• 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:
    Catalytic solids based on complexed titanium trichloride, which can be employed for the stereospecific polymerisation of alpha-olefins preactivated by being brought into contact with an organoaluminium preactivator comprising the product of reaction of a compound (a) chosen from organoaluminium compounds and of a compound (b) chosen from hydroxyaromatic compounds in which the hydroxyl group is sterically blocked. These solids enable propylene to be polymerised with an improved stereospecificity.
    公开号:SU1674687A3
    申请号:SU874203442
    申请日:1987-09-25
    公开日:1991-08-30
    发明作者:Фьясс Поль；Бернард Альбер
    申请人:Солвей Э Ко (Фирма)；
    IPC主号:
    专利说明:

    for a certain amount of titanium trichloride in a solid substrate, and also due to the fact that the preactivator and the substrate meet certain formulas, and the substrate has certain physical characteristics.
    The goal is also achieved by contacting a solid substrate with a pre-activator by introducing it into the suspension of the substrate under certain conditions,
    The goal of the method of stereospecific propylene polymerization is to increase the yield of the isohactic crystalline polymer by using a catalytic system containing as a preactivator the reaction product of an organoaluminum compound of a certain formula and a compound selected from a certain group of hydroxyaromatic compounds, under a certain molar ratio, under certain conditions carrying out the method of polymerization.
    Example 1 .A. Getting predecessor.
    A 800 ml reactor equipped with a two-blade stirrer rotating at a speed of 400 rev / mmn, in a nitrogen atmosphere, is injected 90 ml of dry hexane 60 TICU in pure form. This solution of hexane - T1ST cooled to 0 ± 1 ° C. After 4 h, a solution of 190 ml of hexane and 70 mp of diethylaluminium chloride (DEAC) is added to it, keeping the temperature in the reactor at 0 ± 1 ° C.
    After adding the DEAC-hexane solution, the reaction medium formed by the suspension of fine particles is kept under stirring at 1 ± 1 ° C for 15 minutes. then brought to 25 ° C in 1 hour and kept at this temperature for 1 hour and then brought to 65 ° C in 1 hour. The medium is kept under stirring for 2 hours at 65 ° C.
    In this case, the liquid phase is separated from the solid product, and the solid product is washed 7 times with 200 ml of hexane E in dry form with agitation of the solid product with each washing.
    The reduced solid thus obtained is shaken in 456 ml of solvent (hexane) and 86 ml of di-eoamyl ether (EDIA) are added. The suspension is stirred for 1 h at 50 ° C. The solid thus treated is then separated from the liquid phase.
    The resulting product was shaken in 210 ml of hexane and 52 ml of TICU was added; the suspension is maintained under stirring (150 rpm) at 70 ° C for 2 hours. Then
    the liquid phase is removed by filtration, and the solid product based on the complex titanium trichloride is washed 14 times with 270 ml of hexane. The obtained solid can be represented by the following empirical formula:
    (C2H5), 02 EDIAo.07
    A solid predecessor is in
    the shape of spherical particles with an average diameter of 24 microns. The specific surface of the solid substrate is 195 m / g and the total total porosity is 0.27 cm / g. B. Pre-activation.
    A 800 ml reactor equipped with a paddle stirrer rotating at 150 rpm is injected with 70 g of a solid precursor based on titanium trichloride complex (containing
    about 820 g UHZ / kg in suspension with 280 ml of hexane. Slowly inject (120 minutes) into this solution 120 ml of a solution in hexane of a pre-activator (below called pre-activator A), which was previously prepared by mixing 1 liter of hexane. 30 g of DEAC (compound a) and 176.2 g of 3- (3-5-di-tert.-butyl-4-hydroxyphenyl) propinate p-octadecyl (compound b). The molar ratio between compounds a and b is
    used to produce the preactivator is therefore 2, and the molar ratio between the preactivator A and the solid precursor based on the complex titanium trichloride
    (expressed in moles of the originally used compound a per mole in the solid product) is 0.2. The resulting preactivator can be represented by the following empirical formula:
    (C2H5) i, 5 AltOROo.os Cl
    where OR is the radical of n-octadecyl-3- (3, b-di-tert.-butyl-4-hydroxyphenyl) propionate.
