• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    For the preparation of the trichlorides of titanium and vanadium, a metal is vaporised in vacuo and the vapour thus obtained is reacted at low temperature with MCl4, M being Ti or V. The vaporisation of the metal takes place in a vacuum of between 10<-1> and 10<-6> mm Hg, and the reaction of the metallic vapours and MCl4 takes place at temperatures of between -80 and +20 DEG C in the presence of an inert diluent selected from saturated or unsaturated aliphatic hydrocarbons or from halogenated hydrocarbons. The metal to be vaporised is preferably selected from the group comprising Al, Mg, Cr, Mn, Fe, V and Ti. The trichlorides thus obtained and an organometallic aluminium compound are used in catalytic compositions for the polymerisation of alpha-olefins in high yield.
    公开号:SU1056905A3
    申请号:SU772446350
    申请日:1977-01-28
    公开日:1983-11-23
    发明作者:Корбеллини Маргерита；Греко Альберто
    申请人:Снампрогетти С.П.А. (Фирма)；
    IPC主号:
    专利说明:

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    3)
    about o: l
    The invention relates to a process for the preparation of an olefin polymerization catalyst and can be used in chemical industry plants.
    The catalysts for the polymerization of olefins, obtained by the proposed method, smolder with their BASIC vanadium trichloride and titanium. Such catalysts are used in polymerization processes, olefins in catalytic systems that include, in addition to the catalyst, a cocatalyst — an aluminum compound of the general formula Aj. where R is alkyl, aryl, hydrogen; X - to halogen. n is an integer in the range of 1-3. Known methods for producing titanium trichloride or vanadium are based on the interaction of titanium tetrachloride or vanadium with a reducing metal in a polar organic solvent l and 2.
    The method can be implemented at room temperature with the supply of a reducing agent in the form of TL amalgam or at elevated temperatures with the supply of a reducing agent in powder form.
    As a reducing metal, Mg ij or metals of groups II and III of the periodic system 2 can be used.
    However, the known methods do not result in catalysts characterized by high activity and stability.
    The aim of the invention is to increase the activity and stability of the catalyst.
    This goal is achieved by the fact that a metal-reducing agent selected from the group including aluminum, magnesium, chromium, manganese and iron is evaporated under a pressure of 10 to 10 mm Hg, metal vapors, is contacted with titanium tetrachloride or vanadium in an organic a solvent selected from the group including saturated hydrocarbons, aromatic hydrocarbons, halo-derivatives of these hydrocarbons or their mixtures, at a temperature of from -80 to + 20 ° C.
    Moreover, magnesium is used as a reducing metal, titanium tetrachloride is used as a reducible compound, magnesium is taken at least in a fourfold molar ratio to titanium, and the reaction is carried out in the presence of an excess of organic or inorganic halogen compound.
    Trichloride derivatives of Ti or V are obtained by the reaction of .MCfy with a metal, preferably selected from A, Mg, Cr, Mn, Fe, V, Ti (M-V or Ti) .j
    Evaporation is carried out at temperatures that may vary depending on the metal used and usually lie in the range of 800-2500 ° C.
    The reaction proceeds using ficf, which is used
    either in pure form or diluted with inert solvents selected from aliphatic or aromatic, saturated or unsaturated hydrocarbons, and
    halogenated hydrocarbons such as chlorhexane and fluorobenzene.
    The selection of the solvent or solvent mixture is based on the conditions of use (temperature.
    hardening and evaporation at pressurized pressure.
    In addition, it was found that if in the mentioned method a high ratio of Mg / Ti and reaction
    carried out in the presence of a halogen donor, it becomes possible to obtain a composition that, together with an organometallic aluminum compound, leads to good results in polymerization with high yields of alpha-olefins, especially both ethylene, and mixtures with one or more of its higher homologues.
    Such a composition is obtained by evaporation of magnesium or its alloys with subsequent condensation in an inert diluent, which contains a compound of titanium and a halogen donor. Magnesium evaporation is preferably carried out under vacuum, a torr of -10 mm Hg, at a temperature that varies depending on the pressure used, in the range of 500-1200 ° C.
    Couples metal condensiru.ots
    in solution with stirring, the connection of titanium and the halogen donor at a temperature above the freezing point and below the boiling point of the solution.
