WO1994013708A1 - Procede de polymerisation d'ethylene a l'aide d'un catalyseur renfermant du chrome, et polymere d'ethylene ainsi obtenu - Google Patents

Procede de polymerisation d'ethylene a l'aide d'un catalyseur renfermant du chrome, et polymere d'ethylene ainsi obtenu Download PDF

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WO1994013708A1
WO1994013708A1 PCT/FI1992/000344 FI9200344W WO9413708A1 WO 1994013708 A1 WO1994013708 A1 WO 1994013708A1 FI 9200344 W FI9200344 W FI 9200344W WO 9413708 A1 WO9413708 A1 WO 9413708A1
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chromium
catalyst
polymerization
carrier
process according
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PCT/FI1992/000344
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English (en)
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Hilkka Knuuttila
Kalle Kallio
Marja-Riitta Hakala
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Neste Oy
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Priority to PCT/FI1992/000344 priority Critical patent/WO1994013708A1/fr
Publication of WO1994013708A1 publication Critical patent/WO1994013708A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene

Definitions

  • the invention relates to a method for the homo- and copoly- merization of ethylene with chromium catalyst by using hydrogen for controlling the molar mass and the molar mass distribution.
  • the invention also relates to a homo- or copoly er of ethylene prepared by this method.
  • Ethylene optionally, along with it other monomers, can be polymerized by so-called low-pressure processes using Ziegler-Natta type catalysts, in which the catalyst mainly consists of titanium compounds and organometallic aluminium compounds, and by the aid of catalysts based on chromium.
  • Ziegler-Natta type catalysts in which the catalyst mainly consists of titanium compounds and organometallic aluminium compounds, and by the aid of catalysts based on chromium.
  • the first chromium-based ethylene polymerization catalyst was developed by Hogan and Banks as early as in the middle of 1950's.
  • the catalyst is prepared by treating a silica carrier with chromium trioxide (Cr0 3 ) in an aqueous solution, whereby the hydroxyl groups on the surface of the silica react with the chromium trioxide and form chromate.
  • a polymerization catalyst of ethylene in which titanium tetraisopropylate is added to a silica carrier.
  • the solid product obtained is calcinated and impregnated with a chromium compound, for example a t-butyl chromate, and is then reimpregnated with the above-mentioned titanium compound.
  • the catalyst is activated by heating.
  • Triethyl aluminium solution is added as cocatalyst in the poly ⁇ merization stage.
  • Typical for chromium-containing polymerization catalysts is that the polymerization reaction does not begin immediately after bringing together the monomer and the catalyst, whether this took place by adding a catalyst to the monomer, for example in a gas phase, or by conducting the monomer into a polymerization medium containing the catalyst.
  • the long induction time in the beginning of the polymerization results in an ineffective use of the reactor, especially in batch processes, or in connection with frequent standstills of the reaction e.g. because of the exchange of polymer quality or the maintenance of the reactor.
  • An aim of the invention is to provide a method for the polymerization of ethylene, by which a large polymer yield can be obtained and in which the polymerization induction time is as short as possible.
  • a method is aimed at, by which a polyethylene is obtained having a certain molar mass or a certain molar mass distribution and particularly a broad one.
  • a method is aimed at in which the molar mass can be maximally regulated by means of hydrogen.
  • the layering of a chromium compound onto an inorganic oxide carrier can take place by any method, in which a solid or liquid compound, which is in solution or suspended in a solution, is layered onto another, solid compound.
  • the layering of the chromium compound onto an inorganic oxide carrier takes place by impregnating the inorganic carrier with a solution of the chromium compound. When needed, the thereby obtained impregnant is dried by evaporation immediately after the impregnation before the calcination.
  • the chromium compound layered on an oxide carrier is always calcinated at a high temperature, the chromium compound, independent of its quality, will oxidize to chromium trioxide.
