• 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:
    New highly active and highly stereospecific catalysts for the polymerization of alpha-olefins are disclosed, the starting components of which are (a) an organometallic-compound of Al free from halogen atoms bound directly to the Al atom; (b) an electron-donor compound (such as a Lewis base) in an amount such that 15% to 100% of the organometallic Al compound (a) is combined with the electron-donor compound; and (c) a solid component comprising, at least on the surface, the reaction product of a halogenated Mg compound with a tetravalent Ti compound and with an electron-donor compound, the molar ratio electron-donor compound/Ti being higher than 0.2, and the molar ratio halogen atoms/Ti being higher than 4. Processes for polymerizing the alpha-olefins and mixtures thereof with ethylene in contact with the new catalysts are also disclosed.
    公开号:SU858571A3
    申请号:SU762404899
    申请日:1976-09-27
    公开日:1981-08-23
    发明作者:Лючиани Лючиано；Камилло Барбе Пьер；Касива Нориа；Тоета Акинори
    申请人:Монтэдисон С.П.А. (Фирма)；Мицуи Петрокемикал Индастриз, Л.Т.Д. (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the production of plastics, in particular to the production of polypropylene. A method of producing polypropylene by polymerization of propylene in a mass or medium of a hydrocarbon solvent in the presence of a catalyst of the product of the interaction of trialkylaluminium with the product of joint grinding of a magnesium dihalide with an electron donor and a titanium halide is known. However, this method leads to the production of a product with a low yield in the case of carrying out the process in a hydrocarbon solvent, the use of hydrogen as a molecular weight regulator is impossible, since in its presence the stereoregularity of the final product is reduced. The closest to the proposed method is to obtain polypropylene by polymerization of propylene in a mass or medium of a hydrocarbon solvent in the presence of a catalyst consisting of an alkylene organic compound, an electron donor and a solid reaction product of anhydrous magnesium halide with titanium tetrachloride and an electron donor, and a solid product is used with a specific surface area of 3.0 to 50.7 m / g2. However, the known method allows to obtain the final product with an insufficiently high yield, and namely: with a polymer ization in n-heptane for 5 hours at a pressure of 6 atm is obtained 61000 g / g of titanium with a degree of polypropylene stereoregularity of 89%. The aim of the invention is to increase the yield of the final product. This method is achieved by polymerizing polypropylene in a mass or medium of a hydrocarbon solvent in the presence of a catalyst consisting of an organoaluminum compound, an electron donor, and an anhydrous magnesium halide reaction product with four titanium chloride and an electron donor. with a specific surface of 80,200 m2 / g. Examples 1-11. And comparative examples 1-2. A) Grinding. Anhydrous MgCI. (with a water content of less than 1 wt.%), ethyl benzoate (EB) and in some cases silicon is subjected to joint grinding in vibratory mills having a total volume of one and six liters and containing respectively 3 and 18 kg stainless steel balls with a diameter of 16 mm Grinding is carried out at a temperature of about 4 ° C inside the mill and with a grinding time of 100 hours. The products to be crushed are loaded into the mill, the subsequent grinding and unloading of the crushed product from the mill is carried out under a nitrogen atmosphere. In Example 10, the grinding process is carried out in a 1 liter rotary mill, comprising 120 stainless steel balls with a diameter of 15.8 mg / i and rotating at 50 rpm. In tab. 1, for various tests, data are shown regarding the type and amount of products to be ground, the grinding conditions and characteristics of the products obtained. c) Treatment with titanium tetrachloride. A portion (15-50 g) of the co-milled product is transferred under a nitrogen atmosphere to a 500 cm reactor in which it is in contact with an excess of TiC I,. The TiCl2 treatment is carried out at temperatures} ranging from 80 to within two hours, after which the excess amount of TiC C and the IvttJe solution in it are removed by means of filtration at the temperatures shown in Table 2. 