    The preactivator solution is introduced into the reactor only 15 minutes after the end of the evolution of gas observed during the mixing of compounds a and b. The suspension with the preactivator A added in this way is kept for 1 hour at 30 ° C with stirring.
    After decanting, the resulting pre-activated catalytic
    the solid product is washed 5 times with 100 ml of dry hexane and the solid product is suspended in suspension with each washing, then dried by flushing with nitrogen in a fluidized bed for 2 hours at 70 ° C,
    The pre-activated catalytic solid product thus obtained contains per 1 kg of 641 g, 12 g of aluminum, 31 g of EDIA and about 250 g of pre-activator A.
    C. Polymerization of propylene in suspension in a liquid monomer in the presence of a pre-activated catalytic solid.
    Into an autoclave with a capacity of 5 liters, pre-dried and kept in a dry nitrogen atmosphere, injected with nitrogen purge: 400 mg DEAC (as a solution in hexane 200 g / l), the CI / AI atomic ratio was adjusted to 1.02 by adding dichloride ethylaluminum; 100 mg of a pre-activated catalytic solid (the molar ratio between DEAC and that present in the solid product is about 8); Hydrogen at a partial pressure of 1 bar: 3 liters of liquid propylene.
    The reactor is kept under stirring at 65 ° C for 3 hours. Excess propylene is then degassed and the resulting polypropylene (PP) is collected, i.e. 643 g of dry polypropylene.
    The activity of the pre-activated catalytic solid is 3,340; throughput is increased to 6430 g of polypropylene / g of pre-activated catalytic solid.
    Polypropylene has the following characteristics: 1.1 98.1%; G 678 daN / cm2; MFI 3.16 g / 10 min; PSA 510 g / l.
    Examples 1R-5R are provided as a comparison.
    PRI me R 1R. A solid product based on titanium trichloride complex is obtained, as described in Example 1A, without prior activation, as indicated in Example 1 C.
    The solid product, dried as indicated in example 1. Contains 811 g. 2.8 g of aluminum and 61 g of EDIA.
    The polymerization is carried out in the presence of the thus-obtained non-preactivated solid product under conditions strictly comparable to the conditions defined in Example 1C. At the end of this test, 785 g of dry PP is obtained.
    Therefore, the activity of a is 3230, and the productivity is increased to 7850 g PP / g solid.
    This polypropylene has the following
    characteristics: 1.1. 94.99%; G — 572 daN / cm, MFI 7.3 g / 10 min; PSA - 490 g / l. The differences between the fractions insoluble in boiling heptane and the corresponding moduli G of polymers obtained under comparable conditions of examples 1 and 1R indicate the superior stereospecificity of the catalytic system containing the preactivated catalytic solid product of example 1.
    Example 2R. The solid product based on titanium trichloride complex prepared in Example 1A is preactivated with a solution containing only compound b. Partial dissolution of the solid product is noted, which, moreover, is represented as very fine grains. The polymerization carried out in Example 1C is reproduced with that amount of catalyst that contains
    about 70 mg.
    535 g of PP are obtained, which corresponds to activity of only 2550. This PP is presented in the form of small grains, and its PSA is only 100 g / l, which excludes
    the possibility of its use.
    Example 3R. Reproduce Example 1A and B, with the only exception that a solution in hexane of compound a is sequentially added to a suspension of a solid product based on complex titanium trichloride, and 15 minutes after the completion of the addition of a solution of compound a, a solution in hexane of compound b. The values of the molar ratios between compounds a and b with the separately added additives and between compound a and the amount of TiCb present in the solid product, respectively, are 2 and 0.2. The resulting catalytic product contains 757 g / kg TICI3.
    The polymerization carried out according to Example 1C makes it possible to obtain with the activity of a 3090 only polypropylene, represented as non-polypropylene.
    processing blocks.
    Example 4R. Reproduce Example 3R, but in reverse order of introducing solutions of compounds a and b. See the same phenomenon as in example 2R, i.e. partial dissolution of the solid.
    The polymerization carried out in Example 1C allows, with activity 3450, to obtain only polypropylene, represented in the form of very fine grains, PSA
    which is only 200 g / l, which excludes the possibility of its use.
