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    • 专利摘要:

    公开号:SU940634A3
    申请号:SU792712056
    申请日:1979-01-22
    公开日:1982-06-30
    发明作者:Гутвайлер Клеменс
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    an ester of chromic acid, and then a titanium compound in hexane, for which an alkoxide of the general formula TiCOR is used) where R is iso-C7, H-; or iso-C H, at a molar ratio of Ti / Cr of 3-10: 1 followed by drying, the titanium compound being applied to the carrier after the chromic ester. To obtain a catalyst, readily available compounds of titanium and chromium are used. Since the chromium and titanium compounds used are fully reacted and retained by the support, it is not necessary to wash the catalyst. When using a catalyst prepared according to the proposed method, in the polymerization reaction a floor is obtained with a high yield and with a wide molecular weight distribution. In this case, a high polymer yield is obtained both when using this catalyst in combination with organoaluminum compounds, and in the case of individual use. The polymers obtained on the basis of polyMyr respond to the best samples produced by industry, for example, film based on polyethylene of the Hostal GM 9255 polyethylene firms Hoechst AG, Germany. L p i me R 1. In a solution of 0.296 g (4 mmol) of tertiary butanol in 150 ml of anhydrous hexane, 3 g of anhydrous sulfate, then 0.5 g (5 mmol) and silicon of CrOj, are added with stirring in the absence of air and moisture. In j-). Upon conclusion, the suspension is stirred for another 20 minutes at and then filtered under a gas-protective atmosphere. The red solution of tertiary butyl chromate without any purification is used for subsequent operations. Silicic acid with a specific surface area of MVr, a pore volume of 1.65 cm / g, and an average particle size of 100 microns is dried in a fluidized bed in the presence of argon at A60 ° C and stored in the presence of argon. 26 g of this silicic acid are suspended in 100 ml of hexane and combined with a solution of 2 mmol of tertiary butyl chromate in 150 ml of hexane, with stirring and under an inert gas. Then 10 mmol of Ti (0i-C, H7) 4 J 9 4 are added and the mixture is left for an hour at. After that, they are dried in a vacuum evaporation centrifuge. Half the catalyst of the following composition, May. Silicic acid The rest of the active components are represented in terms of metal. The powder obtained after that is used to polymerize ethylene. 100 liters of the hydrogenated diesel-oil fraction (mp. From 130-170 ° C) are loaded into a 200 l reactor and air is removed by flushing with nitrogen. Then warmed up. The catalyst is then introduced in the form of the aforementioned powder and 1 mmol of the isobutyl-alumina polymer. Ethylene and hydrogen are supplied such that its partial pressure in the gaseous medium is 5% at a total pressure of 6 bar. The pressure after further introduction of ethylene is retained and after 8 hours of polymerization at 85 ° C, 38 kg of polyethylene are obtained, which corresponds to a yield of 2380 g of polymer / mmol Cr per hour. The relative specific viscosity is 5.01 m / g; 190/5 flow index 0.13 g / 10 min; 190/15 1.5 g / 10 min; 190/15, 1 190/5 20.5. G1 p and m e r 2. The catalyst was prepared analogously to example 1, however, 2 mmol of tertiary butyl chromate was applied to 2 g of silicic acid. After that, the suspension is combined with 10 mmol of Ti (0i-CaH-,) and boiled for 1 hour under reflux. A catalyst of the following composition is obtained, mass .: Chromium, 0.38 Titan1, 75 Silicic acid Else. When polymerization in a reactor with a capacity of 200 liters in accordance with Example 1, a total pressure of 7 bar is reached at a content of Hp S% in a gaseous medium. After an 8-hour polymerization, 31 kg of polyethylene will be obtained, which corresponds to a yield of 1990 g of polymer / mmol g in part 5. The relative specific viscosity is 5.09 m / g. Flow index 190/5 0.15 g / 10m 190/15 20 g / 10 m Example 3- 0.811 + g (3 mmol dimethylpentadecyl carbinol CH3 (SNg), 4C (CH3) AOH, 1.5 g MgS04 and 0.8 g (v.mmole) CrOj is stirred with 150 ml of hexane for 1445 minutes under nitrogen at room temperature and then filtered. The filtrate is added to 2 silicic acid, which is dried before that under nitrogen flow, and the suspension is stirred under nitrogen for 1 hour. 3 ml (10 mmol) of