    The highest yields of alpha-olefin polymerization are obtained if a high Mg / Ti ratio is used, especially when this ratio is equal to or greater than 4. It is also necessary to have a halogen donor, which is selected from organic or inorganic halogenated compounds, the latter are used in excess
    in relation to the amount of magnesium. A halogenated compound / magnesium ratio equal to or greater than 2 is also used. Magnetic vapor is condensed in an inert solvent selected from aliphatic or aromatic hydrocarbons,
    The polymerization reaction is carried out in the presence of a catalytic system consisting of a suspension prepared in conjunction with an organometallic aluminum compound in a hydrocarbon solvent medium which may be the same as used in the described procedure. Operating temperatures are in the range of 20-200 ° C, preferably 50-200 ° C, at pressures that range from 1 to 20 atm. If the polymerization is carried out in the gas phase, it is enough to disperse the catalyst in a low boiling solvent ensure that the latter is easy to remove. In this case, the catalyst may also be dispersed on an inert solid support, which may even be a polyolefin resin itself. The conditions that can be selected for the polymerization in the gas phase include a temperature range that is maintained below the melting point of the olefin, and in the special case of ethylene polymerization, the temperature range (preferred) is 40-90 ° C. The pressures are selected in the range of 1-40 atm. Hydrogen can be used as a molecular weight regulator.
    Example 1. Preparation of a mixture of 3 A2CP3-Uses a cozy rotating flask, in the center of which is placed a tungsten filament, which is connected to a source of electrical current. Under the flask have a horizontal cooling bath. At the top of the apparatus is a nitrogen and vacuum fitting. 160 mg of pure aluminum in the form of flakes is placed inside the spiral-twisted tungsten filament. The flask is charged under a nitrogen atmosphere with 250 ml of anhydrous decane containing 30% TiCJ by weight of solvent. The rotating flask is cooled with a bath of -4.0 ° C and then evacuated with a diffusion pump until it reaches a residual pressure of 10 mm Hg. When these conditions are established, the thread is heated until the metal evaporates. The evaporated metal reacts immediately with TiC2 to form a very fine dark brown precipitate. After completion of evaporation, the vacuum is released and the temperature in the flask is brought to room temperature by supplying nitrogen, then the suspension is heated at ISO for 3 hours. After filtration and drying, the thus obtained
    The purple product is identified as AlcJ-.
    Calculated,%: Ti 24,12; 4.52; C2 71.36.
    Found,%: Ti 24.01J AI 4.90; CI 69.80.
    PRI mme R 2. Use the apparatus and method described in example 1. Load 190 mg of pure metallic Mg in the form of a wire and 250 ml of octane containing 2% TiCI. After cooling to and reaching a vacuum at a residual pressure of mm Hg. begin to evaporate the metal and continue it for 5 minutes. “A fine dark purple precipitate is formed. In a flask, the normal pressure and temperature of the surrounding air are set. The sample was kept at 125 ° C for 4 hours, after which the suspension was filtered and the violet precipitate was washed with AND-heptane until TiCl was completely removed, then after drying in vacuum, the solid product (2 g) was identified as TiCfj.
    Calculated,%: Ti 23.76, Mg 5.94; cr 70.28.
    Found%: Ti 22.97 / Mg 5.8; C2 67.1.
    As shown by X-ray diffraction data, both samples, untreated and processed, have a gamma structure.
    Example 3. Use the apparatus and methods described in example 2, using a concentration of TiC2 in and -octane, equal to 14%.
    A dark violet product is obtained, which is filtered, washed with H 2 O-hexane before removal, then it is peresuspended to n-heptane and is identified as CI.
    Example 4. Use the apparatus and method described in Example 1. Load 0.240 g of metallic magnesium in the form of a wire and 300 ml of AND octane containing 0.07% TiCl | and 12% H-chlorohexane. After cooling to -60 ° C, a vacuum D9 of a residual pressure of 10 mm Hg is created and the magnesium is evaporated within 7 minutes. A pale brown product is obtained, which is collected on a filter, washed with H-heptane and kept at 100 ° C in this solvent for 2 hours. Analysis data indicate the formation of a product that has a molar composition.
    Example 5. Use the apparatus and methods described in example 1.
    Load 0.180 g of metallic Mp in the form of flakes and 250 ml of octane, containing 2% TicS. After cooling to create a vacuum
    to a residual pressure of mm Hg, and the evaporation of the metal begins, which is completed in 3 minutes. The formation of a dark purple precipitate. The cools are heated to ambient temperature and the vacuum is released, then the suspension is filtered, washed with H-hexane until TiCl is completely removed, after which the product is dried in vacuum and identified as 2TiCJ, MnC
    Calculated,%: Ti 22.0; All 65.30-, Mp 12.63.