  • the chromium compound can, in addition to the final chromium trioxide, be any chromium compound that can be calcinated to form chromium trioxide. Accordingly, also commercially available chromium trioxide can be used, but also chromium halides, chromium oxyhalides, chromium nitrates, chromium acetates, chromium sulphates, and chromium alcoholates, etc. are usable.
  • Chromium acetyl- acetonate is a usable chromium compound, too.
  • it is preferable to use such an amount of chromium compounds that the chromium (Cr) content of the layered product obtained in the catalyst synthesis is about 0.1 to 2% by weight.
  • the inorganic oxide carrier of the chromium catalyst used in the polymerization method according to the invention is preferably silica (Si0 2 ) , alumina (A1 2 0 3 ) , titania (Ti0 2 ) or some composition thereof.
  • the inorganic oxide carrier is pure silica.
  • the inorganic oxide carrier is a composition based on silica, the alumina content of which is about 1 to 5 by weight. Thereby, the composition can, of course, also contain other components than silica and alumina.
  • the inorganic oxide carrier is a composition based on silica, the titania content of which is about 1 to 10% by weight. Thereby, the silica-titania combination and the silica-alumina-titania combination come in the first place into question.
  • the layered product obtained is calcinated, that is, heated to a high temperature to modify the layered product thermally.
  • the chromium trioxide is attached onto the surface of the inorganic oxide carrier without the chromium trioxide changing essentially in any other respect.
  • the starting material is a chromium compound that can be calcinated to chromium trioxide, such as chromium acetylacetonate
  • the oxidization to chromium trioxide and the attachment of the chromium compound onto the surface of the inorganic oxide carrier occurs simultaneously.
  • the calcination conditions can, in principle, be of any kind leading to a chromium trioxide layered on an inorganic oxide carrier.
  • the calcination of the layered product is carried out during 3 to 15 hours at a temperature of 300 to 1200°C.
  • the reaction time of calcination is about 10 hours at a temperature of about 600°C.
  • the calcination stage can be carrier out, for example, in a fluidized bed.
  • a cooling takes place, during which, when the temperature is about 300°, the air is exchanged to nitrogen to provide an inert atmosphere.
  • the calcination product is reduced and alkylated with dialkyl aluminium ethoxide.
  • dialkyl aluminium ethoxide is diethyl aluminium ethoxide.
  • reaction composition is preferably mixed about 0.5 to 3.0 hours at a temperature of about 20 to 40°C.
  • such a dialkyl aluminium ethoxide amount is used that the molar ratio Al/Cr of the treated product is between about 0.5 to 6.0, preferably between about 1.0 to 2.5. Most preferably, such a dialkyl aluminium ethoxide amount is used in the preparation of the chromium catalyst that the molar ratio Al/Cr of the product is between 1.1 to 1.6.
  • the inorganic oxide carrier used in the invention can be prepared, for example, by impregnating a silica- or a silica-alumina -carrier with a liquid titanium compound or a solution of a titanium compound, by drying the impregnate and by calcinating the dried impregnate.
  • the impregnation with a liquid titanium compound or a solution of a titanium compound takes place with a titanium compound having the formula (II)
  • titanium compounds are titanium tetra-alkylates, of which titanium tetraisopropylate is useful.
  • an inorganic oxide carrier is prepared in this manner by impregnating with a titanium compound and calcinating, it is worth while using for the impregnation such an amount of the titanium compound that the content of the dried impregnate is the above-mentioned 1 to 10% by weight.
  • the obtained composition of silica or silica-alumina and the titanium compound is usually dried by evaporating the medium.
  • any organic ligands of the titanium compound are burnt away simultaneously as the titanium is bound to silica or silica/alumina.
  • the calcination is preferably carried out during about 3 to 10 hours at a temperature of about 300 to 1000°C.
  • the inorganic oxide carrier obtained by this kind of pretreatment is ready for a treatment with a chromium compound.
