• 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:
    A novel process is disclosed for polymerizing and copolymerizing alpha olefins (ethylene included) also in the presence of conjugated diolephins, and more particularly for copolymerizing ethylene with 1,3-butadiene, based on the use of a plural-component catalyst system, one of said components being a novel complex which contains titanium and magnesium. The process gives, in yields higher than 200,000 grams of polymer per g of elemental Ti, ethylene-butadiene copolymers having a distribution of monomeric units characterized by a particular novel 13C-NMR spectrum, a high apparent specific gravity and such a grit size as to impart flowability to the dry product, and a distribution in the presence of sulphur and accelerators such as to acquire a gel content (fraction insoluble in boiling xylenes) over 50%.
    公开号:SU1688788A3
    申请号:SU823469541
    申请日:1982-07-28
    公开日:1991-10-30
    发明作者:Карбонаро Антонио；Ферреро Чезаре；Корбеллини Маргерита
    申请人:Аджип Петроли С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of a catalyst for the copolymerization of ethylene and 1,3-butadiene and can be used in the chemical industry in the preparation of polymeric materials.
    The purpose of the invention is to increase the activity of the catalyst.
    EXAMPLE 1. The process is carried out in a rotating flask, in the center of which a tungsten filament coiled in a spiral is connected to a source of electrical energy. The flask is horizontal and immersed in a cold bath. In the upper part of the flask there are openings for supplying nitrogen and for connecting to a vacuum line.
    2.5 g (103 mg-atom) of magnesium wire is wound around the tungsten coil. 300 ml of n-heptane, 1.17 ml (3.45 mmol) of tetrabutyl-ortho-titanate and 31.5 ml (230 mmol) of 1-chlorohexane are introduced into the flask under a nitrogen atmosphere. The flask is cooled to a temperature of -70 ° C, evacuated to a residual pressure of 10 J mm Hg. Art. and heat the coil to evaporate the metallic magnesium. Upon completion of the evaporation of the magnesium, nitrogen is supplied to the flask in approximately 20 minutes and 5.1 ml (55 mmol) of n-butanol are introduced into the flask to form a suspension. The flask is heated to ambient temperature and then boiled and the suspension is boiled for 2 hours. According to the analysis, the solid fraction of the resulting suspension contains, in May. %: titanium 1.7;
    O 00 00 VJ 00 00
     WITH
    magnesium 19.9; chlorine 39.2 and ether groups 39.7% by weight.
    The resulting suspension is loaded in an amount equivalent to 0.015 mg-atom of titanium in an autoclave with a capacity of 5 liters, equipped with a root stirrer and containing 2 liters of dehydrated and deaerated n-heptane, 10 mmol of triisobutylaluminum, 5 mmol of aluminum dichloride, hydrogen (increasing pressure to 2.9 bar), 230 g of 1,3-butadiene and ethylene (increasing the pressure to 9.7 bar). The contents of the autoclave are heated to 70 ° C and remain at this temperature for 2 hours with continuous feeding of ethylene to maintain a constant pressure in the autoclave. Upon completion of the polymerization, 246 g of copolymer is obtained with a yield of 330,000 g / g of titanium.
    EXAMPLE 2 The process is carried out as described in Example 1, using 2.45 g (100 mg atoms) of magnesium wire. 300 ml of dehydrated n-heptane, 0.312 ml (2.85 mmol) of titanium tetrachloride and 300 ml (220 mmol) of 1-chlorohexane are introduced into the flask. The resulting suspension is diluted with 4.95 ml of iso-amyl alcohol. According to the analysis, the solid fraction of the suspension obtained contains, in wt%: titanium, 1.33; magnesium 20; 45.5 chlorine and ether groups 33.2.
    In the autoclave, described in example 1 and containing the same components, heated to 70 ° C, the resulting suspension is introduced in an amount equivalent to 0.025 mg-titanium atoms, and the process is carried out for 2 hours, as described above. 520 g of copolymer are obtained with a yield of 430000 g / g of titanium.
    If 2 liters of dehydrated and deaerated n-heptane, 8 mmol of triisobutylaluminum, 1 mmol of ethyl dichloride aluminum are loaded into the specified autoclave, and then the resulting suspension in an amount equivalent to 0.005 mg titanium atom, raise the temperature to 85 ° C and introduce hydrogen to pressure 2 bar and ethylene containing 4% n-butene-1, to a pressure of 5 bar, after polymerization for 2 hours, 200 g of copolymer is obtained, which amounts to 800,000 g of polymer (U.TI.).
    Example 3: The process was carried out as described in Example 1 using 2.4 g (98 mg-atoms) of magnesium wire. 315 ml of anhydrous n-heptane were introduced into the flask.
    0.36 ml (3.3 mmol) of titanium tetrachloride and 26.9 (198 mmol) of 1-chlorhexane. The resulting suspension is diluted with 2.7 ml of ethanol. According to the analysis data, the solid fraction of the suspension obtained contains, in wt%; titanium 1.7; magnesium 22.55; chlorine 46.75 and ester groups 29.
    In the autoclave described in example 1, load 2 liters of dehydrated and deaerated n-heptane, 10 mmol of triisobutylaluminum and 5 mmol of ethyl dichloride aluminum.
    The temperature in the autoclave is raised to 70 ° C and hydrogen is introduced (before the addition of 2.9 bar), 230 g of 1,3-butadiene and ethylene (before the addition of 9.7 bar), and then the resulting suspension in an amount equivalent to 0.042 mg atom of titanium.
