• 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 catalytic system for polymerizing olefins comprises: a) a cocatalytic component containing an organometallic compound of Groups I-III of the periodic table, and b) a catalytic component containing titanium obtained by: (i) copulverising a substantially anhydrous magnesium compound containing halogen or manganese compound containing halogen with: a phenol, an organic polymer containing silicon, a titanium halide and an electron-donor compound to produce a copulverized product, and (ii) reacting the copulverized product with a liquid titanium compound containing halogen. The invention also encompasses the novel catalytic component, processes for preparing the catalytic component containing titanium, and the use of the novel catalytic system for polymerizing olefins.
    公开号:SU1306467A3
    申请号:SU833625049
    申请日:1983-07-19
    公开日:1987-04-23
    发明作者:Иван Минк Роберт
    申请人:Стауффер Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

     13
    The invention tj rHocHTcn to methods for the preparation of a component of the catalytic system for the polymerization of olyf; HOBj containing titanium chloride.
    The purpose of the invention is the incorporation of a component of a catalytic system with increased activity by conducting joint and small components in the presence of phenol.
    P. pimer I, RojiytieHHs complex of titanium tetrachloride and ethyl benzoate used in the preparation of the proposed catalyst. .
    The three-liter vessel is equipped with a gas inlet valve, a mechanical agitator with rotating; 5-teflon blades and a 250-ml dropping zoo-rim; ml (1.73 mol) of distilled TiCi-jg is then slowly added 245 mp (1.72 mol) of ethyl benzoate (Aldrich 99.9%) over 1 hour. A yellow precipitate of the com plexus is formed immediately, the mixture is stirred for 2 hours or 2 hours -. natal temperature After pephenos vessel in a vacuum chamber ru.e. equipped with gloves, the mixture is filtered under nitrogen, washed with 2 liters of heptane and dried for 17 hours in a yakuum. The output approaches the theoretical.
    EXAMPLE 2 Preparation of crushed (copolymerized) titanium containing product,
    In a 7 liter mill (Paul Аb- be), 500 g of MgClj, dried under vacuum when heated, containing about 1% of water, and 3,, About kg iuapoB of stainless steel .6 sy in diam


    five
    This downloadable riepei ;; - l for five days from estop; -, 50 rpm, Lctivirving /; The seed is sifted out from the steel 1 ;; chg - ;;. sieve number 30.
    8.0 kg of stainless steel balls with a diameter of 1.6 cm and 250 g (2.62 mol) of activated MgCl2 again urn down into the same mill together with 235 g of phenol (2.55 mol) and 37, 5 PL forces :. New oil viscosity 9 & 10Q NP (General Electric Co. S: F Dfr-SOD). It is sprayed at a speed of 50 rpm for another five days. A load of 132 g of conylex is added to the load. TxSTs X ethyl benzoate g pHmer I. yoku .;
    fO
    15

     .
    -
    the mixture is ground by an en; e five days (only 15 days), the orange-red product is sieved through a No. 30 sieve to separate it from over-heating sharosis and then through 140 kkt. The output is ZAO G.
    Inside the glove. In an atmosphere of nitrogen, a chamber of 212 g of ground product is placed in a two-liter three-neck vessel equipped with a gas inlet valve, a mixer made of teflon fluoroelastomogram, and a 250 ml addition volume adjusted for pressure. With pere-; eE1nivaniya in a nitrogen atmosphere in the reaction vessel with a hood for 1 m at a speed of 625 uo lz then add with such
     375 t-tn (3.41 mol) TiCl; The reaction mixture of the mixture is also stirred / at a speed of approximately 100 rev / min 1, while the reaction-ion vessel is slowly heated to an oil bath. After a temperature equilibrium has been reached for about I h, cycl1 is carried out at an additional 3 h.
    thirty
    35
    40

    .50 -, 55
    The vessel is then olladgate to the environment of the environment for 45 MIN) while the solid phase is precipitated, and the supernatant is removed by means of a canoe. and "Then, under gentle stirring at 40 rpm, 1 liter of toluene and 10 minutes long is added. to wash the precipitate. After the half hour osatoden, the supernatant is again removed with a cannula, Flushing is repeated once more with toluene and 5 times with heptane (all about {3 b - 5 r flushing liquid). After washing O1), the icy flux is transferred to an odiolithic track-neck with an additional amount of heptane. The supernatant is separated by cannula, and the heptane is evaporated in vacuo. After the seedling powder through sieve No. 40, 92 g orange-brown powder is obtained.