  • the method according to the invention for the poly ⁇ merization of ethylene polyethylene having a broad molar mass distribution is obtained by using the above-mentioned chromium catalyst.
  • the molar mass distribution can be affected by adjusting the optional titanium amount and the Al/Cr ratio at the chromium reduction and alkylation stages.
  • the activity of the catalyst according to the invention varies between 3 to 5kg of polyethylene/g of catalyst. The activity is also dependent on the titanium amount and the Al/Cr ratio at the reduction stage.
  • ethylene can be both homo- and copolymerized.
  • alpha-olefins come into question, of which especially the copolymers of butene, 1-hexene and some relatively long- chained 1-olefin that is the so-called LLDPE-polymer is a remarkable application. Since alpha-olefins are compounds that are close to ethylene, they can be used even in greater portions, upto even tenths of molar percentages.
  • Examples 1-16 1% of Cr. silica-alumina as carrier
  • Examples 1-13 Influence of diethylaluminium ethoxide on the activity, hydrogen sensitivity and melt flow rate (MFR)
  • Chromium treatment of the carrier is a Chromium treatment of the carrier
  • the polymerization takes place at normal standard slurry conditions, where the total pressure is 4000kPa, the temperature 105° C, the medium is an isobutane slurry, the partial pressure of ethylene is 1700kPa.
  • the polymerization time is 60 min. See table 1.
  • the catalyst is prepared as in example 1.
  • the polymerization was carried out as in example 1, but in the polymerization hydrogen was used as the chain transfer agent at lObars from a 500ml gas bomb. See table 1.
  • the catalyst is prepared as in example 1.
  • Calcinated chromium trioxide on a silica-alumina carrier (Cr0 3 /Si0 2 -Al 2 0 3 ) is treated with diethylaluminium ethoxide (CH 3 CH 2 ) 2 -Al-0-CH 2 CH 3 so that the molar ratio diethylaluminium ethoxide/Cr is 0.5.
  • l.Og of calcinated carrier is taken, on which is added 5ml of pentane and a genuine slurry is pre ⁇ pared.
  • the polymerization was carried out as in example 1. See table 1.
  • the catalyst was prepared as in example 1.
  • Example 9 The preparation, modification and polymerization of the catalyst were carried out as in example 6, but in the polymerization hydrogen was used at 20bars from a 500ml gas bomb. This gives a hydrogen/ethylene molar ratio 0.24. The results are in table 1.
  • Example 10 The catalyst was prepared as in example 1.
  • Calcinated chromium trioxide -silica-alumina is treated with diethylaluminium ethoxide (CH 3 CH 2 ) 2 -Al-0-CH 2 CH 3 so that the molar ratio diethylaluminium ethoxide/Cr is 2 consult 1.Og of the calcinated carrier is taken, on which is added 5ml of pentane and a genuine slurry is prepared. To the slurry is added dropwise 0.56ml of diethylaluminium ethoxide (a 20% pentane solution) , whereby a change of colour from brownish yellow to green can immediately be observed. To complete the reaction, the slurry is mixed for 2h at 35° C. After this the pentane is evaporated, after which the catalyst is ready for polymerization.
  • Example 11 The preparation, modification and polymerization of the catalyst were carried out as in example 10, but in the polymerization hydrogen was used at 5bars from a 500ml gas- bomb. This gives a hydrogen/ethylene molar ratio of 0.6. The results are in table 1.
  • Examples 14 to 16 present the influence of various reducing agents on the activity, hydrogen sensitivity and melt flow rate.
  • the catalyst was prepared as in example 1.
  • Calcinated chromium trioxide -silica-alumina is treated with triethylaluminium ethoxide (CH 3 CH 2 ) 3 -A1 so that the molar ratio triethylaluminium ethoxide/Cr is 1.
  • l.Og of the calcinated carrier is taken, 5ml of pentane is added on it and a genuine slurry is prepared.
