, the catalyst concentration is 3.87 10 mol Ni / L, and the reaction is carried out.
    The results are summarized in
    table.5. No precipitate is formed on the walls of the autoclave.
    Examples 14-19. The reaction is carried out analogously to example 3, except that instead of tricyclohexylphosphine in this case, various organic phosphorus compounds are used, which are listed in Table 6.
    No precipitate is formed on the walls of the autoclave.
    Example 20: The reaction was carried out analogously to example 3, except that in this case, instead of HFIP, 1.35 mmol of 1,1,1.3-tetrafluoroisopropanol was used.
    The results are summarized in table 7,
    No precipitate is formed on the walls of the autoclave.
    Example21 (by a known method). In order to achieve homogeneity of the catalytic system by increasing the concentration of catalytic components, the following test for the promoter effect is carried out.
    Air is removed from a 100 ml stainless steel autoclave and air is drawn in instead of nitrogen. Next, a solution of 0.1 mmol of nickel naphthenate in 1 ml of chlorobenzene, a solution of 0.1 mmol of tricyclohexylphosphine in 1 ml of chlorobenzene and 8 mmol (0.8 ml) of isoprene are introduced into the autoclave in the order indicated, after which the mixture is added a solution of 1.0 mmol of triethylaluminum in 1 ml of chlorobenzene with ice cooling, and the mixture is stirred. To this mixture is further added a solution of 3 mmol of HFIP in 3 ml of chlorobenzene while cooling with ice and stirring, and then the mixture is stirred for 15 minutes.
    3.7 ml of dry chlorobenzene (catalyst concentration 9.52 mmol Nl / l) are added to the prepared catalytic solution and propylene is fed under a constant pressure of 4 kg / cm2, and then the reaction is carried out with stirring at 20 ° C. .
    After completion of the reaction, the reaction mixture is analyzed as in Example 1.
    The achieved results are summarized in table 8.
    The reaction mixture prepared in this way is transparent, with a small amount of precipitation observed at the bottom of the reaction apparatus.
    PRI me R 22 (comparative). The reaction is carried out analogously to Example 3, except that in this case, instead of HFIP, 1.35 mmol of 1,1,1-trifluoroisopropanol is used.
    The results obtained are summarized in table.
    PRI me R 23 (comparative). Analogously to example 21, but trichlorophenol is used instead of HFIP, and the test is carried out as follows.
    Air is removed from a 100 ml stainless steel autoclave and air is drawn in instead of nitrogen. Then a solution of 0.1 mmol of nickel naphthenate in 1 ml of chlorobenzene, a solution of 0.1 mmol of tricyclohexylphosphine in 1
    ml of chlorobenzene 8 mmol (0.8 ml) of isoprene and 0.5 mmol (9 µl) of water in this order, after which a solution of 1.0 mmol of aluminum triethyl in the mixture is added to the prepared mixture.
    1 ml of chlorobenzene while cooling with ice, and the mixture is stirred. A solution of 1.0 mmol of triethylaluminum in 1 ml of chlorobenzene is then added to the mixture while cooling with ice and the mixture
    stirred. Next, a solution of 3 mmol of 2,4,6-trichlorophenol in 3 ml of chlorobenzene is added to the mixture with simultaneous cooling with ice and stirring and the mixture is again stirred for 15 minutes. 3.7 ml of dry chlorobenzene was added to the prepared catalytic solution (catalyst concentration 0.52 mol Ni / L) and then propylene was added under a constant pressure of 4 kg / cm and the reaction was carried out at 20 ° C while stirring for 1 h. .
    After completion of the reaction, the reaction mixture is analyzed as in Example 1.
    The results obtained are summarized in table.
    The reaction mixture thus prepared is clear, and precipitates can be observed on the bottom of the reaction apparatus.
    Example 24: For a more detailed study of the state of catalyst deposition in the full scale of the reaction system, the reaction is carried out under the following conditions.
    Air is removed from the Schlenk vessel and nitrogen is let in instead. Then a solution of 0.4 mmol of nickel naphthenate in 2.0 ml of toluene, a solution of 0.4 mmol is introduced into this vessel.
    tricyclohexylphosphine in 1 ml of toluene, 32 mmol (3.2 ml) of isoprene and a solution of 4 mmol of aluminum triethyl in 4 ml of toluene in the sequence indicated, after which the mixture is stirred for 5 minutes while cooling with ice. Next, a solution of 0.8 mmol of tert-butyl chloride in 0.8 ml of toluene is added to this mixture, a solution of each of the various additives listed in table. 10 (1.2 mmol) in 12 ml
    toluene and a solution of 12 mmol of HFIP in 8 ml of toluene in this sequence with simultaneous cooling of the mixture with ice and stirring, and the mixture is continued to be stirred for additional
    15 minutes. Dry toluene is added to the catalytic solution prepared in this way in an amount necessary to achieve a final volume of 45 ml. The catalyst concentration is 3.48 mol Nl / L.