1. Then carry out two or more washes with boiling hexane. The resulting solid product is dried under a nitrogen atmosphere, and part of it is subjected to chemical analysis to determine the percentage of titanium and chlorine. Data concerning the conditions of the process in various tests during the treatment with titanium tetrachloride, as well as the characteristics of the products thus obtained, are presented in Table. 1-5. c) Polymerization in a solvent. The process is carried out in a 2500 cm autoclave equipped with a stirrer and pre-purified nitrogen at a temperature. The polymerization proceeds at a temperature at a pressure of propylene (C) of 5.8 or 9 effective atmospheres (maintained; therefore, by adding propylene during the course of pyrization) for four or five hours. Non-aromatic and dehydrated (1000 cm5) n-heptane (n-C), hexane (C |) or heptane (c1 |) are used as hydrocarbon solvents. The process is carried out in the presence of hydrogen, which serves as the molecular weight of polymer . As a trialkyl aluminum, use А 1 (CjHj) (ТЭА) or)) (TIBA); p-ethylanisate (PEA) and ethyl p-toluylate EPT are used as electron donor compounds. The molar ratio of trialkylaluminum to the electron donor compound is from 2.74 to 3.14. The autoclave is filled in the following order in an atmosphere of propylene: a solvent (870 CN), a portion of an alkyl aluminum and an electron donor, pre-mixed for 10 minutes in 160 cm of the indicated solvent, and at the same time a component of the catalyst with a carrier in suspension in 80 cm E solvent containing the rest of the alkylamine and the donor. Hydrogen and propylene are then introduced into the autoclave until the polymerization pressure is reached and the temperature is raised to the desired value. At the end of the polymerization, the solvent was removed by steam distillation, and the polymer thus obtained was dried under nitrogen at 70 ° C. d) Polymerization in liquid monomer. The process is carried out in autoclaves with a capacity of 30 liters and 135 liters, equipped with a stirrer, at a pressure of 26.5 eff. atm, for 5 hours, in the presence of hydrogen (15 ml and 50 ml), serving as a molecular weight regulator. As trialkylaluminium, use A1 () in the amount of 12.5 g (test in an autoclave with a capacity of 30 liters) and A1 (C, HT) d in an amount of 36 g (test in an autoclave with a capacity of 135 liters), subjected in both cases to treatment of compounds electrons, such as p-ethylanisate or ethyl p-toluylate, in molar ratios ranging from 2.2 to 2.74, the autoclave is filled in the specified sequence in propylene atmosphere with alkyl aluminum, in the form of 12% - heptane solution, liquid propylene and a compound serving as an electron donor. The autoclave is heated to the polymerization temperature, and then the catalyst component and hydrogen are introduced into it. At the end of the polymerization process, residual propylene is evaporated and then the polymer is dried under nitrogen at a temperature. In both cases (polymerization in solvent and in liquid monomer), the dry polymer is weighed to calculate its yield relative to the titanium present in the catalyst, in addition, the polymer is extracted with boiling n-heptane, the percentage of polymer insoluble in boiling water is determined. -heptane. The apparent density and the true viscosity (not tetra tetra) of the obtained polymer are also determined. 1-10, data relating to different polymerization cycles and the characteristics of the polymers obtained are given. Example 12. Anhydrous MgCl (with a water content of less than 1 wt.%) Is subjected to co-grinding with compounds that are electrone donors listed in Table 1 under the conditions described in Example 4. The ground product is subjected to treatment with titanium tetrachloride under the conditions of Example 4. The product of the reaction thus obtained has the contents of C1 and Ti, indicated in Table 11. These catalyst components are used in the polymerization processes under the conditions indicated in Example 8, with the only difference that the effective pressure C is equal to 5.4 atm The data on polymer yield and stereoregularity are given in Table. 11. Example 13. 