    Example 5R. The solid product based on titanium trichloride complex prepared in Example 1R (i.e., without prior activation) is used in the polymerization carried out in Example 1 C, except that the solid product hydrogen and propylene are introduced into the polymerization medium besides DEAC. 3- (3 /, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-octadecyl in such an amount that the molar ratio between this product and that present in the solid is about 0.2.
    Prepared with a3286 PP activity, which has the following properties: 1.1 95.2%; G - 575 daN / cm2; MF 5.2 g / 10 min; Р5А-505г / л.
    Example 2. A preactivated, catalytic solid product from Example 1A and B is prepared, not replacing the derivative with 2, b-di-tert-butyl-4-methylphenol. The resulting preactivator (part B) can be represented by the following empirical formula:
    I C2H5 11.5 A1 (OUo.5 -CI
    where OR is a 2,6-di-tert-butyl-4-methyloxyphenyl radical.
    The pre-activated catalytic product obtained in this way contains H, J kg G32 g PS1z, 4 g aluminum, 30 g EDIA and about 170 g pre-activator. Used to carry out the polymerization under the conditions of Example 1C.
    Polymerization allows the production of polypropylene with an activity of 3230, having the following characteristics: 1.1 95.9%: G 636 daN / cm; MFI - 9 g / 10 min: PSA - 500 g / l.
    Example 3. A preactivated catalytic solid obtained in Example 1 A and B was used in the polymerization of propylene in suspension in hexane under the following conditions.
    8, a stainless steel autoclave with a capacity of 5 liters, purified several times with nitrogen, was introduced with 1 liter of purified dry hexane. Then 400 mg of DEAC are successively introduced in the form of a solution in hexane at 200 g / l and the amount of catalytic solid product equivalent to about 51 mg of T1Cl3. In this case, the molar ratio of OEAC / PLC is about 10.
    The autoclave is heated to 65 ° C and adjusted to atmospheric pressure by slow degassing. Then, an absolute hydrogen pressure of 0.3 bar is created in it, then propylene is introduced into the autoclave until a total temperature is reached at a given temperature.
    pressure 11.9 bar. This pressure is kept constant during the polymerization by the introduction of propylene gas. After 3 hours, the polymerization is stopped by degassing propylene.
    The contents of the autoclave were poured onto a Buchner filter, washed three times with 0.5 L of hexane, and dried under reduced pressure at 60 ° C. Collect 251 g of PP,
    insoluble in hexane. In polymerization and washing hexane, there is 0.75 g of soluble polymer, which corresponds to 0.3%. The activity of a is 1643. The productivity rises to 3157 g.
    PP / g pre-activated catalytic solid.
    Insoluble in hexane PP has the following properties: 1.1 98.2%: G 654 daN / cm2; MFI 2.9 g / 10 min; PSA 503 g / l.
    Example 6R. Cited as
    g.
    In the presence of a catalytic solid, obtained as indicated in example 3, but excluding the preliminary activation step, with the catalytic product containing 735 g / kg TlCn, with polymerization south polymerization under the same conditions as in Example 3.
    Receive with activity and 1719 software, 1%
    which is soluble in polymerization h flushing hexane, and the insoluble part has the following characteristics: 1.1 35.7%, G 591 daN / cm2; MFI 9.5 g / 10 min; PSA 479 g / l.
    EXAMPLE 4 A preactivated catalytic solid product is obtained according to the general conditions set forth in Example 1 A and B. However, after processing a suspension of a solid product,
    restored poi stirring for 2 h at 65 ° C. this suspension is cooled-south to about 55 ° C; in this case, propylene is introduced into the gaseous medium of the reactor under a pressure of 2 bar. This is an introduction
    lasts for a time sufficient (about 45 minutes) to produce 100 g of polymerized propylene per kg of solid. The suspension of the pre-humanized thus solid product is then cooled to 40 ° C and the preparation is continued as indicated in Example 1 A.
    The preliminarily activated catalytic
    the solid product contains 1 kg of 611 g, 9 g of aluminum, 14 g of EDIA and about 143 g of pre-activator A and the catalytic solid product used in the polymerization, including the first stage, carried out in a liquid monomer, and the second stage, carried out in the gas phase under x, described in detail below.