titanium isopropylate are added and the mixture is kept for 3 days at room temperature without air access. Then hexane is separated on a rotary evaporator. The powder is colored in green o-blue color, used as a catalyst for polymerization. Composition of the obtained catalyst, weight D: Chromium 0.28 Titanium 1, 73 Silicic acid Else The polymerization is carried out as follows: 1 liter of diesel oil is charged into the autoclave and purged with hydrogen to remove air. Then, as an activator, 3 mmol of poly-iso-butyl aluminum oxide (dissolved in diesel oil) and 0.2819 g (0.018 mmol of chromium) of the above catalyst are added. The autoclave is closed and heated to. At a hydrogen pressure of 0.5 bar and a pressure of ethylene of 5.5 bar, the mixture is polymerized for t hours. Then the pressure is released from the autoclave and it is cooled. The polymer yield is 1–9 g, which corresponds to 2.398 kg of polymer / mmol Cg per hour. Melt index 190/5 1.88 g / 10 min and melt 190/15 17.62 g / 10 min. Example 4. Silicic acid with a specific surface area of 600, a pore volume of 1.12, and an average particle size of 0 mm is dried for 4 hours under an argon atmosphere in a fluidized bed and stored under argon. 26.8 g of this silicic acid are suspended at 20 ° C in 100 ml of hexane and a solution of O, + 605 g (2 mmol) of tert-butyl chromate in 150 ml of hexane is added with stirring and under inert + 6 by gas. Additionally stirred for 30 minutes. Then, 5.685 g (20 mml) of T1 (0-iso-CzH1) 4 is added and the mixture is kept at. The molar ratio of Cr: Ti is 1:10. A catalyst of the following composition is obtained, wt.%: Chromium, 0.39 Titanium, 3.45 Silicic acid, Balance. It is loaded as a suspension for the polymerization of ethylene. The volume of dispersion is 00 ml. 0.75 ml of the hydrogenated fraction of diesel oil (bp 130-170 ° C) is charged to the autoclave and air is removed by flushing with nitrogen. Then 3 mmol of poly-iso-butyl aluminum oxide and 2.0 ml (0.01 mmol of Cr) are added to the above suspension. Then the autoclave is heated to 85.degree. Hydrogen is supplied at a pressure of 3 bar and then ethylene to a total pressure of 15 bar. A pressure of 15 bar is maintained during the polymerization by the introduction of ethylene. After polymerization for k hours, 121.9 g of polymer are obtained, which is equivalent. It corresponds to the yield of g polymer / mmol Cg per hour. Melt index 190/5 0.9 g / 10 min and melt 190/15 5.91 g / 10 min. Example 5. The catalyst is prepared analogously to example 1, but allowed to be absorbed with 2 mmol of t-butyl chromate per 32 g of silicic acid. Then, 1, 7055 g (6 mmol) T1 (0-iso-C H), l are added to the suspension. After a three-day aging, the mixture is evaporated to dryness in a vacuum rotary evaporator. The catalyst contains, by weight .: Chromium, 0.32 Titanium, 0.89 Silicic acid Else The molar ratio of Cr: Ti is 1: 3. Into an autoclave with a capacity of 2 l, 0.75 l of the diZel-hydrogenated fraction is charged. oil (m.p. 1.30-170 ° C), and air is purged with a nitrogen purge. Then 3 mmol of poly-iso-butyl aluminum oxide and 0.2890 g of 10.017 mmol Cg) catalyst are added. Then the autoclave is heated to 85 ° C. A hydrogen pressure of 2 bar is created and then ethylene to a total pressure of 6 bar. A pressure of 6 bar is maintained during the polymerization by the introduction of ethylene. After the "-hour polymerization, they are obtained. S, O g of polymer, which corresponds to a yield of 1529 g of polymer / mmol 1Z Cr h. Melt index 190/5 1.12, and melt 190/15 14.01. , 2 5 190/5 Example 6 Analogously to example 4 on 17 (8 g of silicic acid is applied with i mmol of T-butyl chromate and 4.2637 g of Ti are added (O-iso-Cyc4 4 Cr: H1 - 1: 7.5. After "In-hour exposure at room temperature. The catalyst suspension is used in copolymerization. The catalyst has the following composition, weight,%: Chromium, 0.46 Titanium, 3.19; Silicic acid. Balance. the boil 138-170 ° C) and air are purged with nitrogen and 3 mmol of poly-isobutylaluminum oxide, 2.0 ml (0.01 mmol) of the suspension the lysing agent and the following amounts of butene-1. The autoclave is then heated to. A hydrogen pressure of 3 bar is created and then ethylene to a total pressure of 15 bar. During the 4-hour polymerization, the pressure of 15 bar is maintained by introducing ethylene. -1 The test results are shown in the table.