    Found,%: Ti 22.0; C, 63.4; MP 14.4.
    Example 6. The apparatus and procedure described in example 1 is used. 0.25 g of metallic iron in the form of shavings and 250 m) of anhydrous H-octane containing 5% TiCj are charged. After cooling to -50 ° C, a vacuum equal to mm is created. Hg, and start the evaporation of the metal, which is continued for 5 minutes The result is a solid reddish-brown product, which is collected on a filter, washed with anhydrous hexane and dried in vacuo. 1.87 g of the product FeCJ 2TiC2-} is obtained.
    Calculated,%: Ti 21.99; Fe 12.8i C2 65.19.
    Found,%: Ti 21.73; Fe 12.7u;
    C g 66.90.
    Example 7. Use the apparatus and methods described in example l. 0.120 g of Mg is loaded in the form of a wire and 250 ml of N-octane containing 3 ml of VCI. After cooling to create a vacuum to a residual pressure of 10 mm Hg. and start evaporation of the metal, which lasts 5 minutes. a solid dark brown product is obtained, which is washed with H-heptane to remove excess and peresuspended to H-heptane. Ug V, C is obtained.
    Example iij Use the apparatus and technique described in Example 1. Load 1 g of metallic chromium in the form of pieces and 250 ml and α-heptane containing 10 ml. After cooling to create a vacuum at a residual pressure of mercury. and start evaporation of the metal which lasts 20 minutes until completion, resulting in a greenish product, which is collected on a filter, washed with heptane until excess is removed, and re-suspended from heptane. The composition of the product, CrCi BTiCfj follows.
    Calculated,%: Ti 23.19 Cg 8.37; C2 b8,44.
    found,%: Ti 23.40} Cg 8.20; CI 67.60.
    Example 9. A 5-liter autoclave was charged with 2 liters of anhydrous h-heptane containing the catalyst prepared according to Example 3, with a concentration of 0.03 mg titanium and 4 mg AS from 5 aluminum / ujo-TDI. The mixture is heated to 85 ° C, then a hydrogen pressure of 5 kg / cm is created, and the appropriate amount of ethylene is fed into the system. The polymerization was carried out for 4 hours, keeping the total pressure constant as a result of the addition of ethylene. After the polymerization is complete, the suspension is centrifuged and the polymer is dried in
    5 vacuum at 50 ° C for 4 hours and then weighed.
    The result is 400 g of white polymer, which is equivalent to a specific yield of 6440 g
    Polymer Q per gram of Ti per hour and on atmosphere C, having an index, 60.
    Example 10. The procedure of Example 9 is used, using
    f herewith. as a catalyst, the sample described in example 1, with a concentration of 0.06 mg per liter of titanium, as a cocatalyst AE / U o -HD with a concentration of 4 mg / l. Create a hydrogen pressure equal to
     , 5 kg / cm2, and ethylene pressure, equal to; It is also 5 kg / cm. The polymerization is carried out under constant pressure by adding ethylene for 4 hours and 120 g of white polymer are obtained, which corresponds to a specific yield equal to 1.03 g of polymer per gram Ti per hour and per atmosphere Cj.-, having MF) 6, 5 / MGad ,, e / MDE ,, 49.4 /.
    0 Pr and p 11. A 2-liter autoclave is charged with 1 liter of anhydrous and deaerated H-hexane / catalyst containing 20.8 mg, according to example 6, which corresponds to
    5 0.0941 mg titanium and 4 Mg -Bu / per liter. Create a pressure of hydrogen and ethylene, equal to 20 kg-cm each. The temperature is raised to 85 ° C and the pressure is kept constant in
    l result of constant ethylene feed. After 2 h of polymerization, the reaction medium is cooled, pressure is released from the autoclave and poly1.1 rt is centrifuged, dried under vacuum at and weighed. As a result
    5 get 320 g of polymer having
    MFtr2.6 - 0.12 / MK: T2, 6 4.7 /. The yield of 1750 grams on Grag.1M Ti per hour and on the atmosphere Cj-.