    Separately, air is also removed from a 1.5-liter autoclave made of stainless steel, and nitrogen is released instead, after which 70 ml of dry toluene is introduced into the autoclave, and then it is sealed. The catalyst is then introduced into the reactor in the amount of 45 ml and 440 g of propylene, which is fed in separate portions for 4 hours at 20 ° C with simultaneous stirring, and then the reaction is carried out for 3 hours at 20 ° C and stirring.
    After completion of the reaction, the reaction mixture is subjected to gas chromatographic analysis (using n-pentane as an internal standard), and the mixture is sampled under pressure.
    The results obtained are summarized in table 10.
    After removing unreacted propylene from the autoclave by purging, it is opened and the reaction mixture is drained from it. At the same time, the presence of sediment on the wall or bottom of the reaction apparatus is observed.
    EXAMPLE 25 The reaction is carried out analogously to Example 24, except that instead of 1.2 mmol of stearic acid, it is used in the amount indicated in Table 11.
    PRI me R 26. The reaction is carried out analogously to example 24, except that various additives are used as indicated in Table 12 (each in an amount of 1.6 mmol).
    Example 27: The reaction was carried out analogously to Example 24, except that in this case various carboxylic acids and esters were used, which are listed in Table 13 (each in an amount of 1.2 mmol).
    Example 28: The reaction was carried out in the same manner as in Example 3, except that 0.45 mmol of tert-butyl chloride was replaced with 0.0225 mmol and the reaction was carried out.
    The results are shown in table 14.
    Example 29: The reaction was carried out in the same manner as in Example 3, with the exception that as shown in Table 15, that chlorine compounds were used instead of tert-butyl chloride (0.045 mmol), the reaction was carried out.
    EXAMPLE 30 The reaction was carried out in the same manner as in Example 3, except that 1,1,1,3,3-pentafluoroisopropanol (1.35 mmol) was used instead of the HFIP, and the reaction was carried out.
    The results are summarized in table 16,
    Example 31. The reaction was carried out as in Example 3, except that
    the amount of nickel naphthenate varies from 0.045 to 0.0225 mmol and the reaction is carried out.
    The concentration of the catalytic system is 1.74–0.43 x 3 mol L / l. Catalytic efficiency:
    22.5 x U3 mmol Csg-atm NI h.
    The selectivity for 2,3-dimethyl-butene-2 is 51.5%, the selectivity of dimers is 72.6%, the selectivity of DM B is 84.4%, the degree of isomerization is 61.0%.
    Draft no.
    Example 32. The process is carried out analogously to Example 3, except that the amount of tricyclohexylphosphine is changed from 0.045 to 0.0225 mmol.
    The efficiency of catalysis is 31.8x103 mol Cz / g-atm Nl-h.
    The selectivity for 2,3-dimethyl-butene-2 is 66.5%, the selectivity of dimers is 57.2%, the selectivity of UHF is 70.5%.
    The isomerization coefficient of 94.4%.
    No precipitate is formed.
    权利要求:
    Claims (2)
    [1]
    Invention Formula
    1. A method of dimerizing lower α-olefins by contacting with a catalytic system containing the following components: A — Nickel salt of an organic acid: B — trialkyl aluminum; C - compound of trivalent phosphorus of the formula
    PR1R2R3.
    where Ri.Ra.Ra - independently of each other lower alkyl, cyclohexyl or phenyl:
    P (NR2) 3
    where R is lower alkyl
    R (ORi) 3.
    where RI is phenyl,
    characterized in that, in order to simplify the process, a catalytic system is used, further comprising a component D-fluorinated isopropanol of the formula
    45
    CFmH3.m-CH-CFnH5.r ,, OH
    where each type is an integer and satisfies the formula 4 + n $ 6, and component E is a catalyst coactivator selected from halogenated compounds of the formula
    R RsRsCX,
    where X is chlorine or bromine; RjRsRe is lower alkyl; n -1-3.
    with the following molar ratio of components of the catalytic system:
    B / A 10-20; .5-2; E / HF) ,, 5, and the process is carried out at a concentration of the catalytic system from up to mmol / l per component A.
    2. A method according to claim 1, characterized in that a catalytic system is used, further comprising as an agent that prevents the precipitation of ka0
    [2]
    components, a component (selected from the class of aliphatic alcohols containing 12–18 carbon atoms, aliphatic carboxylic acids containing 10–18 atoms, or their esters in an amount of from 0.1 to 0.4 mol per each mole of AT.
