• 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 process for preparing components of catalysts for the polymerization of alpha-olefins and mixtures thereof with ethylene is disclosed. The process comprises reacting a Ti compound having at least oe Ti-halogen linkage with either (1) a mixture of a hydrocarbyl electron-donor compound ED which does not contain active H atoms and an adduct (a) of a Mg dihalide with at least one hydrocarbyl electron-donor compound AH containing active H atoms, or (2) with an adduct (b) of at least a Mg dihalide with a compound AH and ED defined in (1), adducts (a) and (b) being obtained without co-grinding of the Mg dihalide with compounds AH and ED.
    公开号:SU1233790A3
    申请号:SU813339797
    申请日:1981-06-17
    公开日:1986-05-23
    发明作者:Чеккин Джулиано；Альбиццати Энрико
    申请人:Монтэдисон С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of a catalytic component: polypropylene polymerization.
    The aim of the invention is to obtain a component with increased activity due to the interaction of magnesium dichloride, an electron-donor compound and titanium tetrachloride under certain conditions.
    Example. A, Obtaining a catalyst component,
    To 25 g of anhydrous MgCl (content: -1: 0.5%, crystalline form, crystal diameter, 380 A), suspended in 300 cm of technical h-heptane, while stirring, 8 g of ethyl: benzoate are added dropwise, This operation is performed at room temperature and under nitrogen. After 1 h, 39.2 g of n-butyl alcohol is also added dropwise to this suspension. The temperature rises to 80 ° C and the reaction is continued for 1 hour. At the end of the reaction, the solvent is removed by distillation at 50 G and under reduced pressure, resulting in 70 g of solid product.
    25 g of the product thus obtained are treated with stirring at 210 cm Ticr at 100 ° C for 2 hours. To the suspension, 51 cm of heptane are added dropwise with stirring. After 15 min, stirring is stopped and the solid remains to settle. The liquid is removed by hot siphoning, and the solid is washed for four times, each time with 130 cm of heptane at BO C, and the rest at room temperature until the disappearance of TiCf4.
    This product is partially dried under vacuum, and partially stored in suspension, and the polymerization test is used by the cd.
    The dried solid product is characterized by the following composition, wt.% Ti 3.9; Mg 16.55; benzoic acid ethyl ester 8.6, VOH 2.2, C 59.3, heptane 9.45,
    Benzoic acid ethyl ester 8.6% and 2.2% VOH are determined by xp (matrographic analysis.
    B. Polym p1G1; 2n, and propylene in a solvent.


    233790. 2
    In a stainless steel autoclave, a 2.5-liter tank, equipped with a magnetic stirrer, is introduced into 870 cm of n-hexane, previously saturated with nitrogen, and kept in a weak one; propylene stream. Separately, 130 cm of heptane, 2 g of triisobutyl aluminum and 0.253 g of p-toluic acid meth / dl ester were withdrawn into the flask. After
    After stirring for 5 minutes, take 0.7 cm of the catalyst slurry and add to the solution in the flask. After another 5 minutes the complex compound thus obtained
    5 catalyst is introduced into the propylene stream in an autoclave adjusted to 45 ° C. The autoclave is closed and 275 cm Hg is introduced into it.
    The pressure is then adjusted to 7 atm.
    20 and the temperature is up to 60 ° C. The polymerization is carried out for 4 hours at constant pressure and temperature. At the end of the polymerization, the polymer suspension; 1 centrifuged at room temperature
    25 temperature. As a result of centrifugation, a polymer is obtained in powder, after which it is dried in an oven in a nitrogen atmosphere at 70 C.
    Atactic polymer get in
    JQ by evaporation of the centrifuged solution and dispensing. The analysis of the polymer (polymer in powder + + atactic polymer) makes it possible to obtain the following data on catalyst residues, on the basis of which it became possible to calculate the product yields, ppm: Ti 4.5; Mg 22; Cr 95.