500 ml of kerosene are introduced into a flask equipped with a stirrer. To remove air and moisture, propylene is introduced at a rate of 30 l / h for one hour. At this room temperature, 2.5 mmol of triethylamine and 0.884 mmol of the electron donor compound listed in Table 2 are introduced into this flask. 12. After 5 minutes, the catalyst component prepared according to Example 7 is introduced, with the only difference being. that silicone oil having a viscosity of 20 mist is used at. The mixture is heated at. The propylene is polymerized for 1 hour at atmospheric pressure and is introduced into the autoclave at such a rate as to maintain a constant pressure during the polymerization. After that, propylene is displaced with nitrogen, and the reaction mixture is cooled at room temperature. The solid product is filtered off, washed twice with methanol, then dried at a temperature. The soluble polymer is recovered by evaporation of the kerosene layer in the filtrate. The data on the yield and total stereo regularity of the polymer are presented in table. 12. Example 14. 10 g of a catalyst component prepared according to Example .13, with a content of 2, 1 wt. titanium, suspended in 150 ml of kerosene. 2.2 mmol of diethyl aluminum chloride, diluted with kerosene, are added at room temperature, and then 2.2 mmol of ethyl benzate are added, the mixture is stirred for 1 hour. The solid product is filtered, washed with hexane and dried in vacuo. A 2 liter autoclave containing 750 ml of n-hexane and 3.75 mmol of AISHND-), premixed with 1.25 mmol of methyl p-toluylate, is injected in an amount of dried product that corresponds to 0.03 mmol / l of titanium. . The polymerization process is carried out for 4 hours at a propylene pressure of 8 atm and in the presence of 400 ml of hydrogen. After removing the solid by filtration and drying, 225.9 g of a powdery product are obtained, the stereo-regulatory index of which is equal to 94.2. 5.9 g of polymer soluble in n-hexane are recovered from the filtrate. Example 15. 10 g of MDS12, containing less than 1 wt.% Of water and suspended in kerosene (100 ml), is treated with 18.4 mg of ethyl alcohol for 2 hours. The MgCl complex compound with ethanol chemically reacts with 2 , 5 ml of 2,6-dimethylpheno while for 1 h 11.7 ml of ethyl benzoate at 8 CRC for 1 h and from 22.9 mg at 20 ° C for 2 h in the indicated order. The solid is separated by filtration, washed with n-hexane and dried in vacuo. 10 g of this product is treated with 100 ml of TiCl4 for 2 hours. The excess of T i C I is separated by filtration. The solid is re-washed with n-hexane and then dried under vacuum. An elementary analysis of this product showed the following results, wt%: Ti 3.60 C1 58.0 31 mg of this solid product is subjected to polymerization under the conditions used in Example 14. After removing the solvent by filtration and drying, 130 g of polymer are obtained. The exponent of this polymer is 95.4%. The amount of polymer soluble in hexane and extracted from the filtrate is 30 g. Example 16. Obtaining a catalyst. 1 kg of anhydrous MgCl2, 0.23 l of ethyl benzoate and 0.15 l of silicone oil-50 are placed in a 100-liter vibratory mill, which contains 350 kg of stainless steel balls 15 mm in diameter and in which these substances are mixed for 120 hours at 70C. The mixture thus obtained was 500 g suspended in 5 liters of TiCl, the suspension obtained was allowed to react for 2 hours. At the end of the reaction, the reaction mixture was filtered at the same temperature to separate out the solid components, which were then thoroughly washed with hexane until the detection of free TlCl2 was stopped. The resulting solid component contains 2.0, 23.0 and 64.0% by weight of T1, Md and C1 in terms of atoms and 10.5% by weight of ethylbenoate, respectively. Specific surface 200. Polymerization. An equipment consisting of 4 reactors installed in series A, B, D and E (each has an effective volume of 190, 120, 140 and 200 liters, respectively, and an evaporator drum C (effective volume of 30 liters), installed by reactors B and D. The reactor A is charged with 0.75 mmol / h of Ti as a suspension in hexane of the solid component prepared as above, and a hexane solution of aluminum triethyl and EPT in such quantities that the molar ratios A) / Ti and .A1 / EPT - were 50 and 2.75, respectively, with a total flow rate of 21 l / h on hexane. In addition, 7 m / h of propylene and 13 l / h of hydrogen are charged into the reactor at a pressure in the reactor of 7 kg / cm and a polymerization temperature. As a result, 240000 g of polypropylene / g of Ti with an isotacticity index and melt index of 92, 0.36, respectively, are obtained in the reactor A. The polymer suspension discharged from reactor A is fed to reactor B, into which 4.5 mmol / h of triethylaluminum and 5 l / h of hexane are again fed. Then lead the polymerization in the reactor at