    Example 12. The procedure of example 9 is repeated, using as a catalyst the product described in example 5 in the concentration,. equal to 0.10 mg per liter of titanium. , tt as a cocatalyst
    5 Use Al / T / o-Bu / at a concentration of 4 mg / l. The polymerization was carried out for 3 hours with a hydrogen pressure of 5 kg / cm and an ethylene pressure of 5 kg / cm. 390 g of polymer was obtained having
    .lb 035, 6 Yield: 2700 g per gram-Ti per hour and per atmosphere.
    Example 13. The procedure of example 9 is repeated, using the sample described in example 8 as catalyst, at a concentration of 0.026 mg per 1 liter of titanium and 2 mgl-l: (and o-vi). A hydrogen pressure of 5 kg / cm2 and a pressure of 5.5 kg / cm of ethylene are created. The temperature is raised to and the pressure is kept constant as a result of feeding with ethylene. After 2 h of polymerization, the reaction mass is cooled, depressurized, the polymer is collected on a filter, dried under vacuum and weighed. 108 g of polymer are obtained which gives a MFtT of 0.11, which corresponds to a yield of 3900 g of polymer per gram of Ti per hour and per atmosphere of ethylene.
    In tab. 1 shows the specific activities obtained in the polymerization of ethylene in the presence of TiCTj samples obtained according to examples 1-b inclusive.
    Table 1
    Example 14. A 100 ml two-necked flask, which is flushed with an inert gas, is charged in an inert atmosphere with 30 ml of anhydrous H-hexane, then 0.1 mmol of Ti according to Example 3, 0.1 mmol of AP / -jo-B and then 7 g of anhydrous isoprene, double distilled over LiH. The mixture in the flask is stirred for 2 hours at and then poured into Zio methyl alcohol containing 1% antioxidant. The coagulated polymer is dried under vacuum at room temperature overnight. Under these conditions, the dry polymer yield is 6.3 g, which corresponds to 90% of the monomer introduced. NMR analysis reveals the advantageous presence of a 1,4-cis-type structure. Example 15. A 200 ml bottle that is pre-rinsed with an inert gas is charged under an inert gas atmosphere with 90 ml anhydrous H-hexane and then 0.5 mmol V according to example 7 and 1 mmol AiZEt. The bottle is sealed with a neoprene grip and a perforated Kronglas cap in order to insert a hypodermic needle. At this stage, 14 g of monomer in liquid form is injected with a needle directly attached to a metal bottle that contains butadiene. This bottle is placed in a rotary bath, thermostated at, 1.5. h. After completion of the reaction, the bottle is opened and its contents are poured; 0.5 liters of methanol, which contains 1% ionol. The coagulated polymer is dried in vacuo for 16 hours. Under these conditions, the yield of solid polymer is 1.8 g, which corresponds to 13% of the monomer introduced. IR analysis shows the presence of a 1.4-7-7 structure. Example 16. A 2-liter autoclave was charged with 1 liter of anhydrous and aerated H-hexane containing 340 mg of catalyst, according to Example 8, which corresponds to 1.66 mg-at of titanium and 7 mg-at AlEt per liter. 8 kg / cm of propylene is also charged into the autoclave. The temperature is raised to and the pressure is kept constant as a result of feeding with propylene for 6 hours. After cooling the autoclave, the polymer is collected on a filter and dried in vacuum at 50 ° C. 135 g of polymer having a crystallinity (RX) of the order of
    42% and the residue after extraction with hexane, equal to 85%.
    Example 17. Get catalyst at a ratio of Mg / Ti vyiyu 0.5. The apparatus described in Example 1 is used. A tungsten coil is charged with 800 mg of Mg in the form of needles. A 500 ml flask is charged under a nitrogen atmosphere with 130 ml of anhydrous and deaerated H-heptane, 20 ml of 1-chlorohexane (146 mmol) and 0.15 ml of TiCj (1.35 mmol). The flask is cooled to create a vacuum to a residual pressure of mm Hg, then the coil is heated to evaporate the metal. A greenish brown precipitate formed. After completion of evaporation (about 15 minutes), nitrogen is supplied to the apparatus and the flask is brought to ambient temperature, without interrupting mixing. Suspension analysis: Mg / Ti 24; Cl / Ti 45. Polymerization. A 5-liter autoclave, equipped with a root stirrer, was charged with 2 liters of anhydrous and deaerated H-heptane, 4 mmol of A / i-ViD and some: catalyst prepared according to this example, corresponding to 0.01 mg of elemental titanium. The temperature is raised to 85 ° C, then hydrogen pressure is applied.
