• 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 catalyst system for the polymerization of alpha-olefins is provided. The catalyst system comprises: (a) an organoaluminum containing component, e.g. triethyl aluminum, and (b) a titanium halide containing component. The titanium halide containing component is obtained by reacting a halogen containing magnesium compound, e.g. MgCl2, with an organic phosphite, e.g. triphenyl phosphite, to produce a reaction product. The reaction product is then co-pulverized with a complex of a titanium halide compound and an electron donor compound, e.g. TiCl4 ethyl benzoate, to produce a co-pulverized product. The co-pulverized product is then reacted with a titanium halide compound, e.g. TiCI4. A novel titanium halide containing component is provided as well as a process for producing said component. A process for the polymerization of alpha-olefins is also provided.
    公开号:SU1217245A3
    申请号:SU813310348
    申请日:1981-07-17
    公开日:1986-03-07
    发明作者:Алан Эпстейн Рональд；Минк Роберт
    申请人:Стауффер Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    112
    The invention relates to methods for the preparation of a catalyst component containing titanium halide used in a catalytic system for the polymerization of C.-alefins.
    The aim of the invention is to obtain a component with increased catalytic activity due to pretreatment of magnesium chloride with triphenylphosphine.
    Example 1: Slurry Polymerization A 4.454 liter jacketed autoclave, for example, a polymerization reactor equipped with a mechanical stirrer, is charged with 2 liters of dry heptane at 45-55 ° C. The nitrogen is then purged through the autoclave and the inlet is controlled to purge during the addition of the catalytic system. A syringe is injected with a portion of the organo-aluminum compound and mixed for 5-10 seconds. A weighed portion of the desired electron donor is then added through the inlet and the contents of the reactor are mixed for 5-10 seconds. Then, the catalytic component containing solid titanium halide is added, after which propylene is injected into the autoclave under a pressure of 10 atm and the temperature is maintained at 65 ° C. In the polymerization process, an additional amount of propylene is introduced to maintain the specified pressure. Polymerization samples are taken after 1.5 hours.
    At the end of the polymerization, the polymer mixture is filtered off, washed with isopropanol and dried in an oven at 7D C and the dry polymer is weighed. The polymerization solvent is pumped out to determine the polymer soluble in heptane.
    Block polymerization. A 2.8 liter jacketed autoclave, for example, a polymerization reactor equipped with a mechanical stirrer, is loaded as follows in a catalytic system.
    . Nitrogen was blown through the autoclave and the inlet purge was regulated in te-. the total time of addition of the catalytic system. A syringe of an organo-aluminum compound is introduced using a syringe. An electron donor attachment is added through the inlet. Then, the catalytic component containing solid titanium halide is added. After that add 2l
    17245
    Propylene and the temperature of propylene is raised to. Polymerization samples are taken after 1.5 hours.
    5 At the end of the polymerization, the polymer mixture is filtered, dried in an oven, and the dry polymer is weighed. The catalytic activity is defined as the ratio of the weight of the dry polymer and the weight of the polymer soluble in heptane to the weight of the solid catalytic component.
    The dry polymer is extracted with heptane for 2 hours in a Coxle apparatus. The percentage of heptane-insoluble () is determined as the percentage of heptane-soluble fracid in the dry polymer.
    The isotactic index (AI) (measure of the resulting insoluble polymer)
    20 is defined as
    . and 5 X52 ° 52 {15UER§
    the total weight of the polymer obtained
    25
    thirty
    45
    The total amount of polymer obtained includes the dry polymer and the polymer obtained, which was dissolved in the polymerization solvent.