    The overall indicator of stereoregula, calculated on the basis of 35
    40
    mules
    P
     N powder x g powder
    i g powder + g atactic polymer
    It turned out to be equal to 94%.
    P block is an indicator of centrifuged and dried polymer, and is determined by extraction with boiling heptane for 3 hours.
    Other properties of the polymer in the powder are: Apparent with density, g / cm 0.36 Flow index
    melt, g / min 3.8 / 10 Flexural stiffness, kg / cm 14,800
    Example s 2-5. With reference to Example 1, another type of alcohol is used. The results are presented in Table. one .
    PRI me R s 6-1 1. Compared to example 1, the working operations related to the preparation of the adduct from FgCZ (p-butyl alcohol) ethyl are changed: - Fira benzoic acid.
    The results are presented in Table. 2
    PRI me R s 12-18. Compared to Example 1, the ratios of MICP2 (alcohol) ethyl benzoate are modified. The results are presented in table. 3
    Example 19. In this experiment, an adduct is prepared only from MffCf2 and VLI at a molar ratio of 1: 2 in accordance with the variants described in Example 1, however, it does not add benzoic acid ethyl ester. Benzoate at a molar ratio of benzoate / alcohol 0.2 is added during the treatment with TiCT, after which the reaction is continued as in Example 1. The following results are obtained, in wt%: Ti 3.25; Mg 17.10, CE 61.80; EB 6.9; VTSON 2.2, heptane 8.85.
    Polymerization Evaluation.
    The catalyst residues in the polymer are as follows, ppm: Ti 5.5; Mg 20, CE 86.
    The overall indicator of stereo-con trol (P) is 92.0. The stereo-regularity index defined by a powder (P powder) is 94.5%.
    Melt flow index of powder 3.3 g / 10 min. Apparently with a density of 0.45 g / cm. Bending stiffness 13250 kg / cm.
    Example 20. 4.5 g of MgC (47.5 mmol) is suspended in 73 ml of n-heptane containing 1.1 ml (7.3 mmol) of benzoic acid ethyl ester at 25 ° C, after which the suspension is left to react for 2 hours, 100 ml of a solution of phenol in heptane (8.9 g) are added to this suspension over 10 minutes and the whole mixture is left to react at 80 ° C for 2 hours.
    Heptane is removed at 50 ° C under a vacuum. The resulting white solid is treated with 150 ml of TiCf at 110 ° C for 2 hours. After the termination of this time period, the TiC2 is removed by filtration and the same amount of this BeuiecTBa is added. ) then negligence reacts in
    33790, 4
    for 2 hours at which time it is washed with heptane at 90 ° C until the chlorine ions disappear from the filtrate. This component of the catalyst is. Barely evaporating in vacuum is characterized by the following composition, wt.%: Ti 2.21; Mg 17.20; Ct 62.97; EB 7.2; phenol 1.5; heptane 9.92,
    Such a compound is used as a catalyst component in evaluating the polymerization of propylene, which is produced under the following conditions.
    5 mmol of a mixture of aluminum trialkyls, 5 having the following gas composition after hydrolysis,%: ethane 9; izobutan 49, 4; p -butan 41.2; propane O, 16; isobutene .0.24, reacting at room temperature with 1.25 mmol of methyl-2Q o-p-toluic acid ester in 80 ml of p-heptane (anhydrous and free of sulfur) for 5 minutes,
    50 ml of this solution are combined with 100 mg of the catalyst component, 25 remaining 30 ml are diluted to 1000 ml with p-heptane and injected under pressure in a nitrogen atmosphere into a 3000 ml steel autoclave equipped with a magnetic core stirrer and thermoelectric meter temperature of 40 ° C at which propylene acquires a flowability.
    A suspension of the catalyst component is then introduced into the autoclave. After the autoclave is closed, hydrogen is added to the latter to a partial pressure of 0 atm, then heated to 60 ° C while simultaneously being fed. than propylene, brought to a total pressure of 5 atm. This pressure remains constant throughout the entire polymerization as a result of continued monomer feed.