    PRI me R 3 B. by example: aai sHH olefin (pro.pei.z), ogut, eat-simulated in the presence of the proposed catalyst with
    At 2.3 pp; equipped with a heater, a dc coptrol temp; device and tubes D / P1 input and output ga 31306A6
    9 MMOJsb of triethylamine, 0.54 g of methyl p-toluate, 30 mg of the proposed catalyst of Example 2 and 1/3 atm of hydrogen are added for a moderate course of polymerization; The reactor is stirred at rpm and held at, then propylene monomer is introduced and maintained at a pressure of 32 atm for 1.5 h, after which the residue is poured by introducing gases and the reactor is poured into alcohol. The solid product is filtered from
    Diameter of particles, micron Fraction weight,%
    Example 4. Polymerization in a suspension of olefin (propylene) in the
    the solvent (heptane), carried out in the presence of the proposed catalyst.
    Ana: as in Example 3, in a 4.5-liter reactor containing 2 liters of heptane stirred at 600 rpm, polymerization is carried out, 5 hours with reagents added in the following sequence: 12 mmol of aluminum triethyl, 0.54 g methyl para-toluate, 100 mg catalytic: o1 o component of the example
    dry polymer + polymer, soluble in titanium component
    The isotactic index is calculated as follows:
    TT t 2j 1 TH 22 P252 EL122
    total polymer
    where CJ is the fraction of the polymer, the insolubility- IQ of the Roman in boiling heptane for
    3h
    Examples 5-34. A titanium catalyst is prepared as in Example 2. 4i Using a slurry polymerization method as described in Example 4, using hydrogen as a moderator. reactions, polymerization is repeated weekly for 7 May, with one 50 and the same sample. ,
    Table B, Table 1 shows the results of the determination of the catalytic activity and stereospecificity, measured by the isotacticity index, after 6 months, with the instant polymerization of the catalyst sample.
    the reaction mixture, .. poured heptane and dried in vacuum.
    As a result of block polymerization, 16 g of polypropylene per I g of titanium catalyst are obtained, the isoactivity index (II) is equal to 94.5. The polymer contains about 2 hours per thousand titanium, the polymer has a bulk weight of 0.45 g / ml.
    The resulting polymer (polypropylene) has the following particle size distribution:

    -425
     : 57
    850 78
    1700 90
    2. About 1/5 atm of hydrogen is used to moderate the reaction, propylene is maintained at a pressure of 10 atm.
    After 1.5 h, the reaction is stopped, the product is washed and dried under vacuum. The catalytic component shows the activity of 9.0 g of polymer per 1 g of the catalytic component, II 89. The volumetric weight, catalytic residue and particle size distribution are the same as in Example 3.
    The catalytic activity is calculated as follows:
    Table

    29
    8039 (88.2)
    8046 (89.1) 7299 (88.8)
    6348 (91.8) 7289 (88.0)
    9203 (84.4) 8493 (84.8)
    7 13064678
    Example 41. The elemental analysis according to examples 35-40 in 5 ra-el-LIZ 6 samples of the proposed titanium experiments according to the method described in the first catalyst, obtained by measures I and 2, is presented in table 3.
    Table 3
    9 GR. ten
    blows that the proposed method m6- The data of table 5 show that in
    Compared with the more labor-intensive mode of Example 2, the proposed stereospecific high active catalysts can be obtained in about half the grinding time with an amount of phenol, equal to 1/4,
    Stable activity and stereoSpecificity of the catalyst can be obtained.
    Example 46-67, Results of varying (according to the methods of examples 2) the grinding time and the ratio of the three electron donors — a comp of half the amount of silicone oil and half the amount of comp
    Lexa T1STs x ethyl benzoate, silicon-0 „eks x etibbenzoat. Apart
    first oil and phenol are presented in table.5. Suspension polymerization of the obtained samples are, according to example 4.
    milling stages used in examples 1 and 2, it can be excluded. two or three donors can be milled in one stage.