    Example 20: The synthesis procedure described in Example 17 is used using the following reagents: 1.100 mg (46 mg-at) Mg, 0.2 ml
    (0.68 mmol) Tic / Ozo-Pr / 2 and 20 MP, g Vg, which corresponds to 142 mmol in 200 ml of H-octane.
    After the reaction, the suspension analysis is as follows: Mg / Ti -. 48 / (Br + C2) / Ti 83.5.
    When ethylene was polymerized under the conditions of example 17, 265 g of polymer was obtained having an MFI of 8.5 g /
    equal to 5 kg / cm2, and ethylene pressure equal to 3.5 kg / cm. Ethylene is fed continuously in order to keep the total pressure constant for 1 hour. 350 g of polyethylene is obtained, having H17S 9.8 g / 10 min and d 0.9690 g / cm. Specific activity 200000 g of polymer per 1 g of titanium per hour and on the atmosphere of ethylene.
    Example 18. The method of synthesis was carried out analogously to example 17, using bromohexane as the haloalkyl. the result is a suspension having the following composition according to analysis: Mg / Ti 16.5; (Br + 33. When ethylene is polymerized under the conditions of Example 17, 165 g of polymer a are obtained, having an MRI of 4.18 g / 10 min, i which corresponds to a specific activity of 98,000 g / g Ti per hour and per atmosphere of ethylene.
    Irimer19. According to Method 5 of Dicke according to Example 17 and using the same reagents, several catches of various Mg / Ti ratios are obtained, the activities of which in the polymerization of ethylene, which is carried out under CONDITIONS of Example 17, are given in Table 2.
    table 2
    10 minutes, which corresponds to a specific activity of 157,000 g of polymer per gram of Ti per hour and an atmosphere of ethylene.
    Example 21. Use the method of synthesis described in example 17, using the following reagents: 1.050 mg (43) Mg, 15 ml (lio mg-at) CgH, SG and 0.2 ml (0.67 mg-at in 170 ml N -octane T1 (0). P 0.05 mm Hg; t.
    After evaporation of the magnesium, the flask is filled with nitrogen and left overnight. Suspension analysis: Mg / Ti 52; sg / ti 90.
    Polymerization of ethylene, which was carried out under the conditions of example 17, gave 125 g of polymer having a MFI of 6.7 g / 10 min and a reasonable activity of 75,000 g of polymer per gram of Ti per hour and per atmosphere of tylen.
    Example 22. The apparatus described in example 1 is used. 1096 g of pure metallic magnesium in the form of a wire is placed into a tungsten filament, while a 1 l flask is charged with 130 cm of anhydrous ligroin containing 1 TiCl and 66.7 mmol of SnCJi, the magnesium is completely evaporated in a 40 min at a vacuum of 0.09 mm Hg by rotating the flask at -60. The flask is brought to ambient temperature and pressure and stirring is continued for another 1 hour. During this time, the suspension changes its color from dark brown to greenish-white. Filtration is carried out on a G 3 porous diaphragm, washing with heptane and solid is resuspended in heptane.
    Analysis of the suspension, mmol / l:
    Ti 5.77; Mg I8i; sn i7o; every 731.
    Example 23. A tungsten filament is placed with 1.0 g of pure magnesium wire. The flask is charged with 130 ml of anhydrous toluene and 1 mmol of TiCS, which gives a yellow tint to the solvent. Then, 2 mmoles of diethyl phthalate are added dropwise at -78. The solution changes color from yellow to light green. Then 66.7 mmol of anhydrous SnCy, which gives a yellowish orange hue, are added, and an orange oily substance precipitates at the bottom of the flask. Magnesium is evaporated for 40 min under vacuum at 0.06 I “IM Hg. by rotating the flask at. -78 ° C. The flask is then brought to ambient temperature and pressure, and its contents are stirred for 1 hour. During this time, the suspension changes color from dark brown to yellow. The suspension is collected on a filter, washed without water with heptane and re-suspended in heptane.
    Analysis of the suspension, mmol / l: Ti 7.74; Mg 235; Sn 190; cf 897.
