• 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 novel catalyst system for the polymerization or copolymerization of olefines, more particularly to ethylene is disclosed. For preparing the novel catalyst system, a titanium compound (Ti IV) is previously attached to a solid supporting member, whereafter the so anchored Ti is reacted with vapors of a metal, in the presence of a halogenated compound or not. Very high polymer yields are obtained and examples are given.
    公开号:SU1093238A3
    申请号:SU813274741
    申请日:1981-01-26
    公开日:1984-05-15
    发明作者:Корбеллини Маргерита；Гамба Алессандро；Бузетто Карло
    申请人:Аник С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    :about
    :about
    N3
    ic
    70 The invention relates to a process for the preparation of a catalytic composition based on titanium trichloride and a supported metal chloride. A known method of preparing a catalyst for the polymerization or copolymerization of olefins by the conversion of titanium tetrachloride with metallic aluminum to titanium trichloride, grinding the latter with an auxiliary organic component containing oxygen or nitrogen, or phosphorus, or sulfur, or silicon, or a hydrocarbon compound or its derivative, to. disappearance from (.- or crystals of titanium trichloride, followed by extraction of crushed titanium trichloride with a solvent and mixing it with an aluminum organic compound flj. The disadvantages of this method include the multi-stage, the difficulty of grinding to the disappearance or p of titanium trichloride crystals. After carrying out titanium trichloride. Diffraction analysis, the closest to the invention in its technical essence and the effect achieved is a method for obtaining a catalytic com positions for the polymerization of olefins based on titanium trichloride and a metal chloride selected from the group of magnesium, manganese, chrome, aluminum, iron, vanadium titanium, by evaporation in vacuum at Hg of a metal selected from this group, and reacting the resulting vapors with tetrachloride titanium or vanadium at.-80-20 with G2. However, according to this, a catalyst is obtained with an insufficiently high activity (3900-64.00 g / g Ti h-atm). The purpose of the invention is to obtain an α-roll of lytic composition with increased activity. To achieve this goal, according to the method for producing a catalytic composition for the polymerization of olefins based on titanium trachloride and a metal chloride selected from the group of magnesium, chromium manganese, including evaporation of magnesium or manganese in vacuum, or chromium and reacting the resulting vapors with tetrachlochloride titanium at 1 82 (- 80) - (+ 20) C 5 first titanium tetrachloride is applied on the carrier alumina or silica, and then interact with metal vapors. The method according to the invention, in comparison with the known, allows to obtain a catalyst with superior activity (14000-16000 g / g Ti h-atm). The proposed method is carried out as follows. A solid substrate is treated with a compound of tetravalent titanium under conditions where sorption is possible. Then, the obtained product is reacted with vapors of one or several metals from the group of magnesium, manganese, chromium in the presence of an inorganic or organic halide donor compound (or without it). At the same time, the above reaction is better in the presence of an organic diluent, in which the titanium compounds and the halide donor, if used, are quenched before contacting them with metal vapors. The evaporation of metals is carried out under pressure; Neem Hg at 300-2500С depending on the metal used. The reaction of metal vapors with a titanium compound, regardless of the presence or absence of a halide donor, takes place at relatively low temperatures, below the boiling point of the diluent at the pressure used (it is usually (-80) - (+ 20) C). As indicated, it is better to conduct such reactions in the presence of an organic diluent, which is an aliphatic or aromatic hydrocarbon or mixtures thereof. Organic halides may be used as halide donors, preferably of the formula. / 12-1 (Xx, where X is chlorine or bromine, m is the number 1-18, X 1-4, and such halides can also serve as diluents. also inorganic halides of highly valence elements that exist in at least two oxidation states, for example, SnCi, SbClj, POCfj, VCt4. The compound of tetravalent titanium uses fourfluoride titanium.The use of the catalytic composition obtained by the proposed method 3 on a solid substrate — alumina and and silica yields a much higher polymer yield than with known catalysts, for example, more than 150 kg of polyethylene per gram of titanium, and even without a diluent (for example, in the gas phase), a polymer is obtained in high yield. torus together with an organometallic aluminum compound of the formula AgKrHz p (1 p. 3), where X is X. POR or bromine, R is a hydrocarbon radical, for example alkyl, aryl, cycloal kil, alkaryl or aralkyl. The polymerization is carried out at 20200 0 and a pressure of 1-60 atm. Example 1. 