    285 28.6A, 25
    285 28.64.25
    285 28.64.25
    JO5 to1,55
    125 61,32
    with half the amount of silicone oil and half the amount of comp
    Eks x etipbenzoat. Apart
    milling stages used in examples 1 and 2, it can be excluded. two or three donors can be milled in one stage.
    , T a b l and c a 5
    ii RiMer 68, Varying Sport: Oio, in 11 Al-Mining according to Example 2.
    All reagents and their relative amount are the same as in Example 2, except for the order of addition and the degree of grinding.
    According to Example 68a, MgCl2 is re-consumed for five days, then all three electrons (TiCl4, ethyl benzoate, phenol, silicone oil) are added simultaneously; the mixture is milled.: ten days and sopulveriat ekst
    As in Example 2, it is rigged with a mixture of tog1uola and titanium tetrachloride, jsHTofl in a ratio of T1SC: toluene
     gfi seru b8b procedure is analogous to example 68a, except that the second grinding lasts 5 days, so that the total grinding process lasts 20 days, including
    Continuation of table.5
     prior to measurement, until the moment of extraction with a mixture of luol,
    In accordance with Example 68c, MgCLi is not ground, simply dried in an oven. All organic electron donors are added first and the total mixture is ground for five days before extraction.
    In the implementation of Example 68d, a simplified version of Example 68c is repeated; instead of the solid TiCl complex X. ethyl benzoate, the same molar amount of liquid NaCl – eoate is used.
    By agreement of the standard procedure of Example 4, suspension polymerization of propylene is carried out. Catalytic activity and 31 the following
    R

    imer
    Activity, g PP / g cat
    (eleven)
     0409 (89, 2). 9788 (9, A) 10357 (90.2) 10306 (89.4) 69
    m post-treatment temperatures (extraction stages | mixes TiCl / toluene, described in example 2. The amount of MgClj, phenol, a group of TiCli x ethylbenzoate and silicone oil is the same as in example 2. Grinding in three stages, the duration of each 5 days, as described in example 2. For each variant, 10 g of MgCl1-modified pulverized powder is treated with 20 ml of TiCl,.;, in 30 ml of toluene, as in Example 2. The time and temperature are changed as shown in Table 6 , the component is washed, filtered, dried in vacuo and tested in the process of suspension polymerization propylene as described in Example 4.
    Table 6
    ..
    As can be seen from table 6, ak iitocTb catalyst directly:., E is associated with a duration of post-treatment failure. In addition, temperatures can be used in the post-processing stage.
    Example 70. Variation in the amount and ratio of TiCl / toluene used in the extraction stage of post-processing of Example 2, in three organic electron donors, in the stage of soporiverizacin, as well as the variation of the duration of the rewinding stage. stranded vice.
    20
    25
    Except for the aforementioned cases (Table 7), the amount of phenol MgClj used, Kot. nJseKca TiCl.x ethyl benzoate is the same as in Example 69. The duration of the three stages of grinding-gnn in a ball mill is also five days, except in certain cases. Each time the post-treatment in T1C14- / toluene is carried out at 100 ° C for 2 hours. After separation, washing and vacuum drying. the activity of the catalytic component is assessed in the process of suspension polymerization of propylene carried out in accordance with Example 4. As follows from Table 7, with a shorter grinding time, the proposed catalyst retains its stereo-specific properties; a decrease in the amount of electron donor can reduce the catalytic activity The treatment does not depend on the amount of TiCl4 - nor. from) on / od solvent / TiCl.
    Example 7. Equipment for producing the proposed titanium catalyst, includes a 1-20-l1 enamel-enameled reactor jacket mixed with a steam jacket, a Furidabrand filter 0.6 m in size made of stainless steel, a zmaledirovanny rotating drying drum with a volume of 1 53.28 dm, ball mill volume of 28.3 dm, loaded steel balls weighing 50 kg j27 cm in diameterTable 7
    1/2 phenol, 1/2 ethyl benzoate; 5, - A, 3 days transfer in DJapo howl mill.