    After 4 hours, the polymerization is stopped and the polypropylene is isolated by treatment with methanol with acetone. 375 g of polypropylene are obtained, corresponding to a yield of 170,000 g of polymer / g of Ti, with a heptane residue of 92%, H; I, 90 DL / g,
    5 Example 21, The procedure is similar to Example 20, however 95 mmol of 4-tri-butylphenol is used.
    Analysis of the product obtained after reaction with and drying 55 in vacuo gives, in May,%: Ti, 2.49; Mg 20.07; benzoic acid ethyl ester, 9,4-tributylphenol 2.0; Cf 60.2; t eptan 6,24.
    40
    Evaluation of the polymerization, performed analogously to example 20, shows the following results: g polymer / g Ti 230,000, heptane residue 92.5%; 2; I, 54 dl / g.
    PRI me R 22. The procedure is similar to example 20, however, use 95 mmol of paracresol.
    Analysis of the product obtained after reaction with TiCl and drying in vacuo gives, in wt%: p-cresol, 1.9; C- 60.0; Mg 19.1 EB 7, Ti 2,3, - heptane 9.7.
    An evaluation of the polymerization performed under the conditions specified in Example 20 shows the following results: g polymer / g Ti 220,000, heptane residue 92; 1.85 dl / g.
    Example 23. The procedure is similar to example 20, however, use 95 mmol of beta-naphthol.
    Analysis of the product obtained after reaction with T1S4 and drying in vacuo, allows to obtain, in wt.%: Beta-naphthol, 8; CE 61.0 Mg 1 9., 8; EB 7.1 j Ti 2.4, heptane 7.9.
    The evaluation of the polymerization performed under conditions similar to example 20 yields the following results: g polymer / g Ti 230,000 heptane residue 91.6%, H; 2.00 dl / g
    Example 24. 17.41 g of MgC3, 3.3 (51 mmol), obtained in microspheroidal form (particle diameter 50 microns) by cooling from a melt2 MgCEj-C, H, C) H 0.2EV 7.8 4.2 17.1 59 , 5 2.0 9 ,.
    MgCB 2-mesoamyl alcohol .0.2 EB
     2-proplnol
     0.2 KB
    3.0 3.4517.4 60.15 1.8 5.7 j h, 5 27
    WITH
    8.6 3.4517.5 59.95 2.3 8.2 .., 5 20 2C n ;; 011 0.2 EB 7.0 1.0523.4567.2 1.0 0.3 d 93
    4N-C4H jOH using a NIRO ATOMIZER nebulizer, suspended in 200 ml of n-heptane, where 2, 9 ml (25.6 mmol) of benzene chloride and 100 ml are added dropwise at the same time. . After 30 minutes at the end of the addition, 200 ml are added dropwise to the ego;
    which the temperature gradually rises to. The mixture is reacted for 1 hour, then the solid component is separated by filtration and further processed with another portion of Ticr (200 ml). After a 2-hour reaction at 110 ° C, TiCJ is removed by filtration and the solid is washed with m-heptane at 90 ° C until the ion filtrate disappears.
    chlorine. As a result of the analysis, it was established that the catalyst component is characterized by the following composition,%: Mg 27.26; Ti 2.01; CF 55.5; EB 8j BuGH 2,2 heptane 5.03
    An evaluation of the polymerization of propylene, performed analogously to example 20, shows the presence of a polymer with a yield of 208,000 g of polymer / g of Ti; heptane residue 93%, p. 2.12 dl / g. 80% of the polymer particles are in the range of 105-710 microns. Particles with a .105 micron size are missing.
    In tab. 4 shows the content of ED and Ti, extracted by treating the solid catalytic component TiCf at 80 ° C for 2 h.