  • To the slurry is added dropwise triethylaluminium (a 20% pentane solution) , whereby a change of colour from brownish yellow to green can immediately be observed.
  • the slurry is mixed for 2h at 35° C. Then, the pentane is evaporated, after which the catalyst is ready for polymerization.
  • Example 15 The catalyst was prepared as in example 1. '
  • the catalyst was prepared as in example 1.
  • Calcinated chromium trioxide -silica-alumina is treated with triethyl borane (CH 3 CH 2 ) 3 B so that the molar ratio triethylborane/Cr is 1.
  • l.Og of the calcinated carrier is taken, 5ml of pentane is added onto it and a genuine slurry is prepared.
  • To the slurry is added dropwise 0.56ml of triethylborane (a 20% pentane solution) , whereby a change of colour from brownish yellow to green can immediately be observed.
  • the slurry is mixed for 2h at 35° C. After this the pentane is evaporated, after which the catalyst is ready for polymerization.
  • Examples 17-26 Influence of diethylaluminium ethoxide on the activity, hydrogen sensitivity and melt flow rate (MFR) .
  • a commercial catalyst intermediate namely a silica-titanium cogel was used, impregnated with chromium acetylacetonate and containing 1% of chromium.
  • This carrier was dried in a fluidized bed with dry air at 150° C for 2 hours and calcinated for 5 hours at 550° C. The air was exchanged to dried nitrogen at the end of the activation stage when the temperature had decreased to 400 - 300° C.
  • Ethylene was polymerized by the aid of catalysts in an 3- liter autoclave reactor, in which 1.8 liters of isobutane was used as medium. At the temperature 105° C used the partial pressure of ethylene was 1700kPa at a total pressure of 40000kPa. The 140mg catalyst amount used gave a yield of 410gPE. See table 3.
  • the activation of the catalyst carrier was carried out as in example 17.
  • the reduction/alkylation of the catalyst 3.0g of calcinated catalyst was slurried in about 30ml of dry pentane in an inert atmosphere and to the slurry was added dropwise freshly prepared diethylaluminium ethoxide (DEALOX) so that a molar ratio Al/Cr of was achieved. The colour of the catalyst changed from yellowish to greenish indicating reduction of the chromium. The slurry was mixed for 2 hours at 35° C to ensure the reduction reaction. The polymerization of the catalyst was carried out as in example 17, but the catalyst amount used was 120mg, which gave a yield of 615gPE. See table 3.
  • DEALOX diethylaluminium ethoxide
  • the polymerization of the catalyst was carried out as in example 18, but in the polymerization hydrogen at 5 bars from a 500ml hydrogen bomb was used as the chain transfer agent, which gave the hydrogen/ethylene molar ratio 0.06.
  • the catalyst amount used was 120mg, which gave the yield
  • the polymerization of the catalyst was carried out as in example 18, but in the polymerization hydrogen at 10 bars from a 500ml hydrogen bomb was used as the chain transfer agent, which gave the hydrogen/ethylene molar ratio 0.12.
  • the catalyst amount used was 120mg, which gave the yield 344gPE.
  • the activation of the catalyst carrier was carried out as in example 17.
  • calcinated catalyst 3.0g was slurried in about 30ml of dry pentane in an inert atmosphere and and to the slurry was added dropwise freshly prepared diethylaluminium ethoxide (DEALOX) so that an Al/Cr molar ratio of 2.0 was achieved.
  • the colour of the catalyst changed from yellowish to greenish indicating reduction of the chromium.
  • the slurry was mixed for 2 hours at 35° C to ensure the reduction reaction.
  • Example 23 The activation and the reduction/alkylation of the catalyst carrier were carried out as in example 22.
  • the polymerization of the catalyst was carried out as in example 22, but in the polymerization hydrogen at 10 bars from a 500ml hydrogen bomb was used as the chain transfer agent, which gave the hydrogen/ethylene molar ratio 0.12.