    The rotating tumble dryer is used to reduce the water content in 10 kg of MgC (commercial grade is from 2.5-3.0 to 1.5-2.2% of moisture by heating for 8 hours while blowing with nitrogen at 0.06 atm
    The ethyl benzoate complex is obtained by loading 60 liters of heptane and 2 kg of ethyl benzoate into the reactor. Then, with stirring, 2.6 kg of TiCb were slowly added to the reactor. with such an eye

    so that the temperature is maintained at 40 ° C. After completion of the reaction, stirring is continued for another 20 minutes, after which additional HzO l of heptane is added. The mixture is then filtered off and dried on a filter with nitrogen. Yield 4.4 kg x ethyl benzoate complex.
    Dry Mp.Cl is ground for 8 hours at 30 °, after being completely cooled, it is discharged,
    In a ball mill load 3 kg of pre-ground MgClj, 0.5 kg of silicone oil and 3 kg of liquid phenol (at). The ball mill works with complete cooling for 4 hours. Then, 1.5 kg of T1SC complex X ethyl benzoate is added and grinding is continued for an additional 4 hours, after which the ground soprovolat unload (about 7 kg). The sopour verification is then repeated with three organic electron donors, obtaining a sufficiently intermediate one. product for post-processing stage.
    Post-processing was carried out by loading into the reactor 45 liters of toluene, 12 kg of co-sulperizate and adding quite slowly 36 kg of TiCl. so that the temperature remains below. After completion of the addition, the reactor is heated to 90 ° C and maintained at this temperature for 2 hours, after
    additionally added
    80 l of toluene and solid precipitate are taken off. The pressed precipitate is first washed with 140 l to.t of luol, then 140 l of heptane and dried with a stream of nitrogen. Output predla-;
    titanium catalyst 9 KG.
    Catalytic activity and stereospei.ifich yustt product is checked in the polymerization reaction according to
    Example 4. With a catalytic activity of 7300 g / g, nsotactically, the index is 91.9; and with a catalytic activity of 4.900 g / g - 91.6.
    Example 72. The use of the proposed catalyst in the polymerization of ethylene.
    Ethylene is polymerized in an -I-liter round-bottomed vessel, mounted on a shaking table with a 5 centimeter stroke, shaking speed of 265 per minute for i, 5 hours at a pressure of 2 atm. As a catalyst, alkyl aluminum or alkyl magnesium is used in an environment free of moisture and air. After treatment, sodium peroxide is used to remove traces of transition metals by removing it with nitrogen, after which it is washed, rinsed with acid, washed and dried.
    The vessel, heated to approximately purge with nitrogen and cooled to 70 s, then 300 mp of heptane is added. Then, in an inert atmosphere, 0.1 g of a titanium catalyst is transferred from the vial to the reaction vessel and 5.6 is added. ml of a 26% solution of triisobutylaluminum in heptane using a syringe for subcutaneous injection. The reaction begins by opening the feed valve of monomeric ethylene. After an hour and a half shake, the monomer is carefully withdrawn, thus stopping the reaction; ation. Then 500 ml of isopropyl alcohol is added, the solid polymer is separated, the mixture is washed with 400 ml of an alcohol mixture, water 2: 1 and dried in a vacuum. Co catalytic activity, Tavil 555 g PE / per g titanium catalyst.
    Comparative example I. Efficiency of using two, rather than three electron donors, used in the preparation of the titanium catalyst proposed.
    . Using the procedures of Examples If 2 and 4, a control experiment (Example 1a) was performed using TiCl / toluene reagent for the post-treatment extraction step. Then, the same procedure is repeated, but is used without ns using the TiC – C complex of ethylbeisoate (example b) and phenol (example Jd) as electron-donators.
    For each of the titanium components being compared, polymerization of propylene in suspension form is carried out according to an example, half a year by the results of catalytic activation and thermospecificity. Table 8 shows.
    Table 8
    bepzoat
    1c Silicone 888 85.3 oil
    Id Phenol
    6255 87.1
    Comparative example 2.
    The efficiency of using two, rather than three electron donors, used in the preparation of the preliminarily titanium catalyst component ™, is that, plus the use of pure TiCl reagent without solvent in a post-processing extraction step.
    The procedures of comparative 0 examples G are repeated, but use pure T1SC without solvent. A test preparation was carried out using all three methods .; electric donors (example. 2a) then. without complex TicCx ethyl benzoate (pri p 26) ", without silicone oil (example 2c) and without phenol (example 2d),
     Dp of all these comparative results was carried out using the standard PSP method according to the procedure of Example 4, which was standardized with the use of a catalytic activity and obtained stereo-specific properties of% j, j in Table 9.