    In a 5 liter autoclave, used in Examples 1 and 3, 800 mg of DEAC are injected in a stream of nitrogen, an amount of catalytic solid equivalent to 100 mg of T) C 1c. In this case, the molar ratio DE AC / T1C 3 is about 10.
    In an autoclave, an absolute hydrogen pressure of about 0.2 bar is created. Then, 2 l of liquid propylene is introduced with stirring and the autoclave is heated to 60 ° C. Polymerization is carried out at this temperature for 30 minutes. Then the autoclave is degassed at a pressure of 15 bar with simultaneous heating to 70 ° C. An absolute hydrogen pressure of 1 bar is created in it, then propylene is introduced into the autoclave until a total pressure of 28 bar is reached at a given temperature. After 3 hours, the polymerization is stopped by degassing propylene and a formed PP is obtained, i.e. 1150 g of dry PP.
    Consequently, the activity of a pre-activated catalytic solid product is 3286. The productivity increases to / 027 g PP / g pre-activated catalytic solid. This PP has the following characteristics: 1.1 97.9%; G 698 daN / cm2; MFI 3 g / 10 min; P5A 520g / l.
    Example 7R. It is given as a comparison.
    A preactivated, catalytic solid product is obtained according to the indications of Example 4, but excluding the preactivation step. This solid product contains per kg 718 g, 3.8 g aluminum and 84 g EDIA. Used in the polymerization carried out according to the conditions set forth in Example 4, it makes it possible to obtain, with an activity of about 3168, PP, which has the following properties; 1.1 96.4%; G 620 daN / cm2; MFI 3 g / 10 min; PSA 516 g / l.
    Examples 5-7. Preactivated catalytic solids are obtained according to the conditions mentioned in Example 4, except that the molar ratio between compounds a and b used
    to obtain pre-activator A (see example 1 B) (examples 5 and 6), as well as a molar ratio between pre-activator A and a solid trichloride-based product
    titanium (expressed in moles x originally
    used compound a per mole T,
    available in a solid) (Example 7).
    Preactivator A, obtained according to
    Examples 5-7, can be represented by the following empirical formula:
    C2H5 11.5 Al (OR) o.5 CI
    where the radical is n-octadecyl-3- (3, 5-di-tert.-butyl-4-oxyphenyl) propionate.
    Preactivated catalytic solids are used in slurry polymerization of propylene
    in hexane according to the general conditions mentioned in Example 3.
    Specific operating conditions for the preparation of catalytic solids and polymerization results are given below in
    Table 1.
    Example 8. A preactivated catalytic solid product was prepared according to the instructions of Example 4 and used in the polymerization carried out according to the conditions set forth in Example 1, except that the reactor was held at 75 ° C under stirring for 2 hours. .
    Under these conditions, the preactivated catalytic solid product allows to obtain a PP with an activity of a 5010 PP. characterized by the following properties: 1.1 98.1%; G 688daN / CM2; MFI 5.9 g / 10 min; PSA 510
    g / l.
    Examples 9 and 10. Pre-activated catalytic solids are obtained according to the conditions mentioned in Example 1 A and B, except for
    what is used as compound a, respectively triethyl aluminum (TEAI) (example 9); ethyl aluminum dichloride (EADC) (Example 10).
    Pre-activated Kata
    Lytic solids are used in the polymerization of propylene in suspension in liquid monomer under the general conditions mentioned in Example 1 C.
    The properties and characteristics of the pre-activated catalytic solids used and the polymerization results are given below in Table 2.
    权利要求:
    Claims (9)
    [1]
    Claim 1. Catalytic product for stereo-specific polymerization of alpha-olefins, containing a solid support based on a complex of titanium trichloride and an organoaluminum preactivator deposited on it, characterized in that, in order to increase the activity of the catalytic product, it is - the driver contains the reaction product of an organoaluminum compound of the general formula
    RnAICb-n,
    where R-CaHs, i-C-jHg, SeGs;
    n 1-3,
    and compounds selected from the group of hydroxyaromatic compounds, the hydroxyl group of which is sterically blocked, including 2,6-di-tert-butyl-4-methylphenol, 3- {3, 5-di-tert-butyl-4-hydroxyphenyl ) p-octadecyl propionate, with a molar ratio in the preactivator of the aluminum-organic compound and the hydroxyaromatic compound, is 2-50: 1, with the amount of the preactivator being 230- j90 g / kg of titanium tricychloride in a solid substrate.
