• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    There are disclosed new starting components for use in preparing catalysts for the polymerization and copolymerization of olefins. The new starting components are compounds having the general formulae R2AlOR'' and/or RAl (OR'')2, in which R represents alkyl radicals containing 1 to 12 carbon atoms and R'' has one of the following structures: <IMAGE>
    公开号:SU751312A3
    申请号:SU762378456
    申请日:1976-07-06
    公开日:1980-07-23
    发明作者:Джаннини Умберто；Альбиццати Энрико；Пароди Сандро
    申请人:Монтэдисон С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    neither diethyl-2, b-di-tert-butyl cresoxyaluminium or diisobutyl-2, b-di-tert-butyl creoxy alumina, or diethyl-2, b-di-tert-butylphenoxy aluminum and the ratio of components.
    The advantage of the proposed method of producing a catalyst is its reduced flammability, since the organo-aluminum compounds used are solid and have a low vapor pressure. Another advantage is the stabilizing effect on the polymer of the substituted phenol, which is formed during the decomposition of the organo-aluminum compound.
    Example. 14 ml of solution A1 (C2H5) e (100 mmol) is dissolved in 25 ml of anhydrous and deaerated heptane. A solution of 22 g (100 mmol) of 2, b-di-tert-butyl-p-cresol DBC is added dropwise over 2 hours to the resulting solution.
    The solution is then heated to and at this temperature, the reaction is carried out until a 1M solution of diethyl-2, b-di-tert-butyl cresoxyaluminium is formed.
    The md-T i-j JOMnoHeHT catalyst is obtained by dry grinding in a steel ball mill a compound of the formula CF TiooOHN and anhydrous magnesium chloride (mdSR) in a weight ratio of 26: 100. An X-ray analysis should produce a spectrum with a peak intensity at the lattice distance of 2.43-3.20 A.
    22.6 mg of this component is injected, together with 8 ml of this solution containing an aluminum compound, and 1000 ml of anhydrous and desorbed n-heptane into a 3 l stainless steel polymerization autoclave equipped with an anchor stirrer and heated to 85 ° C.
    Hydrogen is then fed at a pressure of 7 atm and ethylene at a pressure of 6 atm until the total pressure in the autoclave reaches 13 atm. This pressure is kept constant during the polymerization process using a continuous supply of ethylene.
    The polymerization process is stopped after 4 hours, the polymer obtained is separated by filtration and dried. 230 g of polyethylene (194000 g of polymer / g of titanium) are obtained, having a characteristic viscosity of 1.6 dl / g.
    The experiment was repeated using 18 mg of catalyst and 8 mmol of a solution of the compound of formula (CjH) 2-AOC in n-heptane as a cocatalyst. In this case, polyethylene is produced in small quantities. This experience shows that catalytic components of the type, where
    R is a phenyl radical, which does not contain at positions 2 and / or 6 substituents, which create steric hindrances higher than CjHj, are practically inactive. 5 Example2. The experience of Example 1 was reversed, but 24 mg of the MD-Ti component using dry grinding in a steel ball mill of the compound of the formula and anhydrous magnesium chloride in a weight ratio of 19: 100 (Mg: Ti 11 molar ratio) was used. In this case, 390 g of polyethylene (420000 g of polymer / g of Ti-tane) are obtained, having a characteristic
     viscosity equal to 1.55 dl / g.
    Example 3. The experiment of example 2 is repeated, but 9.4 mg of Mg: Ti component and a gas mixture, which consists of ethylene under pressure, are used.
    and 9 at and hydrogen at 4.
    This gives 280 g of polyethylene (760000 g of polymer / g of titanium) having a characteristic viscosity of 2.55 dl / g. For comparison, the experiment was carried out using an organo-aluminum compound of the formula () 2L1OR, where OR is a 2,6-dimethylphenoxy group.
    To this end, 1.22 g of 2,6-dimethyl phenol (10 mmol) dissolved in 20 ml of n-heptane are mixed with 1.4 ml of A1 () 3 (10 mmol) and reacted at 80 ° C.
    The polymerization experiment described above is repeated using 20 ml of the Mg-Ti component and a solution of the compound of formula RgAlOR indicated above. Only 2 g of polyethylene is obtained.
    0 in another comparative test, an organo-aluminum compound is used. diethyl 2-tert-butylphenoxy aluminum.
    To this end, 1.53 ml (10 mmol)
    5 2-tert-butylphenol, dissolved in 20 ml of n-heptane, is added dropwise to 1.4 ml of the compound of the formula A1 (C2H5) 3 (10 mmol). The mixture is then heated to and maintained.
    0 temperature until the end of the reaction. Then the experiment with polymerization is repeated using 16 mg of the Mg-Ti-KOM component and the solution of the organo-aluminum compound indicated above. With
    With this it turns out. Only 3.5 g poly.ethylene.
    These two comparative experiments indicate that when titanium compounds are introduced in position 3 and / or b
    60 of the formula R AIOR of the radical R, a substituent that creates steric hindrances equal to or less than the steric hindrance from the CgH group, the resulting catalyst is
    65 almost inactive.