    Priority points:
    01/06/86 according to claim 1,
    03.22.86 according to claim 2
    Table t
    "1.1 h, 4 5J.4 8b, (
    s
    Catalytic activity on propylene conversion subjected to propylene, zero propylene / g-aton nickel in I h.
     fractions, -letilbuteno (LM10 in dimers. (, 3-D11meti.1-2-puten /, Zpinetilbuten) Yuo.
    Tabliya2
    3И, 0 «5jn, 3xlO fife, 6В2, В4,878,1) 4,41,511,3О
    40.09 (127.9x10 72,578,84,474,47,21,512,5О
    50,13531,0x10 78, U74,76,168,68,81,614,9О
    60.22537,5x10 H7.S71,44,467,012,01,814,8О
    O.h 1.35 1.8 L25
    2ЛЗхШ 27, JxK 3J, Jx10 30.9x10
    / 9.9 72.5 71.0 64, i
    74, P63.9
    78,84,4
    79.45,6
    82,65,3
    0.3 0, b
    KN.VhYu 811,2x10
    93.1 71.4
    61.11 60.6 77.8 6.2
    2.0 3.0
    0.3 7.5
    6.8 2.0
    1.5 1.5
    93.5 0.8
    94.2 94.4 91.9 93.9
     Tavlitsa
    11.3 7.2 5.8 ".6
    8.0 1.5
    1.5 1.4
    5.9 2.5 13.3
    11.4
    0.8
    LTD
    13.7
    94.4 93.0 93.6
    Spreadsheets
    18.5 11.5 7.2 9.0 1.5 11.6
    1.2 O
    0.6
    92.0
    TaOlchtsa.5
    2P tb, 6xl№
    79.4
    75.P 6b, 0
    9,5xW
    61, P 89.0 4,
    4,0x1 (1 7,8x11I
    Я5, П Ь7,2
    B4, h 86, b
    64.8 4.8
    10,497,869,5 81,394,5
    g0,898,86,4 82,79i, 1
    31,497,167,1 81,294,9
    Table
    9, P
    11.0 7.8 6.2
    12.0
    Table
    84.1
    1.5 1.3
    8.2
    94.5
    TARlitza9
    7
    17.5 2.3
    9.4 .3
    8.3 10.0
    About 94.5
    Table 10
    Table 11
    Table 12
    Compiled by N. Kirillov Tehred M. Morgenthal
    Proofreader M.Sharoshi
    Editor N. Gunko
    Pack 3829 Circulation Subscription
    VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk emb. 4/5
    Production of the Novy Combine Patent, Uzhgorod, Gagarin st., 101
    Proofreader M.Sharoshi
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS5198242A|1975-02-17|1976-08-30|Isopurentorimaano seizoho|
    US4155946A|1977-06-29|1979-05-22|Sumitomo Chemical Company, Limited|Process for dimerizing lower alpha-olefins|
    US4482640A|1983-05-02|1984-11-13|Phillips Petroleum Company|Ethylene oligomerization|IT8629545V0|1986-06-12|1986-06-12|Fina Ernesto|SET BALLOON URETERAL CATHETER BALLOON FOR EXTRACTION OF URETERAL STONES|
    JP2550641B2|1988-02-29|1996-11-06|住友化学工業株式会社|Method for dimerizing lower α-olefins|
    US4973788A|1989-05-05|1990-11-27|Ethyl Corporation|Vinylidene dimer process|
    FR2650760B1|1989-08-08|1991-10-31|Inst Francais Du Petrole|NOVEL CATALYTIC COMPOSITION AND ITS IMPLEMENTATION FOR THE OLIGOMERIZATION OF MONOOLEFINS|
    US5245097A|1991-12-18|1993-09-14|Phillips Petroleum Company|Ethylene oligomerization|
    US5221775A|1992-03-19|1993-06-22|Phillips Petroleum Company|Ethylene dimerization|
    CA2095270C|1992-05-08|2004-02-17|Kotohiro Nomura|Dimerization of lower .alpha.-olefins|
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    JP2988207B2|1993-03-04|1999-12-13|住友化学工業株式会社|Production of 2,3-dimethyl-2-butene|
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    US5663469A|1996-02-05|1997-09-02|Amoco Corporation|Production of vinylidene olefins|
    US5625105A|1996-02-05|1997-04-29|Amoco Corporation|Production of vinylidene olefins|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP61001168A|JPH0662450B2|1986-01-06|1986-01-06|Method for dimerizing lower α-olefin|
    JP61064531A|JPH0698309B2|1986-03-22|1986-03-22|Method for preventing catalyst precipitation|
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