  • the catalyst amount used was 130mg, which gave a yield of 336gPE.
  • the polymerization of the catalyst was carried out as in example 22, but in the polymerization hydrogen at 20 bars from a 500ml hydrogen bomb was used as the chain transfer reagent, which gave the hydrogen/ethylene molar ratio 0.24.
  • the catalyst amount used was 120mg, which gave a of yield 387gPE.
  • Example 25 The activation of the catalyst carrier was carried out as in example 17.
  • the colour of the catalyst changed from yellowish to greenish indicating reduction of the chromium.
  • the slurry was mixed for 2 hours at 35° C to ensure the reduction reaction.
  • the polymerization of the catalyst was carried out as in example 25, but in the polymerization hydrogen at 20 bars from a 500ml hydrogen bomb was used as a chain transfer agent, which gave the hydrogen/ethylene molar ratio 0.24.
  • the catalyst amount used was 120mg, which gave the yield 328gPE.
  • Preparation and calcination of the carrier 1% Cr is impregnated onto a silica-alumina(2.5%) - titania(5%) -carrier as Cr0 3 from an aqueous solution. After this the water is evaporated, which is succeeded by activation of the catalyst.
  • the catalyst is calcinated in air at 650° C for lOh. Cooling in nitrogen at 300° C thereafter. The catalyst was treated inertly.
  • the polymerization took place at normal conditions.
  • the total pressure was 4000kPa, the temperature 105° C, the environment being an isobutane slurry, and the partial pressure of ethylene being 1700kPa.
  • the polymerization time was 60 min. and the catalyst amount 142mg. In the polymerization 300g of polyethylene was formed.
  • the polymerization was carried out as above, but for the regulation of the molecular weight hydrogen was used, which acted as the chain transfer agent.
  • the amount of the hydrogen corresponded to 10 bars and was fed from a 500ml gas container.
  • the hydrogen was flushed with ethylene into the actual polymerization reactor.
  • the catalyst amount was 135mg. In the polymerization 225g of polyethylene was formed.
  • the calcinated chromium trioxide is treated with diethyl ⁇ aluminium ethoxide (CH 3 CH 2 ) 2 -Al-0-CH 2 CH 3 so that the molar ratio diethylaluminium ethoxide/Cr is 2.
  • 1.218g of the calcinated carrier is taken, 5ml of pentane is added onto it and a genuine slurry is prepared.
  • To the slurry is added dropwise 0.45ml of diethylaluminium ethoxide (a 20% pentane solution) , whereby a change of colour from brownish yellow to green can immediately be observed.
  • the slurry is mixed for 2h at 35° C. After this the pentane is evaporated, after which the catalyst is ready for polymerization.
  • the polymerization took place at normal conditions.
  • the total pressure was 4000kPa, the temperature 105° C, the environment an isobutane slurry, the partial ethylene pressure 1700kPa, the polymerization time 60 min. and the catalyst amount 128mg.
  • the polymerization 673g of polyethylene was formed.
  • Example 30 The preparation, chromium treatment and calcination of the carrier and the modification of the catalyst were carried out as in example 29.
  • the polymerization was the same as in example 29, but for the regulation of the molecular weight hydrogen was used, which acted as the chain transfer agent.
  • the amount of hydrogen corresponded to 10 bars from a 500ml hydrogen bomb, the hydrogen being flushed into the actual polymerization reactor.
  • the catalyst amount was 128mg. In the polymerization 550g of polyethylene was formed.
  • the calcinated chromium trioxide is treated with triethylaluminium (CH 3 CH 2 ) 3 -A1 so that the triethyl aluminium/Cr molar ratio is 2.
  • 1.264g of the calcinated carrier is taken, 5ml of pentane is poured on it and a genuine slurry is prepared.
  • To the slurry is added dropwise 0o39ml of triethylaluminium (a 20% pentane solution), • whereby a change of colour from brownish yellow to dark green can immediately be observed.