    Preparation of the catalyst component with a carrier pressure of 3 kg / cm and. In reactors A and B, 290000 g of polypropylene per 1 g of Ti are obtained with an isotacticity index of 92.2% and a melt index of 0.32. The polymer slurry discharged from reactor B is then sent to the flash drum C, where the unreacted propylene monomer is removed and sent to reactor D, where 1000 l / h of ethylene and 80 l / h of hydrogen are additionally supplied along with nitrogen gas that maintains pressure in the reactor 2.5 kg / cm. The composition of the gas in the reactor D,%: hydrogen 7,3- ,. nitrogen 45.5; ethylene 25.8; propylene 0.9; hexane 20.4. As a result of polymerization in the reactor D at 60 ° С, 27000 g of polymer per 1 g of Ti are obtained with a melt index of 0.39 and a bulk density of 0.350. The polymer slurry discharged from reactor D is sent to reactor E, to which 1,700 l / h of ethylene, 70 l / h of hydrogen, 4.5 mmol / h of triethyl aluminum and 10 l / h of hexane are additionally supplied. The polymerization is carried out at a polymerization pressure of 2.0 kg / cm and a temperature of 60 ° C, the composition of the gas in the reactor is E,%: hydrogen 3.2; nitrogen 3,4; ethylene 35.6; propylene 0.1 and hexane 22.6. As a result of polymerization in reactor E, 24,000 g of polymer is obtained per 1 g of Ti with a melt index of 0.24 and a bulk density of 0.350. The resulting polymer contains 17.6 parts by weight. ethylene polymer per 100 weight.h. polypropylene. Thus, the proposed method allows to obtain a high stereoregular product with a high yield. Table 1
    Shredding
    Volume of a vibration mill, l
    The volume of the mill rotated MgCU, l MgCl ,, g
    The number of EB (ethyl benzoate), g
    The molar ratio MDS}, / E T I 1, g
    Duration of grinding, h
    530,651.5. 651.5
    280 158.5 158.5
    3/1 6.5 / 1 6.5 / 1
    50
    50
    100
    Characteristics of the ground product. X-ray
    spectrum
    Tetrachloride treatment
    Silicone oil and the amount of T i C I., G
    Duration of grinding, h
    Continued table. one
    200,100
    100
    100 Spectrum A means the spectrum, s of which the most intense magnesium chloride line appears at d 2.56 A has a relatively reduced intensity and asymmetric broadening, forming a circle g whose peak in intensity ranges from d 2 = 44 L to 2.97 A. Spectrum B means a spectrum in which the indicated maximally intense line is absent, and instead there is a circle in which the peak intensity is shifted relative to such a line and lies in the range from d "2.44 A to d 2.97 A. fl 9M500, fUSwv 100 and pTJSi 50 - are polydimethylsiloxanes having a viscosity of 500, 100 and 50 centistokes, respectively. T a b l and d a 2
    Indicators
    Characteristics of the ground product
    x
    X-ray spectrum
    Treatment with titanium tetrachloride Ti C b, g
    Ground product, g
    The crushed product of comparative example 1, g
    Processing temperature, С. Filtration temperature, С
    Characteristics of the product treated with T i C 1
    Elementary analysis / weight
    Shredding
    The volume of the vibration mill /
    Volume of a rotating mill, l
    MgClj, g
    Ethyl benzoate (EB), g
    MGL / EB ratio
    Silicone oil / amount TiCI, g
    L Duration of grinding
    Characteristics of the crushed duct
    Processing tetrachloride tnom (TiCI)
    T i C b, g
    Continued table. 2
    AT
    AT
    375 25
    130 135
    Table
    96.5 30.6 5/1
    100
    375
    150
    Washing with boiling heptane (quant.) F g
    Characteristics of the product treated with TiCI
    Elementary analysis, wt.%:
    Ti
    C1 Specific surface m / g
    Shredding
    Volume of a vibration mill, l.