    Example 24 A tungsten filament is charged with 809.5 mg of pure magnesium in the form of a wire, while a flask is charged with 100 ml of anhydrous toluene and 1 m: .1 mole of TiCI, which dyes the solvent yellow. Then at room temperature and with stirring, the ext. &Amp; 2 mmol of diethyl phthalate is added. The solution takes a light green tint. Next, 43.3 mmol of SnCI H-But is added, which gives yellowish oran; A drop of color, and an oily residue is deposited on the bottom of the flask. Magnesium is evaporated for / 40 min under a vacuum of 0.07 mm Hg by rotating the flask at
    0 to 78 ° C. The flask is adjusted to ambient pressure and temperature and stirring is continued for 2 hours at room temperature. Suspension during this time changes from 5 to dark brown.
    on light gray. Filtration, washing with anhydrous heptane and resuspension in heptane are carried out. Analysis, suspensions, mmol / l:
    0 Ti 7.18; Mg 66; Sn. 80: cf 349.
    Example 25. 970 mg of pure magnesium wire is placed on tungsten. In a flask that contains 100 ml of anhydrous heptane and
    5 1 mmol of TiCIjj, 60 mmol of SbCI, distilled, are added at room temperature with stirring. The solution remains clear. As a result of evaporation of the magnesium, the suspension becomes yellowish-brown.
     Then a powder is formed, which gradually darkens, changing color from gray to black. Filtration, washing with anhydrous heptane and resuspension in
    5 of this solvent.
    Analysis of the suspension, mmol / l: Ti 4.60J Mg 226} Sb 95; cr 1,058.
    . Example 26. On a tungsten filament put 831.8 mg of pure
    0 magnesium wire. In a flask that contains 100 ml of anhydrous, H-heptane, is added at room temperature. temperature and with stirring 51.3 mmol of distilled POC2 and
    5 1 mmol A yellow precipitate formed. Magnesium is evaporated, maintaining the temperature at -78 ° C. . Suspension has a yellowish-brown color. The flask is brought to ambient temperature and pressure and stirred for 2 hours at room temperature. The suspension becomes pale yellow. Filtration, washing with n-heptane and resuspension in the last solvent are carried out.
    5 Analysis of suspension, mmol / lt
    Ti 9.62; Mg 226.;, P .390; CI 655.
    Experiments on the polymerization of ethylene in the presence of catalytic mixtures obtained according to examples
    0 22-26, wire according to example 17 with t polymerization time of 2 hours, hydrogen pressure of 5 kg / cm, and ethylene pressure of 5 kg / cm. The results obtained are given in Table 3,
    Table 3
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING CATALY-
    OLEPHIN POLYMERIZATION CONTAINER by reacting titanium or vanadium tetrachloride with a reducing metal in an organic solvent medium, characterized in that, in order to increase the activity and stability of the catalyst, a reducing metal selected from the group consisting of aluminum, magnesium, chromium , manganese and iron, evaporate under a pressure of 10 '* - 1СГ% в4 mercury, metal vapors are contacted with titanium or vanadium tetrachloride in an organic solvent selected from the group consisting of saturated hydrocarbons, ar aromatic hydrocarbons, halogen derivatives of these hydrocarbons or mixtures thereof, at a temperature of -80 to + 20 ° C.
    [2]
    2. The method of pop. 1, characterized in that magnesium is used as a reducing metal, titanium tetrachloride is used as a reducible compound, magnesium is taken at least four times in molar ratio to titanium, and the reaction is carried out in the presence of an excess of organic. .go or inorganic halogen compound.
    7069901
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    同族专利:
    公开号 | 公开日
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    AU2147277A|1978-07-27|
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    GR60862B|1978-09-01|
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    DE2703604B2|1980-07-10|
    EG13429A|1981-06-30|
    ES455759A1|1978-01-01|
    TR19781A|1979-12-04|
    GB1576431A|1980-10-08|
    JPS5294891A|1977-08-09|
    NO152562C|1985-10-16|
    MY8200212A|1982-12-31|
    DD130130A5|1978-03-08|
    AU512820B2|1980-10-30|
    YU165782A|1985-04-30|
    PH15890A|1983-04-14|
    LU76666A1|1977-06-28|
    YU44358B|1990-06-30|
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    IN145866B|1979-01-06|
    IE45018L|1977-07-30|
    YU44359B|1990-06-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT1974876A|IT1054583B|1976-01-30|1976-01-30|Titanium or vanadium trichloride prepn. - by reacting the tetrachloride with metal vapour, partic. magnesium, for obtaining olefin polymerisation catalyst|
    IT2525776A|IT1065073B|1976-07-13|1976-07-13|Titanium or vanadium trichloride prepn. - by reacting the tetrachloride with metal vapour, partic. magnesium, for obtaining olefin polymerisation catalyst|
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