• 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:
    Components of catalysts for the polymerization of ethylene and of mixtures thereof with olefins, in the form of emulsions or dispersions in an inert liquid medium or in inert gas phase of a liquid phase comprising a compound or composition containing a compound of the metals of the Groups IV to VI of the Periodic System, immiscible in aliphatic hydrocarbons or which components are obtained from emulsions or dispersions in an inert liquid medium or in gas phase of a precursor of the catalyst component, which in the liquid state is immiscible with the normal aliphatic hydrocarbons.
    公开号:SU1545943A3
    申请号:SU823524065
    申请日:1982-12-16
    公开日:1990-02-23
    发明作者:Куффиани Илларо；Лонджи Паоло；Цуккини Умберто；Пеннини Джанни
    申请人:Монтэдисон С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the plastics industry and can be used in the preparation of homo and ethylene copolymers.
    The purpose of the invention is to increase the ability of the catalyst to form a polymer in the form of particles with an adjustable shape and size.
    The method is carried out as follows.
    Magnesium chloride is reacted with tetrachloride or tetrabutoxy-titanium and an additive.
    As an additive, 1,2-dichloroethane is used in a molar ratio of magnesium chloride: 1,2-dichloroethane 0.52 or

    cm
    2
    31545
    acetyl chloride in a molar ratio of magnesium chloride: acetyl chloride 0.16, or hydrochloric acid, introduced in the form of gaseous hydrogen chloride in an amount that provides a temperature increase from 20 to 30 ° C. N-heptane or oils are used as a dispersing agent: Cortis with a content of 7- May .7, aromatic hydrocarbons, 28 May.% G of naphthenic and 65% by weight paraffin or Zircon with a content of 20% by weight of aromatic hydrocarbons, 39 wt.% Naphtha-i new and 41 wt.% Paraffin. Index melt measured at 190 C.
    All the polymers obtained do not have irregularities in the powder and are spherical particles.
    Examples and 2. Obtaining a component of catalyst A.
    9.5 g (0.1 mol) of anhydrous powdered magnesium chloride (water content below 1 wt.%), 39.3 g (0.3 mol) of aluminum chloride and 128 cm of anhydrous toluene (molar ratio of magnesium chloride: aluminum chloride: toluene 1: 3: 12) is loaded in this order into a 500 cm flask which is pre-purged with nitrogen, equipped with a mechanical stirrer, an addition funnel, a reflux condenser and a thermometer. The resulting toluene suspension is heated to and kept at this temperature for 2 hours. Then, the resulting mixture is cooled to 45 ° C and 15.7 cm51.2-dichloroethane is added to it through an addition funnel.
    After heating at 100 ° C for 1 hour, a red-brown liquid is obtained, to which, after being re-cooled to 45 ° C, 0.1 mol of TiCl4 is added. The molar ratio of MgCl2 TiCl4 is 1: 1.
    After an additional 15 minutes of stirring at 45 ° C, the resulting solution reaches a volume of 178 cm. The viscosity at 20 ° C is 3.5 cSt. The density at 20 ° C is 1.13 g / cm3.
    Dispersion of catalyst components A.5
    The device for dispersing or emulsifying the catalyst components, which is used in all the examples, consists of a small turbomixer rotating at a speed of 1 2000 rpm / min, which is inserted into a Keller flask with a volume of 150 cm, equipped with a graduated dropping funnel on
    3
    four
    four
    0
    94
     ,

    0
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    0
    0
    five
    34
    50 cm-3 and a thermometer. Temperature control is carried out by immersing the flask in a methanol / dry ice cooling system. Before use, the device is flushed with nitrogen. The dispersible oil is introduced in this order into the flask and then introduced into the catalyst component for 5 minutes with very vigorous stirring while cooling and maintaining the temperature at 20 ° C in example 1 and 50 ° C in example 2. Then stirring is continued for 10 more minutes
    At the end of the dispersing operation and after reducing the stirring speed to 50%, the resulting emulsion is introduced into the polymerization autoclave in the amounts indicated in the table.
    Polymerization of ethylene.
    The polymerization in all examples was carried out in a 2.5 l stainless steel autoclave equipped with a spiral blade stirrer operating at 600 rpm with an automatic thermostatic system.
    At the time of introduction of the catalytic dispersion, the autoclave, which has been thoroughly purged with nitrogen, contains already 1 liter of anhydrous hexane and 7.5 moles of triisobutylaluminum, which is maintained at 60 ° C with stirring. After the catalyst components are introduced into the hexane, the temperature is increased to 75 ° C, the pressure is up to 3 atm H (partial pressure), and after that the final pressure in the autoclave is adjusted to 1 4 atm with ethylene. The contents of the autoclave are then stirred for 2 hours, maintaining a constant pressure due to the continuous supply of ethylene. The ethylene feed is stopped, the reactor is cooled to room temperature, the polymer is discharged and separated from hexane by filtration, and then dried with a stream of nitrogen at 70 ° C for 8 hours.
    The amounts of reagents used in the preparation of dispersions of the catalyst component in various types of oils and the polymerization results are shown in the table.