    Table 1
    21
    96
    0.43
    92.5 95 4.6 0.38
    93.5 95 4.5 0.36 80.5 92.5
    E; m to m
    SES
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    askew s
    rt ttСЧcdШ q)
    naat k
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    V
    S
    I u to "as
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    SES
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    Table 4
    Editor L.Gratillo
    Compiled by V.Teplkova
    Tehred I.Popovich Proofreader E.Sirohman
    Order 27fie / 59 Circulation 527Subscription
    VNIIPI USSR State Committee
    for inventions and discoveries I13035, Moscow, Zh-35, Raushsk nab., d, 4/5
    Production and printing company, Uzhgorod, st. Project, 4
    Continued. Tab.4
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING A CATALYTIC COMPONENT FOR POLYMERIZING PROPYLENE, including the interaction of magnesium dichloride, an electron-donor compound and excess titanium tetrachloride, which is a reaction medium, at 100-110 ° С, washing with a hydrocarbon solvent, characterized in that, in order to obtain a component with increased activity, titanium tetrachloride is reacted with an electron-donor compound that does not contain active hydrogen atoms and is selected from aromatic alkyl esters and the adduct d magnesium iodide with an electron-donor compound containing active hydrogen atoms' and selected from aliphatic alcohols, phenol and orthosubstituted phenol, while the electron-donor compound containing active hydrogen atoms is present in the adduct in an amount of 0.5-6 mol per mole of dichloride magnesium, and the electron-donor compound that does not contain active hydrogen atoms is used in an amount of 0.066-0.4 mol per mol of the electron-donor compound contained in the adduct, or titanium tetrachloride is reacted ana with an adduct of magnesium dichloride with the indicated electron-donor compounds not containing active hydrogen atoms and containing active hydrogen atoms, the compound not containing active hydrogen atoms is present in an amount of 0.066-0.4 mol per mole of electron-donor compound containing active hydrogen atoms, the amount of electron-donor compound not containing active hydrogen atoms remaining in the component after extraction with titanium tetrachloride at 80 ° C for 2 hours is 0.49-2.12 mol per 1 g of tita and in the absence of titanium compounds capable of extracting titanium tetrachloride at 80 C.
    SU m , 1233790 AZ "12
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    同族专利:
    公开号 | 公开日
    NL188041B|1991-10-16|
    ES471372A1|1979-10-01|
    NL7807259A|1979-01-08|
    SE7807331L|1979-01-05|
    BR7804265A|1979-03-20|
    SE440226B|1985-07-22|
    PL208159A1|1979-04-09|
    ZA783796B|1979-07-25|
    NO155775C|1987-05-27|
    GB2000514A|1979-01-10|
    RO77020A|1982-04-12|
    TR20939A|1983-01-21|
    JPS5439484A|1979-03-26|
    US4294721A|1981-10-13|
    AU3766378A|1980-01-03|
    DK290378A|1979-01-05|
    FR2396768B1|1981-04-30|
    IN150539B|1982-11-13|
    AU522016B2|1982-05-13|
    DE2828887C2|1990-04-05|
    NO155775B|1987-02-16|
    DK160255B|1991-02-18|
    DE2828887A1|1979-01-25|
    IT1114822B|1986-01-27|
    AR218315A1|1980-05-30|
    ATA484678A|1981-01-15|
    DK160255C|1991-07-22|
    JPS6411650B2|1989-02-27|
    FR2396768A1|1979-02-02|
    YU156178A|1982-10-31|
    PL113953B1|1981-01-31|
    GB2000514B|1982-01-20|
    AT363681B|1981-08-25|
    GR71672B|1983-06-21|
    PH14962A|1982-02-05|
    NL188041C|1992-03-16|
    NO782229L|1979-01-05|
    HU179253B|1982-09-28|
    US4439540A|1984-03-27|
    BE868682A|1979-01-03|
    CA1124257A|1982-05-25|
    MX150092A|1984-03-15|
    YU41592B|1987-10-31|
    PT68238A|1978-07-01|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT25345/77A|IT1114822B|1977-07-04|1977-07-04|COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS|
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