    0.36 4.03
    158.3 3957
    0.966
    11.2
    权利要求:
    Claims (1)
    [1]
    Claim
    A method of producing a catalyst for the polymerization of ethylene or copolymerization of ethylene and propylene by impregnating a carrier - silicic acid with a solution of a chromic ester and a titanium compound in hexane, followed by drying, characterized in that, in order to simplify the method, titanium alkoxide is used as a titanium compound general formula
    Ti (0R) 4 where R is iso-C ^ Hj or iso-C5H ^ and , with a molar ratio Ti / Cr = 3 _ 10: 1, moreover, the titanium compound is applied to the carrier after the chromic ester.
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    同族专利:
    公开号 | 公开日
    EP0003321B1|1981-11-25|
    AR223166A1|1981-07-31|
    EP0003321A1|1979-08-08|
    DE2802819A1|1979-07-26|
    BR7900393A|1979-08-21|
    ES476947A1|1979-06-16|
    CA1132967A|1982-10-05|
    AU523171B2|1982-07-15|
    US4305841A|1981-12-15|
    DE2961377D1|1982-01-28|
    IN150108B|1982-07-24|
    ZA79232B|1980-02-27|
    AU4354279A|1979-08-02|
    JPS54110190A|1979-08-29|
    引用文献:
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    RU2702232C2|2015-04-29|2019-10-07|Шеврон Филлипс Кемикал Компани Лп|Methods for preparing catalysts|
    RU2743038C2|2015-09-18|2021-02-12|Шеврон Филлипс Кемикал Компани Лп|Methods of producing catalyst|US3071601A|1957-04-05|1963-01-01|Robert S Aries|Oxidation of propylene|
    US3409681A|1964-06-25|1968-11-05|Exxon Research Engineering Co|Method of making novel bimetallic heterogeneous catalysts and their use in hydrocarbon conversions|
    US3622521A|1967-08-21|1971-11-23|Phillips Petroleum Co|Olefin polymerization with chromium and titanium-containing compounds|
    US3773742A|1971-02-02|1973-11-20|Hercules Inc|Tetraneopentyltitanium and use as polymerization catalyst|
    US3798250A|1971-12-30|1974-03-19|Hercules Inc|Tetraalkylchromium compounds|
    DE2118366A1|1971-04-15|1972-11-02|Phillips Petroleum Co., Bartlesville, OkIa. |Chromium/titanium-contg catalyst for olefin polymerisation|
    GB1415649A|1971-12-23|1975-11-26|Bp Chem Int Ltd|Olefin polymerisation process and catalyst for use therein|
    US3752795A|1972-03-24|1973-08-14|Standard Oil Co|Polymerization of olefins with a chomyl bis(triorganotitanate catalyst|
    GB1429174A|1972-06-12|1976-03-24|Bp Chem Int Ltd|Polymerisation process and catalyst|
    DE2233115A1|1972-07-06|1974-01-24|Veba Chemie Ag|PROCESS FOR THE PRODUCTION OF POLYAETHYLENE|
    US4016343A|1975-08-22|1977-04-05|Chemplex Company|Tetravalent chromium alkoxide polymerization catalyst and method|US5326165A|1991-06-26|1994-07-05|Irvine Scientific Sales Co.|Mixing apparatus|
    US5401816A|1993-09-27|1995-03-28|Phillips Petroleum Company|Transition metal catalyst, method of preparing catalyst, polymerization process employing catalyst, and polymer produced|
    EP0962468A1|1998-06-05|1999-12-08|Fina Research S.A.|Catalysts for polyethylene production and use thereof|
    EP1155054A1|1998-12-29|2001-11-21|Chevron Phillips Chemical Company Lp|Improved chromate ester catalyst and method of using same to produce high performance polyethylene products|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19782802819|DE2802819A1|1978-01-23|1978-01-23|METHOD FOR PRODUCING A CATALYST|
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