    Examples 3-5. Obtaining catalyst components A.
    The catalyst component A used in Examples 3-5 is prepared as follows.
    0.2 mol of anhydrous powder of magnesium chloride and 0.4 mol of tetrabutyxytitanium
    s154
    (molar ratio 1, 0: J, 0 i.iiin — pressed into a 1000 cm flask equipped with a mechanical stirrer, a reflux condenser, a thermometer and an implanter funnel. The flask is heated at 40 ° C for 3 hours. The solution obtained is cooled to 60 ° C, diluted with 640 cm 5 of anhydrous n-heptane. Then hydrochloric acid gas is introduced using a glass tube immersed directly in the liquid phase at 20 ° C with stirring, in such a quantity as to keep the system temperature around. This processing occurs first pomut the solution, and then the oily reddish phase, which is not miscible with heptane.
    After 3 hours, the hydrochloric acid is stopped and the oily suspension is heated with stirring at 60 ° C for 30 minutes, the above liquid suspension is transferred to a dropping funnel at room temperature, and then the oily phase is separated.
    The viscosity at 20 ° C is 180 cSt and the density at 20 ° C is 1.056 g / cm3. For dispersion, the components of catalyst A in various types of oils use the same operating conditions that were accepted for examples I and 2. The results obtained are shown in the table.
    PRI me R 6. Obtaining component of catalyst A.
    0.2 mol of anhydrous powdered MgCli and 0.16 mol of tetrabutoxy-titanium (molar ratio 1.0: 0.8) are charged in this order into a 250-cm flask equipped with a mechanical stirrer, a reflux condenser and a thermometer.
    The flask is heated while stirring the suspension at 140CC for 3 hours. A milky liquid is obtained, to which, after cooling, to room temperature (20 ° C), 1.2 mol of acetyl chloride is added in 30 minutes. With stirring, the suspension obtained is heated at boiling (73 ° C) for 2 hours. Then unreacted acetyl chloride is removed by distillation. The temperature in the flask is allowed to rise to 125 ° C. At this moment, the residue is oil 54436.
    piston reddish-brown mass. It is obtained 90 gm1 and it is 1.25 g / cm at 20 ° C.
    The polymerization results are shown in the table.
    invention formula
    five
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    0
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    0
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    0
    five
    权利要求:
    Claims (4)
    [1]
    1. A method for preparing a catalyst for the polymerization of ethylene and its copolymerization with alpha-olefins by reacting magnesium chloride with a titanium compound selected from the group including titanium tetrachloride and tetrabutoxy titanium, at a molar ratio of magnesium chloride and titanium compound 1.0: 0, 8-1.0: 2.0 and an additive when heated, characterized in that, in order to increase the ability
    t the catalyst to form a polymer in the form of particles with a controlled shape and size; as an additive, I, 2-dichloroethane is used in a molar ratio of magnesium chloride: 1,2-dichloroethane 0, 52 or acetyl chloride at a molar ratio of magnesium chloride: acetyl chloride 0, 16 or hydrochloric acid, introduced in the form of gaseous hydrogen chloride, in an amount to increase the temperature of the reaction mixture from 20 to 30 ° C, followed by dispersing the resulting liquid product in n-heptane. Or in oil containing 7-20 wt. % aromatic hydrocarbons 28-39 May. % of naphthenic hydrocarbons and 41-65 wt.% paraffin hydrocarbons.
    [2]
    2. A method according to claim 1, characterized in that the magnesium chloride is pre-reacted with aluminum chloride in toluene at a molar ratio of 1: 3: 12, respectively, followed by the reaction of the reaction product with 1,2-dichloroethane and titanium tetrachloride .
    [3]
    3. A method according to claim 2, characterized in that the magnesium chloride is successively reacted with tetrabutoxytitanium, the product is diluted with n-heptane and the introduction of gaseous hydrogen chloride.
    [4]
    4. A method according to claim 1, distinguished by the fact that the reaction of magnesium chloride is carried out with tetrabutoxytitanium and acetyl chloride.