  • the slurry is mixed for 2h at 35° C. After this the pentane is evaporated, after which the catalyst is ready for polymerization.
  • the polymerization took place at normal conditions.
  • the total pressure was 4000kPa, the temperature 105° C, the environment an isobutane slurry, the partial pressure of ethylene 1700kPa, the polymerization time 60 min. and the catalyst amount 130mg.
  • the polymerization 443g of polyethylene was formed.
  • the polymerization was the same as in example 31, but for the regulation of the molecular weight hydrogen was used, which acted as the chain transfer agent.
  • the amount of hydrogen corresponded to 10 bars and was fed from a 500ml hydrogen bomb, the hydrogen being flushed with ethylene into the actual polymerization reactor.
  • the catalyst amount was 13mg. In the polymerization 433g of polyethylene was formed.
  • Calcinated chromium trioxide is treated with trimethylaluminium (CH 3 ) 3 A1 so that the molar ratio trimethylaluminium/Cr is 2.
  • 1.242g of the calcinated carrier is taken, on which is added 5ml of pentane and a genuine slurry is prepared.
  • To the slurry is added dropwise 0.50ml of trimethylaluminium (a 10% heptane solution) , whereby a change of colour from brownish yellow to brownish green can immediately be observed.
  • the slurry is mixed for 2h at 35° C. After this the pentane is evaporated, after which the catalyst is ready for polymerization.
  • the polymerization takes place at normal conditions.
  • the total pressure is 4000kPa, the temperature 105° C, the environment being an isobutane slurry, the partial pressure of ethylene 1700kPa, the polymerization time 60 min. and the catalyst amount 129mg.
  • the polymerization 610 of polyethylene was formed.
  • the polymerization was in other respects the same as in example 33, but for the regulation of the molecular weight hydrogen was used, which acts as the chain transfer agent.
  • the amount of hydrogen corresponded to 10 bars and was fed from a 500ml hydrogen bomb, which was flushed with ethylene into the actual polymerization reactor.
  • the catalyst amount was 124mg. In the polymerization 529g of polyethylene was formed.
  • Example 35 The preparation and calcination of the carrier were carried out as in example 27.
  • Calcinated chromium trioxide is treated with dimethylaluminium ethoxide (CH 3 ) 3 -Al-0-CH 2 CH 3 so that the molar ratio dimethylaluminium ethoxide/Cr is 2.
  • 1.347g of the calcinated carrier is taken, on it is added 5ml of pentane and a genuine slurry is prepared. To the slurry is added dropwise 0.77ml of dimethylaluminium ethoxide (a 10% heptane solution) , whereby a change of colour from brownish yellow to green can immediately be seen. To complete the reaction, the slurry is mixed for 2h at 35° C. After this the pentane is evaporated, after which the catalyst is ready for polymerization.
  • the polymerization took place at normal conditions.
  • the total pressure was 4000kPa, the temperature 105° C, the environment an isobutane slurry, the partial pressure of ethylene 1700kPa, the polymerization time 60 min. and the catalyst amount I36mg.
  • the polymerization 411g of polyethylene was formed.
  • the polymerization was in other respects the same as in example 35, but for the regulation of the molecular weight hydrogen was used, which acted as the chain transfer agent.
  • the amount of hydrogen corresponded to 10 bars and was fed from a 500ml hydrogen bomb, the hydrogen being flushed with ethylene into the actual polymerization reactor.
  • the catalyst amount was 124mg. In the polymerization 290g of polyethylene was formed.
  • Calcinated chromium trioxide is treated with triethylborane (CH 3 CH 2 ) 3 -B so that the molar ratio triethylborane/Cr is 2.
  • 1.292g of the calcinated carrier is taken, on which is added 5ml of pentane and a genuine slurry is prepared.
  • To the slurry is added dropwise 0.49ml of triethylborane (a 14% heptane solution) , whereby a change of colour from brownish yellow to brownish green can immediately be observed.