    After polymerization for 2 hours, 420 g of copolymer are obtained.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method for preparing the catalyst for copolymerization of ethylene and 1,3-butadiene by
    the interaction of tetrabutyl orthotitanate or titanium tetrachloride with vapors of the magnesium reducing agent obtained by evaporation of magnesium at a pressure of 10 3 mm Hg and condensed at a temperature of
    -70 ° C, with a molar ratio of magnesium and titanium compound of 29.7-35.0 in anhydrous heptane in the presence of 1-chlorohexane in a molar ratio with magnesium: 1: (2-2.21 and with a compound of titanium (60-77) : one,
    in a nitrogen atmosphere at the boiling of the reaction medium for two hours, characterized in that, in order to increase the catalyst activity, the resulting suspension is boiled in the presence of an aliphatic alcohol selected from the group ethanol, butanol and isoamyl alcohol, at a molar ratio of the titanium compound and alcohol 1: (14-16).
    类似技术:
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    同族专利:
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    GB2103226A|1983-02-16|
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    IT8123212D0|1981-07-29|
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    DK323082A|1983-01-30|
    FR2510587B1|1986-04-18|
    RO85330A|1984-10-31|
    NL188164B|1991-11-18|
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    ES515557A0|1984-09-01|
    NO161376B|1989-05-02|
    RO85330B|1984-11-30|
    DE3228372A1|1983-02-10|
    ZA824952B|1983-04-27|
    NO822580L|1983-01-31|
    AU8637582A|1983-02-03|
    BG42524A3|1987-12-15|
    IE821816L|1983-01-29|
    GR76205B|1984-08-03|
    CH654317A5|1986-02-14|
    SE453296B|1988-01-25|
    PL134909B1|1985-09-30|
    DD202582A5|1983-09-21|
    LU84288A1|1983-04-13|
    AT386215B|1988-07-25|
    FR2510587A1|1983-02-04|
    US4446289A|1984-05-01|
    TR21778A|1985-07-03|
    IE53869B1|1989-03-29|
    CS241115B2|1986-03-13|
    YU164782A|1985-04-30|
    NL8203012A|1983-02-16|
    AU553262B2|1986-07-10|
    ES8406895A1|1984-09-01|
    SE8204474D0|1982-07-27|
    BE893965A|1983-01-28|
    DK162650C|1992-04-21|
    HU196437B|1988-11-28|
    NO161376C|1989-08-09|
    JPH0412284B2|1992-03-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO1995035163A1|1994-06-20|1995-12-28|Institut Kataliza Imeni G.K.Boreskova Sibirskogo Otdelenia Rossiiskoi Akademii Nauk|METHOD OF PRODUCING A DEPOSITED CATALYST FOR THE POLYMERISATION OF ETHYLENE AND COPOLYMERISATION OF ETHYLENE WITH α-OLEFINS|NL7018333A|1969-12-22|1971-06-24|
    US3859231A|1972-10-13|1975-01-07|Gulf Research Development Co|Simplified process for manufacture of catalyst component|
    US4194992A|1976-01-30|1980-03-25|Snamprogetti, S.P.A.|Method for the polymerization of olefines and means suitable thereto|
    IT1054583B|1976-01-30|1981-11-30|Snam Progetti|Titanium or vanadium trichloride prepn. - by reacting the tetrachloride with metal vapour, partic. magnesium, for obtaining olefin polymerisation catalyst|
    IL51283A|1976-01-30|1979-11-30|Snam Progetti|Process for preparing a co-catalyst for use in the polymerization of a-olefins,a co-catalyst prepared by the process,a catalytic system comprising such a co-catalyst and a process for polymerizing an a-olefin using such catalytic system|
    GB1578745A|1976-05-24|1980-11-12|Bp Chem Int Ltd|Polymerisation catalyst component|
    US4246384A|1978-11-08|1981-01-20|Phillips Petroleum Company|Magnesium reducing agent for producing titanium trihalide catalyst component|
    IT1115152B|1979-03-07|1986-02-03|Anic Spa|PROCESS FOR THE COPOLYMERIZATION OF ETHYLENE WITH MULTI-UNSATURATED HYDROCARBONS|
    US4342855A|1980-08-27|1982-08-03|Idemitsu Kosan Company Limited|Process for the production of polyethylene|IT1176299B|1984-06-22|1987-08-18|Anic Spa|METHOD FOR THE PREPARATION OF A ZIRCONIUM OR AFHNIUM CATALYST AND PROCESS OF POLYMERIZATION OR COPOLYMERIZATION OF UNSATURATE COMPOUNDS USING THE SAME|
    EP0176641B1|1984-10-05|1989-02-15|Pony Industries Incorporated|Hydrocarbon fluid friction reducing composition containing olefin copolymer and process for producing same|
    DE3581741D1|1985-11-21|1991-03-14|Pony Ind Inc|METHOD FOR POLYMERIZING ALPHA OLEFINS WITH A ZIEGLER CATALYST.|
    FI87891C|1991-07-16|1993-03-10|Neste Oy|METATESKATALYSATOR FOER OLEFINER|
    FR2691970B1|1992-06-04|1995-08-25|Bp Chemicals Snc|PROCESS FOR THE PREPARATION OF A POLYMERIZATION CATALYST.|
    JP5394630B2|2007-10-22|2014-01-22|東邦チタニウム株式会社|Method for synthesizing alkoxymagnesium, method for producing solid catalyst component for olefin polymerization|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT23212/81A|IT1137631B|1981-07-29|1981-07-29|PROCEDURE FOR HIGH YIELD POLYMERIZATION AND COPOLYMERIZATION OF HYDRAULICALLY UNSATURATED COMPOUNDS AND MEDIA SUITABLE FOR SOCPO|
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