    with Cir-Cortis Cir-n-Hep Cortis Kosol Kosol Tan
    20 20 20 50 20
    0.15 0.03 0.05 0.02 0.20
    . j
    270 234 268 103 230
    205 299 206 396 380
    0.23 0.18 0.23 0.12 0.07
    8.9 10.0 7.4 7.5 9.3
    0.23 0.24 0.28 0.21 0.28
    类似技术:
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    同族专利:
    公开号 | 公开日
    AT47404T|1989-11-15|
    JPS58113211A|1983-07-06|
    ES8607345A1|1986-06-01|
    BR8207449A|1983-10-18|
    AU9169382A|1983-06-30|
    ES518515A0|1986-06-01|
    GR78407B|1984-09-27|
    IN158358B|1986-10-25|
    CA1195680A|1985-10-22|
    ZA829392B|1983-11-30|
    JPH0480045B2|1992-12-17|
    KR840002857A|1984-07-21|
    IT8125840D0|1981-12-24|
    NO163190C|1990-04-18|
    NO824222L|1983-06-27|
    NO163190B|1990-01-08|
    AU565828B2|1987-10-01|
    KR900002359B1|1990-04-12|
    DE3279988D1|1989-11-23|
    IT1169291B|1987-05-27|
    US4517307A|1985-05-14|
    EP0083074A1|1983-07-06|
    EP0083074B1|1989-10-18|
    AR248145A1|1995-06-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4156063A|1971-06-25|1979-05-22|Montecanti Edison, S.p.A.|Process for the stereoregular polymerization of alpha olefins|
    US3953414A|1972-09-13|1976-04-27|Montecatini Edison S.P.A.,|Catalysts for the polymerization of olefins to spherically shaped polymers|
    IT1054410B|1975-11-21|1981-11-10|Mitsui Petrochemical Ind|CATALYSTS FOR THE POLYMERIZATION OF ALPHA OLEFINS|
    IT1078995B|1977-05-24|1985-05-08|Montedison Spa|CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    JPS54158489A|1978-06-05|1979-12-14|Mitsubishi Petrochem Co Ltd|Polymerization of olefin|
    US4395359A|1979-02-27|1983-07-26|Union Carbide Corporation|Polymerization catalyst, process for preparing, and use for ethylene homopolymerization|
    DE3065499D1|1979-04-11|1983-12-15|Mitsui Petrochemical Ind|Process for producing spherical carrier particles for olefin polymerisation catalyst, catalyst comprising such carrier particles, and use of such catalyst in olefin polymerisation|
    EP0019312B1|1979-04-30|1983-08-17|Shell Internationale Researchmaatschappij B.V.|Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions|
    US4250287A|1980-03-14|1981-02-10|Hercules Incorporated|1-Olefin polymerization catalyst|
    US4325837A|1980-08-12|1982-04-20|Phillips Petroleum Company|Catalyst, method of producing the catalyst, and polymerization process employing the catalyst|IT1178466B|1984-03-20|1987-09-09|Montedison Spa|CATALYSTS FOR THE HOMO AND COPOLYMERISATION OF ETHYLENE AND POLYMERS OBTAINED|
    EP0258089B1|1986-07-31|1990-10-24|Montedison S.p.A.|Process for preparing solid components of catalysts, or precursors of such components, in the form of microspheroidal particles, suitable for the preparation of ethylene polymers|
    DE3765351D1|1986-07-31|1990-11-08|Montedison Spa|METHOD FOR THE POLYMERIZATION OF ALPHA OLEFINS OR THEIR MIXTURES WITH AETHYLENE USING A MICROSPHAEROIDAL, PARTICLE-SHAPED, SOLID CATALYST COMPONENT OR A PRE-PREPARATORY CATALYST.|
    US5648309A|1990-06-01|1997-07-15|Hoechst Aktiengesellschaft|Process for the preparation of a poly-1-olefin|
    IT1262934B|1992-01-31|1996-07-22|Montecatini Tecnologie Srl|COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE|
    FI95387C|1992-12-29|1996-01-25|Borealis As|Process for polymerizing olefins and prepolymerized catalyst composition and process for its preparation|
    CA2136278A1|1993-12-17|1995-06-18|Viviano Banzi|Catalyst for the preparation of elastomeric ethylene-propylene copolymers|
    ES2265376T3|2001-06-20|2007-02-16|Borealis Technology Oy|PREPARATION OF CATALYST COMPONENT FOR POLYMERIZATION OF OLEFINS.|
    AT328912T|2001-06-20|2006-06-15|Borealis Tech Oy|Preparation of a catalyst component for olefin polymerisation|
    EP1323746B1|2001-12-19|2009-02-11|Borealis Technology Oy|Production of supported olefin polymerisation catalysts|
    EP1323747A1|2001-12-19|2003-07-02|Borealis Technology Oy|Production of olefin polymerisation catalysts|
    EP1375528A1|2002-06-18|2004-01-02|Borealis Polymers Oy|Method for the preparation of olefin polymerisation catalysts|
    EP1403292B1|2002-09-30|2016-04-13|Borealis Polymers Oy|Process for preparing an olefin polymerisation catalyst component with improved high temperature activity|
    ES2377948T3|2003-06-20|2012-04-03|Borealis Polymers Oy|Process for the preparation of a catalyst composition for the polymerization of olefins|
    US8222175B2|2004-12-31|2012-07-17|Borealis Technology Oy|Process for the preparation of an olefin polymerisation catalyst|
    US7749934B2|2005-02-22|2010-07-06|Rohm And Haas Company|Protected catalytic composition and its preparation and use for preparing polymers from ethylenically unsaturated monomers|
    EP1862479A1|2006-05-31|2007-12-05|Borealis Technology Oy|Olefin polymerisation catalyst|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT25840/81A|IT1169291B|1981-12-24|1981-12-24|CATALYST COMPONENTS FOR THE POLYMERIZATION OF ETHYLENE AND ITS MIXTURES WITH OLEFINS AND ITS CATALYSTS OBTAINED FROM THEM|
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