    Volume of a rotating mill, l
    MgClj, g
    Ethylbeneate (EB), g
    MgClg / SB molar ratio
    Silicone oil / amount, g
    TiCl.r
    L
    Duration of grinding
    Treatment of titanium tetrachloride
    TiCi4, g
    The crushed product, g Processing temperature, C Filtration temperature
    Continued table. 3
    800
    2.6
    1.65
    1.55 58.4
    Table 4
    96.5651,5
    30.6157 5D6.5 / 1
    100 / 13.9
    100
    100
    100
    15
    85857116 Indicators Characteristics of the product treated with TIC 1d Elemental analysis, wt.% TJ CJ a Specific surface, m / g - "." .. ".." .. "". "" .. "." .. Indicators
    Shredding
    f
    Volume of a vibration mill, l MgCI, g
    Ethyl benzoate (EB), g Molar ratio MdS
     g
    treatment with titanium tetrachloride (T1C1d)
    T C b, g
     g
    The crushed product, g Processing temperature, C Filtration temperature, C
    Characteristics of the product treated with T IC 1.
    Elementary analysis, wt.% :, T1 C1
    .Specific surface, m / g
    Continued table. four
    45
    10.1 6.8 / 1 54
    135 20 80 80
    1.4 3.1
    80 a I 9 I 10 1.65 2.00 1.1 62.05 62.55 66D 172 Table 5 - - .V i (Example I
    17858571.18
    The results of the polymerization of propylene a b l
    Polymerization process Autoclave capacity, l Polymerization medium and volume, cm Effective pressure Сj, atm
    and c a 6
    2.5 2.5 30 BC / 1000 H.c: J / 1000 CZ / 23000 55, 26.5
    Polymer intrinsic viscosity, dl / g
    Polymerization process
    Autoclave capacity, l
    The medium of polymerization and volume, cm
    Effective pressure Cj, atm
    Polymerization temperature, C
    The duration of polymerization
    Alkyl Aluminum Type
    The number of alkylaluminum, g
    Type of donor
    The molar ratio of alkylaluminum to the donor
    Continued table. 7
    .1,8
    2.1
    2.0
    Table 8
    2.5 2.5
    2.5
    ЗД4
    3.14
    .14
    Continued table. eight
    Polymerization process
    Autoclave capacity, l
    The medium of polymerization and volume, cm
    Effective pressure, atm
    Polymerization temperature, C
    The duration of polymerization
    alkyl aluminum type
    The number of alkylaluminum, g
    Type of donor
    The molar ratio of aluminum alkyl to the hole f
    Amount of hydrogen, n. Polymerization results Yield, g / poly / gT1 Stereoregulatory index,%
    Characteristics of the obtained polymer
    Apparent to the density of the polymer, kg / l
    Polymer intrinsic viscosity, dl / g
    Indicator stereoregularity92
    MB - mbtilbenzoat MMA - methyl methacrylate NBE - di-n-butyl zfir
    Table 10
    0., 28
    0.43
    0.4
    1.9
    82
    94.5
    93
    权利要求:
    Claims (2)
    [1]
    94 25 Donor elektronovBK K i, BK - benzoic acid POBK - para-hydroxy-benoic acid AUC-c, α-aminoacetic acid ABA-amidobenzoic acid. Claims The method of producing polypropylene by polymerizing propylene in a mass or medium of a hydrocarbon solvent in the presence of a catalyst consisting of an organoaluminum compound, an electron donor and a solid product of the reaction of anhydrous magnesium halide with titanium tetrachloride and an electron donor, is different with that, with a view to increasing 85857126 Table 12 POBA AUK 1 AB NBE and no final product yield, using a solid product with a specific surface area of 80-200. Sources of information taken into account in the examination 1. UK Patent I 1387890, cl. SIR, pub. 1974.
    [2]
    2. Published for Germany №2347577, cl. 39 to 3/10, published. 1974 (prototype).
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    同族专利:
    公开号 | 公开日
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    ZA765709B|1977-09-28|
    FR2378046A1|1978-08-18|
    HU174805B|1980-03-28|
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    DK415776A|1977-05-22|
    BR7606438A|1977-08-30|
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    FR2332288B1|1979-09-21|
    FR2332288A1|1977-06-17|
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    引用文献:
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    申请号 | 申请日 | 专利标题
    IT29525/75A|IT1054410B|1975-11-21|1975-11-21|CATALYSTS FOR THE POLYMERIZATION OF ALPHA OLEFINS|
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