3 g of SiO-grade 5 Davison Chemical with a specific surface area of 285, a pore diameter of 168 L and a pore volume of 1.2 are dried for 7 hours at 250 ° C, then bale t under reflux in a nitrogen atmosphere in 150 MP of tetrachloride-titanium for 4 hours. Filtration in a hot state in nitrogen atmosphere is carried out through a sintered glass diyfragm. The product is washed on the filter with anhydrous hexane, then suta in vacuum. A product j containing 4.61% (2.9 mmol) of titanium is obtained. It is loaded into a rotating flask of an apparatus for evaporating a metal in a vacuum. In the center of the flask establish tungsten 5 spiral, which is connected to the network. Under the flask establish horizontal cooling bath. At the top of the device there is an inlet for nitrogen to create a vacuum. 2.7 g of magnesium (112 mmol) are loaded into the coil, then the titanium compound 320 ml of octane and 33 mphlohexane (240 mmol) is additionally loaded into the flask. The flask is cooled to (-50) "(C and begin to rotate, mm Hg are spawned, and the vacuum coil is heated to evaporate the metal. A brown-black suspension is formed. At the end of the evaporation, which lasts about 20 minutes, nitrogen is fed into the device The flask is brought to room temperature and heated again for 2 hours. The chemical analysis shows that the product obtained, in addition to the presence of silicon oxide, has an empirical formula: 38 TiMg3eC. For polymerization of ethylene, a 2 l autoclave equipped with a stirrer is loaded 1 l heptane (deaerated and dehydrated), 2 mmo It is isobutylaluminum and a small amount of the composition obtained (equivalent to 0.005 mmol of titanium). Then, peratura will be raised to 85 ° C, then 2 atm of hydrogen and 2 atm of ethylene are fed and the total pressure is kept constant for 2 hours. properties: MP12 (, AZTMD 1236 - 65T) 0.45 gUH min / MG1 / MG12,. (, 32 and a density of 0.971 g / cm. Specific activity - 16 thousand g. of polymer per 1 g of titanium per hour and 1 atm ethylene. Then, under these conditions, a substrate containing 4.61% titanium but untreated in magnesium and chlorhexane vapors is used. It has a specific activity of only 200 g of polymer per 1 g of titanium per hour and per 1 atm of ethylene. GI2, polymer 0.02 g / 10 min. Example 2. According to the method of example 1, But using an aluminum oxide substrate (AK Z O grade B) with a specific surface of 360 and a pore volume of 1.5 ml / g, dried for 8 hours, a product is obtained that contains 2.39% titanium treated with magnesium vapors in the presence of chlorhexane in Example 1. The empirical formula of the product TiMg SI, except alumina. The product obtained is used to polymerize ethylene under the conditions of Example 1. A specific activity of 30 kg of polymer per gram of titanium per hour per bar of ethylene is obtained. The resulting polyethylene has 0.65 g / 10 min, a density of 0.970 g / cm. A substrate containing 2.39% titanium but not treated with magnesium vapor and chlorhexane has, during the polymerization of ethylene, the specific activity of only 260 g of polymer per gram of titanium per hour per 1 atm of ethylene. The polymer thus obtained is not. get in the molten state under a load of 2.16 kg o Example 3. A 1 L autoclave equipped with a stirrer that is carefully / (evaporated and dehydrated in a hot state is loaded under nitrogen atmosphere with this amount of catalyst prepared in Example 1j
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING A CATALYTIC COMPOSITION FOR POLYMERIZATION OF OLEFINS based on titanium trichloride and a metal chloride selected from the group of magnesium, manganese, chromium., Including evaporation in vacuum of magnesium or manganese, or chromium and the interaction of the obtained vapors with titanium tetrachloride at -80 + 20 ° C wherein (which, in order to obtain one of the catalytic composition with increased Coy asset • NOSTA initially tetrachloride 'is supported on titanium - aluminum oxide or silicon oxide and then reacted with metal vapor.