    Receiving component. 16 g
    (0.17 mol) MgCfg is reacted with 40 g (0.13 mol) of triphenylphosphite in 100 ml of heptane at 95–100 ° C for 135 minutes. The product is filtered35 Occur, washed twice with 75 ml of heptane and dried in vacuum. 15.4 g of this product are ground with 4.2 g (12.4 mmol) of TiCl in ethyl, nzoate; within 72 h. 10 g of crushed
    40 products are suspended in 30 ml of hepta-tane and reacted with 60 ml (104 g, 55 mol) of TiCt for 1 h at 100 ° C. The final product is filtered off, washed four times with 75 ml.
    heptane and dried in vacuo. Active: the backbone of the catalytic system in sus-. polymerization using triethyl aluminum and anisic acid ethyl ester in molar
    50 4: 1 ratio (12: 3 mmol / mmol) as a component containing organo-aluminum, equal to 6082 g of polypropylene per gram of catalyst and II equal to 87.3% when using
    55 as the organo-aluminum component of triethylaluminum and methyl-ti- toluate in the same molar ratio, activity 6020, II 90.5%.
    five
    Propylene and the temperature of propylene is raised to. Polymerization samples are taken after 1.5 hours.
    At the end of the polymerization, the mixture of polymers is filtered off, dried in an oven, and the dry polymer is weighed. The catalytic activity is defined as the ratio of the weight of the dry polymer and the weight of the polymer soluble in heptane to the weight of the solid catalytic component.
    The dry polymer is extracted with heptane for 2 hours in a Soxhlet apparatus. The percentage of heptane-insoluble () is determined as the percentage of heptane-soluble fracidium in the dry polymer.
    The isotactic index (AI) (measure of the resulting insoluble polymer)
    defined as
    and 5 X52 ° 52 {15UER§
    the total weight of the polymer obtained
    25
    thirty
    The total amount of polymer obtained includes the dry polymer and the polymer obtained, which was dissolved in the polymerization solvent.
    Receiving component. 16 g
    heptane and dried in vacuo. AktivP r and me 2 (comparative). Using the same compounds, equipment, and procedure as described in Example 1, the titanium-containing component is prepared on an MgC carrier, except that the pretreatment with organic phosphite is omitted. After the component has been filtered, washed four times and dried under vacuum, it is used in four separate polymerization reactions with four separately prepared samples of triethyl aluminum. In two polymerization reactions, ethylanized with a donor for a co-active catalyst. In two polymerization reactions, ti-toluic acid methyl ester was the donor for the jointly acting njero catalyst.
    The table shows the catalyst activity values in grams. Compiler V.Teplovka Editor G. Volkova Tehred 3. Pali Corrector. M. Samborska
    Order 1006/62 Circulation 527 Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries 113035 ,. Moscow, Zh-35, Raushskay nab., D.4 / 5
    Branch PSh1 Patent, Uzhgorod, Proektna St., 4
    1217245
    liter per gram of catalytic component and stereoregularity index.
    Ethylanisate
    4888 4237
    87.7 88.9
    Methyl ether
    h-toluic acid |
    4514 4731
    91.3 92.6
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING A CATALYST COMPONENT containing titanium chloride by co-grinding magnesium chloride with a complex of titanium tetrachloride and an electron-donating compound - ether, carboxylic acid, followed by the interaction of the crushed product with titanium tetrachloride, characterized in that, in order to obtain a component with increased catalytic activity, Before grinding, magnesium chloride is pretreated with triphenylphosphite at 95-100 C for 135 minutes.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1217245A3|1986-03-07|Method of producing catalyst component
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    同族专利:
    公开号 | 公开日
    ZA813733B|1982-06-30|
    ES504073A0|1982-06-01|
    YU177981A|1984-02-29|
    CA1159044A|1983-12-20|
    KR830006339A|1983-09-24|
    NO812459L|1982-01-19|
    CS225839B2|1984-02-13|
    JPS5755904A|1982-04-03|
    AU7133981A|1982-01-21|
    BR8104176A|1982-03-16|
    KR840001831B1|1984-10-22|
    ES8205134A1|1982-06-01|
    PT73326B|1982-07-30|