    Example 4. 99.4 mg of Mg-Ti component obtained by dry grinding of TiC 1 ethyl benzoate and anhydrous magnesium chloride (MgClj) in a weight ratio of 55: 100 (Mg / Ti 6.5 molar ratio) and detected by X-ray analysis spectral properties similar to those of the Mg-Ti component of Example 1 are introduced together with b ml of a solution of the compound of the formula (C2H5) 2A1 (DBC) (Mg / Ti 58 molar ratio) obtained in accordance with Example 1 and 350 MP of sweet anhydrous n-heptane to a polymerization autoclave made of stainless steel Commercially capacity of 1000 ml, equipped with anchor stirrer, and heated up, and before it is fed into the autoclave under pressure of 0.15 atm / in portly. Following this, propylene is fed into the autoclave until the total pressure is 5 atm, which is then maintained during the polymerization process by the continuous supply of propylene. After 2.5 hours, the reaction is stopped. The polypropylene thus obtained is separated by treatment methanol and acetone. Its amount is 435 g (88000 g polymer / g titanium). The polymer has an intrinsic viscosity of 1.67 dl / g. The residue that is extracted using boiling heptane is 54.5%.
    Example5. B ml of a solution of the compound of formula (C2H5) 2A1 (DBC) prepared in accordance with Example 1, brought to 50 ml with n-heptane, is reacted with 162 mg of ethyl p-anisate for 10 minutes at 25 ° C. In this case, 97 mg of the Mg-Ti component, of the same type as in Example 4, and the solution of the compound of the formula () M (DBC) are used. After 5 hours of polymerization under the same conditions of polymerization as in Example 4, 100 g of polypropylene (22000 g of polymer / g of titanium) are obtained, having a characteristic viscosity of 2.13 dl / g, and the residue, which is extracted with heptane and is 89.6%.
    PRI me R b. A solution of 11 g (50 mmol) of 2, b-di-tert-butyl-p-cresol and 60 ml of anhydrous deaerated pentane is added dropwise in 126 ml (50 mmol) of the compound of formula A 1 (iso-C Hd) for 2 hours. Thus, a 0.8 m solution of the compound of the formula (tleo-C H,)) A (DBC) is obtained. The experiment of Example 4 is then repeated. 47.4 mg of the Mg-Ti component and 7 ml of a solution of the compound of the formula (iso-C4Hd) 2A1 are used. polymer / g titanium) having an intrinsic viscosity of 1.11 dl / g and a residue that is extracted with heptane and 70.5%.
    PRI me R 7.
    A stainless steel autoclave having a capacity of 3000 MP and equipped with an anchor stirrer is filled with 50 g of completely dry polypropylene in powder form along with 5 mg of Mg-Ti component obtained by dry grinding TICI and anhydrous magnesium chloride (MgCl 2) in a weight ratio of 19: 100 and together with 8 mmol of a solution of the compound {СН), (DBC) (molar ratio Al / Ti 200) prepared in accordance with Example 1 and diluted to 50 ml with heptane. After evaporation of the solvent while in the autoclave under a pressure of 0.5 atm, hydrogen and ethylene are fed until the total pressure in the autoclave reaches 15 atm. This pressure is kept constant during the polymerization by the continuous supply of ethylene. The polymerization is stopped after 2 hours. In this way 100 g of polyethylene (500000 g of polymer / g of titanium) are obtained.
    Example 8.1,39 ml of the compound AHCjH) (10 mmol) is dissolved in 22 ml of anhydrous deaerated n-heptane. A solution of 1.78 g - (10 mmol) of 2-tert-butyl-4, 6-dimethylphenol in 27 ml of n-heptane is added to the mixture over 1 hour. The mixture is then heated to this temperature and maintained until the end of the reaction.
    The experiment from Example 3 is then repeated. In this case, 20 mg of the Mg-Ti component are used. The result is 98 g of polyethylene (125,000 g of titanium polymer).
    EXAMPLE 9 2 g (10 mmol) of 2,6-di-tert-butylphenol dissolved in 50 ml of n-heptane is added dropwise to a solution of 1.4 ml of the compound of formula A1 () ( 10 mmol) in 20 ml of anhydrous and de-aerated n-heptane.
    The mixture is heated to a temperature of 80 ° C and this temperature is maintained until the end of the reaction. The experiment of example 3 is then repeated. In this case, 21 mg of the Mg-Ti component are used. B-result gives 240 g of polyethylene (288000 g of polymer / g of titanium
    EXAMPLE 10 20 mmol of 2,6-di-tert-butyl-p-cresol, dissolved In 20 ml of anhydrous deaerated n-heptane, are added dropwise to 20 ml of the solution prepared in accordance with Example 1, containing (C2H) 2 A1 (DBK).
    The solution obtained is mixed with 10 ml of n-heptane and heated to 90 ° C. This temperature is maintained until the end of the reaction. A compound of the formula (): A1 (DBK) is obtained. The experiment of Example 3 is repeated, using 19 mg of the MD-Ti component and 80 ml of solution. The result is 60 grams of polyethylene (81,000 grams of polymer / grams of titanium).
    权利要求:
    Claims (1)
    [1]
    1. USSR patent in application number 1956352 / 23-04, cl. B 01 J 37/00 C 08 F k / 6k, 1972.
    Patent of the USSR №414770,
    2
    01 J 31/12; B01 J 31/38,
    cl. E 1974.
    Patent of the USSR №315329,
    3
    Cl, B 01 J 37/00; B01. J 27/06, 19.73 (ethrotype).
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    同族专利:
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    NO762347L|1977-01-11|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT25217/75A|IT1039828B|1975-07-09|1975-07-09|COMPONENTS OF PEARL CATALYSTS POLYMERIZATION OF OLEFINS AND CATALYSTS OBTAINED FROM THEM|
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