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3153634A|1956-09-26|1964-10-20|Sun Oil Co|Gamma alumina supported titanium and zirconium subhalides polymerization catalysts and preparation thereof|
    US3769373A|1956-12-27|1973-10-30|Ici Ltd|Polymerisation of unsaturated hydrocarbons|
    US3094568A|1959-12-01|1963-06-18|Gulf Research Development Co|Process for alkylating aromatics in the presence of a heavy metal halide, an organic halide and an organo aluminum halide|
    US3166542A|1960-01-18|1965-01-19|Cabot Corp|Surface treated inorganic solid polymerization catalyst and method of polymerization therewith|
    NL125687C|1960-12-29|
    US3365434A|1963-09-05|1968-01-23|Eastman Kodak Co|Metal-reduced transition metal halide catalyst|
    US3432513A|1964-02-12|1969-03-11|Continental Oil Co|Olefin polymerization process for producing highly isotactic polymers|
    NL128168C|1965-02-10|
    FR1550186A|1967-08-31|1968-12-20|
    GB1189038A|1968-09-11|1970-04-22|Mitsui Petrochemical Ind|Novel Process for the Polymerisation of Ethylene and Novel Catalyst for use therein|
    US3923687A|1970-07-14|1975-12-02|Chisso Corp|Process for activating catalyst component useful for polymerizing propylene|
    IT951956B|1971-12-27|1973-07-10|Sir Soc Italiana Resine Spa|PROCEDURE FOR THE POLYMERIZATION OF OLEFINS|
    IT1004430B|1974-03-28|1976-07-10|Snam Progetti|PROCESS FOR THE POLYMERIZATION OF ALPHA OLEFINE CATALYST USED IN THIS PROCESS AND METHOD FOR ITS PREPARATION|
    IT1013081B|1974-03-28|1977-03-30|Snam Progetti|PROCEDURE FOR THE POLYMERIZATION OF ALPHA OLEFINE CATALYST USED IN THIS PROCEDURE AND ME TODO FOR ITS PREPARATION|
    IT1009869B|1974-04-17|1976-12-20|Snam Progetti|PROCEDURE FOR THE POLYMERIZATION OF ALPHA OLEFINE CATALYST USED IN THIS PROCESS AND METHOD FOR ITS PREPARATION|
    IL51283A|1976-01-30|1979-11-30|Snam Progetti|Process for preparing a co-catalyst for use in the polymerization of a-olefins,a co-catalyst prepared by the process,a catalytic system comprising such a co-catalyst and a process for polymerizing an a-olefin using such catalytic system|IT1130243B|1980-02-01|1986-06-11|Anic Spa|CHEMICAL COMPOSITION BASED ON TRIALHYGEN TITANIUM, METHOD FOR ITS PREPARATION AND PROCESS OF POLYMERIZATION OR COPOLYMERISATION OF UNSATURATED COMPOUNDS USING THE SAME|
    US4524195A|1983-10-19|1985-06-18|Phillips Petroleum Company|Process and catalyst for olefin polymerization|
    US4740570A|1985-01-18|1988-04-26|E. I. Du Pont De Nemours And Company|Metal halide vaporization into diluents|
    US4650778A|1985-01-18|1987-03-17|E. I. Du Pont De Nemours And Company|Metal halide vaporization into diluents|
    JPH0284405A|1988-09-20|1990-03-26|Mitsubishi Petrochem Co Ltd|Production of ethylene polymer|
    FI87891C|1991-07-16|1993-03-10|Neste Oy|METATESKATALYSATOR FOER OLEFINER|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT25233/77A|IT1081277B|1977-06-30|1977-06-30|CHEMICAL COMPOSITIONS BASED ON TRIALHYGEN TITANIUM PROCEDURE FOR THEIR PREPARATION AND USE|
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