    VShPY Order 1470 / 5B
    The method of obtaining the composite system; dp for olefins containing chloe by co-grinding the shock of anhydrous ciwoKcaHOM chloride and ethylbenzoatolex of titanium tetrachloride with benzoate followed by the obtained joint product with tetrachloro in an inert carbohydrate without it bo-uo C, but with. for the sake of KcjMnoHBHTa with increased activity, combining into powder without phenol.
    Circulation 5Sh Subscription
    : -.- ai.f, .. b-bub-.t -., .....-. r -. ,, ir-i, .- -t-t, L-ir-r
    Shuffle poly. np-i-hej Uzhgorod, st. Project, 4
    Table 9
    Comparative example 3 (according to a known method, US patent No. 4157A35). .20 g MgCU (Vacuum and milled in vacuum), 6 ml of ethyl benzoate and 3 ml of C1SHICON oil (SF 96/100 General Electric Tractor Company) grind 10U, h in the presence of 1750 g of large stainless steel balls 15 with diameter 15; Y mm at ambient temperature environment.
    iO, 5 g of the product is added to titanium tetrachloride (60 mp) at ambient temperature. The mixture is heated to 80--82 from 2 h 0 min, then filtered at about and washed with heptane (about 500 ml) until the washing liquid becomes colorless and dried overnight. After polymerization, the activity is 5284 g / g, and the isotactic index is 85.2,
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for producing a component of a catalytic system; dp polymerization of olefins containing titanium chloride, by co-grinding into powder anhydrous magnesium chloride with polycywoKcaHOM and ethyl benzoate or a complex of titanium tetrachloride with ethyl benzoate followed by reaction. By using the co-milled product obtained with titanium tetrachloride in an inert hydrocarbon medium or without it, BW-C, characterized in that In order to obtain KcjMnoHBHTa with enhanced catalytic activity, co-grinding is carried out in the presence of phenol.
    类似技术:
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    同族专利:
    公开号 | 公开日
    AU1490883A|1984-02-16|
    ES524569A0|1984-12-01|
    ZA833570B|1984-04-25|
    AU561271B2|1987-05-07|
    YU166183A|1986-04-30|
    CS247166B2|1986-12-18|
    BR8304261A|1984-03-13|
    JPS5947207A|1984-03-16|
    DK335683A|1984-02-10|
    EP0101136A3|1984-09-26|
    ES8501776A1|1984-12-01|
    KR840005823A|1984-11-19|
    CA1202952A|1986-04-08|
    PT77148A|1983-09-01|
    RO88830A|1986-06-30|
    NO832841L|1984-02-10|
    DK335683D0|1983-07-21|
    EP0101136A2|1984-02-22|
    US4450242A|1984-05-22|
    DD232283A5|1986-01-22|
    DD218625A5|1985-02-13|
    PT77148B|1986-01-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US4312782A|1980-05-12|1982-01-26|Stauffer Chemical Company|Titanium halide catalyst for polymerization|
    US4364853A|1981-09-18|1982-12-21|Stauffer Chemical Company|Catalyst for polymerizing olefins|JPS6247445B2|1981-06-11|1987-10-08|Toyo Stauffer Chem Co|
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    EP0197310A3|1985-03-07|1988-07-20|Mitsubishi Petrochemical Co., Ltd.|Catalyst components for polymerizing olefins|
    US4945142A|1988-11-14|1990-07-31|Conoco Inc.|Composition and process for friction loss reduction|
    US5028574A|1988-11-14|1991-07-02|Conoco Inc.|Composition and method for friction loss reduction|
    US6878659B2|2000-05-24|2005-04-12|Toho Titanium Co., Ltd.|Solid catalyst component for olefin polymerization and catalyst|
    US20030069372A1|2001-10-09|2003-04-10|Formosa Plastics Corporation, U.S.A.|Olefin polymerization catalyst and process for preparing polyolefins with said catalyst|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/405,977|US4450242A|1982-08-09|1982-08-09|Catalyst for polymerizing olefins|
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