  • the slurry is mixed for 2h at 35° C. After this the pentane is evaporated, after which the catalyst is ready for polymerization.
  • the polymerization took place at normal conditions.
  • the total pressure was 4000kPa, the temperature 105° C, the environment an isobutane slurry, the partial pressure of ethylene 1700kPa, the polymerization time 60 min. and the catalyst amount 124mgggi In the polymerization 355g of polyethylene was formed.
  • the polymerization was in other respects the same as in example 37, but for the regulation of the molecular weight hydrogen was used, which acts as the chain transfer agent.
  • the amount of hydrogen corresponded to 10 bars and was fed from a 500ml hydrogen bomb, the hydrogen being flushed with ethylene into the actual polymerization reactor.
  • the catalyst amount was 131mg. In the polymerization 296g of polyethylene was formed.
  • the polymerization took place at normal conditions.
  • the total pressure was 4000kPa, the temperature 105° C, the environment an isobutane slurry, the partial pressure of ethylene 1700kPa, the polymerization time 60 min. and the catalyst amount 124mg.
  • the polymerization 355g of polyethylene was formed.
  • the polymerization was in other respects the same as in example 39, but for the regulation of the molecular weight hydrogen was used, which acted as the chain transfer agent.
  • the amount of hydrogen corresponded to 10 bars and was fed from a 500ml hydrogen bomb, the hydrogen being flushed with ethylene into the actual polymerization reactor.
  • the catalyst amount was 131mg. In the polymerization 296g of polyethylene was formed.
  • Silica-alumina-titania -carrier 5% by wt. of Ti, 1% by wt. of Cr as Cr0 3

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Préparation de polymères d'éthylène par polymérisation d'éthylène seul ou par copolymérisation d'éthylène avec un ou plusieurs comonomères. Le comonomère est de préférence une ou plusieurs 1-oléfines. La réaction de polymérisation s'effectue à l'aide d'un catalyseur à base d'oxyde de chrome. On place l'oxyde de chrome sur un support constitué normalement d'un oxyde inorganique tel que la silice, l'alumine, le dioxyde de titane, etc., ou leurs mélanges. On soumet l'oxyde de chrome sur le support à un traitement par éthoxyde de dialkylaluminium, de manière que le catalyseur ainsi obtenu soit particulièrement sensible à l'action de l'hydrogène au cours de la polymérisation. Autrement dit, le poids moléculaire du polymère et sa répartition sont régulables en fonction de la quantité d'hydrogène.
PCT/FI1992/000344 1992-12-17 1992-12-17 Procede de polymerisation d'ethylene a l'aide d'un catalyseur renfermant du chrome, et polymere d'ethylene ainsi obtenu WO1994013708A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007015927A1 (fr) * 2005-07-27 2007-02-08 Univation Technologies, Llc Moulage par extrusion-soufflage de résines de polyéthylène
US7388059B2 (en) * 2004-06-28 2008-06-17 Japan Polyethylene Corporation Ethylene polymer, catalyst for producing thereof and method for producing thereof
WO2009108174A1 (fr) * 2008-02-27 2009-09-03 Univation Technologies, Llc Catalyseurs à base de chrome modifiés et procédés de polymérisation pour les utiliser
WO2010150410A1 (fr) 2009-06-26 2010-12-29 日本ポリエチレン株式会社 Résine de polyéthylène, catalyseur utilisé pour la production de celle-ci, son procédé de fabrication, article moulé en matière plastique, creux, contenant la résine de polyéthylène et utilisation de l'article moulé en matière plastique creux
US8129484B2 (en) 2005-07-27 2012-03-06 Univation Technologies, Llc Blow molding polyethylene resins