    [2]
    2. The product according to claim 1, wherein the pre-activator corresponds to the following empirical formula:
    Ro, 5-2,5A (OR) o.5 CI-o-2,
    where with R C2Hs:
    R is 2,6-di-tert-butyl-4-methylphenyl radical or 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate p-octadecyl radical; with R-I-C4He, CeHi3 R is a radical of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate p-octadecyl.
    [3]
    3.Product on PP. 1 and 2, I distinguish it by the fact that the preactivator is applied
    on a solid substrate corresponding to the following formula:
    TICl3tAI (C2H5), 02 (i-C5Hll) o, 07.
    [4]
    4.Product on PP. 1-3, about tl and h and y y and y with the fact that the solid substrate consists of spherical particles with an average diameter
    24 microns, its specific surface is 195 m / g and the total total porosity is 0.27 cm 3 / g.
    [5]
    5. Method for producing a catalytic product for stereospecific polymerization of alpha-olefins by contacting a solid support based on a complex of titanium trichloride with aluminum 5
    five
    0 5
    0
    five
    0
    five
    0
    five
    an organic preactivator, characterized in that, in order to obtain a catalytic product with increased activity, the reaction product of an organoaluminum compound of the general formula
    RnAICl3-n.
    where R is C2Hg l-GiHg, CeHi3.
    n-1-3.
    and compounds selected from the group of hydroxyaromatic compounds, the hydroxyl group of which is sterically blocked, including 2,6-di-tert-butyl-4 methylphenol and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-octadecyl, with a molar ratio in the preactivator of aluminum-organic compound and hydroxyeromatic compound, is 2–50: 1 w, while the amount of preactivator is 230–390 g / kg titanium trichloride, which is in a solid substrate
    [6]
    6. The method of p. 5, characterized in that the solid substrate is contacted with the preactivator by introducing the preactivator into the suspension of the substrate in an inert hydrocarbon solvent, holding in contact at 30 ° C for 1 hour, followed by isolation of a catalytic product and washing with an inert hydrocarbon solvent before using the polymerization of alpha-olefins.
    [7]
    7. A method for stereospecific propylene polymerization in the presence of a catalytic system, containing diethyl aluminum chloride and a catalytic product containing a solid substrate based on a complex of titanium trichloride previously activated by contacting with an organulyuminium predactivator, which is used in order to increase the yield of isotactic crystalline polymer catalytic system containing as a preactivator the reaction product of an organoaluminum compound formulas
    ,
    where R is C2Hs, i-C-jHg, CeHu,
    n 1-3,
    and compounds selected from the group of hydroxyaromatic compounds, the hydroxyl group of which is sterically blocked, including 2,6-di-tert-butyl-4-methyl-pheno /, .b-di-tert-butyl-oxyphenyl repeat n- octadecyl, with molar
    the ratio in the pre-activator of alumotmium-organismic and oxyaromatic chains is 2-50: 1, with the total number of “M1tvrv sest vt 230-39
    TttMMf m dylo d oklskydmeyt / a D iDCMfe- SChD Yayaurshffa FW "School of Civil Defense Jt 71 D
    doi nidagazhmv.
    [8]
    8. The filler according to claim 7, characterized in that the polymerization is carried out in Suvlei in an inert hydrocarbon solvent.
    [9]
    9. Speiov under item 7. different tep. that the polymerization is pregled in the liquid state or in the gas phase.
    Table 1
    table 2
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    同族专利:
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    申请号 | 申请日 | 专利标题
    FR8613649A|FR2604439B1|1986-09-26|1986-09-26|CATALYTIC SOLID FOR USE IN THE STEREOSPECIFIC POLYMERIZATION OF ALPHA-OLEFINS, PROCESS FOR PREPARING THE SAME, AND METHOD FOR POLYMERIZING ALPHA-OLEFINS IN ITS PRESENCE|
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