    RO82690B|1984-01-30|
    EP0044445A2|1982-01-27|
    DD202443A5|1983-09-14|
    PT73326A|1981-08-01|
    RO82690A|1984-01-14|
    US4325836A|1982-04-20|
    EP0044445A3|1982-02-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1257221A|1968-02-28|1971-12-15|
    CA920299A|1968-08-01|1973-01-30|Mitsui Petrochemical Industries|Process for the polymerization and/or copolymerization of olefins with use of ziegler-type catalytsts supported on carrier|
    US3670043A|1970-03-23|1972-06-13|Donald H Kubicek|OLEFIN CONVERSION PROCESS USING COMPLEXES OF Ti, Zr AND Hf WITH ORGANOALUMINUM AS OLEFIN REACTION CATALYSTS|
    US4107414A|1971-06-25|1978-08-15|Montecatini Edison S.P.A.|Process for the stereoregular polymerization of alpha olefins|
    NL160286C|1971-06-25|
    US4013823A|1972-06-09|1977-03-22|The B. F. Goodrich Company|Process for preparing elastomeric copolymers of ethylene and higher alpha-olefins|
    US3953414A|1972-09-13|1976-04-27|Montecatini Edison S.P.A.,|Catalysts for the polymerization of olefins to spherically shaped polymers|
    JPS5645404B2|1976-03-01|1981-10-26|
    DE2744559A1|1976-10-07|1978-04-13|Mitsubishi Petrochemical Co|PROCESS FOR MANUFACTURING CATALYST COMPONENTS FOR OLEFIN POLYMERIZATION|
    US4148756A|1977-04-25|1979-04-10|Exxon Research & Engineering Co.|Novel trialkyl aluminum cocatalyst|
    US4130503A|1977-12-23|1978-12-19|Phillips Petroleum Company|Phosphite in MgX2 supported TiX3 /AlCl3 catalyst system|
    US4243552A|1978-12-11|1981-01-06|Phillips Petroleum Company|Polymerization catalyst and process|US4680350A|1981-09-10|1987-07-14|Stauffer Chemical Company|Purified catalyst support|
    US4384984A|1981-09-30|1983-05-24|Stauffer Chemical Company|Titanium catalyst for polymerizing olefins|
    US4451688A|1981-12-03|1984-05-29|Nippon Oil Company, Limited|Process for preparing polyolefins|
    US4431570A|1982-05-14|1984-02-14|Standard Oil Company |Retreating comminuted olefin polymerization catalyst with a titaniumcompound and an ester|
    US4431571A|1982-05-14|1984-02-14|Standard Oil Company |Retreating comminuted olefin polymerization catalyst with a titanium compound, a haloalkylchlorosilane and an ester|
    US4431572A|1982-05-14|1984-02-14|Standard Oil Company |Retreating comminuted olefin polymerization catalyst with a titaniumcompound, a chlorocarbon and an ester|
    US4981928A|1983-08-04|1991-01-01|Exxon Research And Engineering Company|Supported polyolefin catalyst for polymerization of ethylene under high temperatures|
    IT1197320B|1986-10-02|1988-11-30|Ausimont Spa|CATALYSTS FOR THE PREPARATION OF ELASTOMERIC, SATURATED AND UNSATURED OLEFINIC COPOLYMERS, AND VOPOLYMERS WITH THEM OBTAINED|
    US5248737A|1987-05-08|1993-09-28|Aristech Chemical Corporation|Method of making amine/propylene copolymers|
    US5270410A|1989-04-25|1993-12-14|Shell Oil Company|Process for the production of elastomeric, primarily syndiotactic polypropylene and catalysts for use in said process|
    US5270276A|1989-04-25|1993-12-14|Shell Oil Company|Process for the production of elastomeric, primarily syndiotactic polypropylene and catalysts for use in said process|
    US4971936A|1989-07-10|1990-11-20|Shell Oil Company|Catalyst component for making primarily isotactic elastomeric polypropylene or polybutene|
    US5089573A|1990-02-26|1992-02-18|Shell Oil Company|Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process|
    US5118767A|1990-02-26|1992-06-02|Shell Oil Company|Process for producing mildly elastomeric primarily isotatic polypropylene and poly-1-butene|
    US5118649A|1990-02-26|1992-06-02|Shell Oil Company|Process for the production of elastomeric primarily isotactic polyolefins and catalysts for use in said process|
    US5118768A|1990-05-11|1992-06-02|Shell Oil Company|Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process|
    US5164352A|1990-05-11|1992-11-17|Shell Oil Company|Process for the production of elastomeric, primarily isotactic polyolefins and catalysts for use in said process|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/170,262|US4325836A|1980-07-18|1980-07-18|Novel titanium halide containing catalyst|
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