WO2012086780A1 (fr) 2010-12-24 2012-06-28 日本ポリエチレン株式会社 Polyéthylène ayant une distribution du degré de ramification améliorée
WO2012133713A1 (fr) 2011-03-30 2012-10-04 日本ポリエチレン株式会社 Polymère d'éthylène, procédé pour la production d'un polymère d'éthylène, procédé pour la production d'un catalyseur de polymérisation et moulage creux en plastique comprenant un polymère d'éthylène et son utilisation

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DE2723416A1 (de) * 1976-05-24 1977-12-15 Stamicarbon Verfahren zur polymerisation von alkylenen
SU607835A1 (ru) * 1976-05-05 1978-05-25 Предприятие П/Я В-8952 Способ получени полиэтилена
EP0291824A2 (fr) * 1987-05-20 1988-11-23 QUANTUM CHEMICAL CORPORATION (a Virginia corp.) Compositions améliorées de catalyseur à base de chrome et polymérisation utilisant celle-ci

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WO2007015927A1 (fr) * 2005-07-27 2007-02-08 Univation Technologies, Llc Moulage par extrusion-soufflage de résines de polyéthylène
US7915357B2 (en) 2005-07-27 2011-03-29 Univation Technologies, Llc Blow molding polyethylene resins
US8129484B2 (en) 2005-07-27 2012-03-06 Univation Technologies, Llc Blow molding polyethylene resins
TWI449718B (zh) * 2008-02-27 2014-08-21 Univation Tech Llc 經改質之鉻基觸媒及使用彼之聚合方法
WO2009108174A1 (fr) * 2008-02-27 2009-09-03 Univation Technologies, Llc Catalyseurs à base de chrome modifiés et procédés de polymérisation pour les utiliser
JP2011513533A (ja) * 2008-02-27 2011-04-28 ユニベーション・テクノロジーズ・エルエルシー 修飾クロム系触媒およびそれを用いる重合方法
US9303103B2 (en) 2008-02-27 2016-04-05 Univation Technologies, Llc Modified chromium-based catalysts and polymerization processes for using the same
WO2010150410A1 (fr) 2009-06-26 2010-12-29 日本ポリエチレン株式会社 Résine de polyéthylène, catalyseur utilisé pour la production de celle-ci, son procédé de fabrication, article moulé en matière plastique, creux, contenant la résine de polyéthylène et utilisation de l'article moulé en matière plastique creux
EP2447287A4 (fr) * 2009-06-26 2013-02-27 Japan Polyethylene Corp Résine de polyéthylène, catalyseur utilisé pour la production de celle-ci, son procédé de fabrication, article moulé en matière plastique, creux, contenant la résine de polyéthylène et utilisation de l'article moulé en matière plastique creux
US9193809B2 (en) 2009-06-26 2015-11-24 Japan Polyethylene Corporation Polyethylene based resin, producing catalyst for the same, method for producing the same, hollow plastic molded article containing polyethylene based resin, and use of the same
EP2447287A1 (fr) * 2009-06-26 2012-05-02 Japan Polyethylene Corporation Résine de polyéthylène, catalyseur utilisé pour la production de celle-ci, son procédé de fabrication, article moulé en matière plastique, creux, contenant la résine de polyéthylène et utilisation de l'article moulé en matière plastique creux
WO2012086780A1 (fr) 2010-12-24 2012-06-28 日本ポリエチレン株式会社 Polyéthylène ayant une distribution du degré de ramification améliorée
WO2012133713A1 (fr) 2011-03-30 2012-10-04 日本ポリエチレン株式会社 Polymère d'éthylène, procédé pour la production d'un polymère d'éthylène, procédé pour la production d'un catalyseur de polymérisation et moulage creux en plastique comprenant un polymère d'éthylène et son utilisation
US10301409B2 (en) 2011-03-30 2019-05-28 Japan Polyethylene Corporation Ethylene-based polymer, manufacturing method of ethylene-based polymer and manufacturing method of catalyst for polymerization, and molded article of hollow plastics containing ethylene-based polymer and use thereof

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