WO2005026215A1 - ポリオレフィンの製造方法および気相重合装置 - Google Patents
ポリオレフィンの製造方法および気相重合装置 Download PDFInfo
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- WO2005026215A1 WO2005026215A1 PCT/JP2004/013080 JP2004013080W WO2005026215A1 WO 2005026215 A1 WO2005026215 A1 WO 2005026215A1 JP 2004013080 W JP2004013080 W JP 2004013080W WO 2005026215 A1 WO2005026215 A1 WO 2005026215A1
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- polyolefin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/087—Heating or cooling the reactor
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
Definitions
- the present invention relates to a method for producing a polyolefin, particularly a polyolefin such as a propylene block copolymer, in more detail >>; gas-phase polymerization using an olefin polymerization catalyst prevents the polymer from adhering to the polymerization tank wall and the polymerization stirring blade.
- the present invention relates to a production method and a vapor-phase polymerization apparatus capable of suppressing production of polyolefin for a long term, continuously and stably.
- Polyolefins such as polypropylene and propylene block copolymers, have high activity and improved tacticity by improving Ziegler / Natta catalysts.
- the above has been achieved.
- it has become possible to reduce the metal components such as the transition metal catalyst component present in the polymer and the amorphous polypropylene component.
- the polymerization method does not require solvent recovery or whip-making processes, recovers monomers, facilitates polymer drying, Because of its advantages such as being able to cope with the diversification of polymerization, a polymerization method using a gas phase method has attracted attention.
- a crystalline homopolymer or copolymer of propylene is produced in the first polymerization tank, and propylene and other ⁇ -olebuin such as ethylene are produced in the second polymerization tank.
- propylene block copolymer is a composition having excellent strength, rigidity and heat resistance of the crystalline polypropylene, as well as excellent impact resistance due to the rubber-like random copolymer, particularly excellent at low temperatures. For this reason, it has been widely used as exterior materials such as pampers, automotive parts such as interior materials such as instrument panels and doors, containers and sheets.
- the method for producing polyolefin by the gas phase method is a very excellent process.
- the gas phase polymerization tank is divided into a polymer powder portion and a gas phase portion regardless of the gas phase fluidized bed type or the stirred fluidized bed type. Therefore, the effects of stirring and homogenization may not be sufficient when compared with the solution method or slurry method, due to insufficient flow, stirring, and uniformity of the entire tank.
- the second random copolymer polymerization tank in the production of the propylene block copolymer since the copolymer is rubbery and has high adhesiveness, adhesion between the polymer and the copolymer particles is high.
- adhesion to the wall of the polymerization tank and the stirring blade is likely to occur.
- This adhesion only makes it difficult to achieve stable and long-term continuous production.
- This adhesion causes problems such as high molecular weight and gelation, resulting in deterioration of the quality of the final molded product.
- small clumps generated by the adhesion of particles may cause troubles such as clogging of the polymer powder transfer pipe.
- the filter may be clogged in the monomer circulation piping for cooling.
- quality deterioration refers to insoluble or hardly meltable components due to gelation due to long-term stagnation due to adhesion, resulting in deterioration of physical properties and deterioration of commercial value, such as deterioration of appearance of molded products and starting point of destruction That is.
- Also disclosed is a method of supplying an active hydrogen compound to a random copolymerization reaction system at a rate of 0.001 to 1 mol per 1 g of aluminum in a highly stereoregular polymerization catalyst for example, see Japanese Patent Application Laid-Open No. H11-163,086). (See Sho 61-69821).
- this publication merely shows an example of batch polymerization instead of continuous polymerization. Therefore, although it is shown that the specific method of supplying the active hydrogen compound and the bulk specific gravity of the obtained polymer are increased, no particular description is given of the adhesion preventing effect. This is a natural result of the uniformity of the batch polymerization.
- a method of supplying alcohol to a transfer channel between a crystalline polypropylene polymerization tank and a propylene random copolymer polymerization tank in a monomer circulation system for cooling and a method for supplying alcohols are specifically described.
- these methods are methods in which the inhibitor of the activity of the olefin polymerization catalyst is not directly supplied to the polymerization tank. These methods attempt to improve the dispersibility by supplying a catalyst activity inhibitor to a polymer powder transfer or monomer supply pipe, but as a result, the catalyst activity inhibitor is This is an excellent method because it is supplied to the polymerization tank.
- Japanese Patent Application Laid-Open No. 11-141155 discloses that a heptane solution of isopropanol having a concentration of 17% by mass is weighed in a transfer conduit connecting the former reactor and the latter reactor of two reactors. An example of feeding is shown. As a comparative example, a method of measuring and feeding the same solution directly to the subsequent reactor was shown. It is. As a result, the amount of lumps and agglomerates in the powder bed of the latter stage reactor was 45 to 35% in the case of the example operating for 3 weeks compared to the comparative example, and the reactor wall It is shown that the amount of film and sediment on the baffle plate has been reduced to 25 to 35%, respectively. Although the reduction effect has been quantitatively evaluated, it is clear that there is a limit to the reduction of lumps, aggregates, and sediments even with the improved method, which is not always satisfactory.
- An object of the present invention is to provide a method for producing a polyolefin and a gas-phase polymerization apparatus which can stably and continuously produce without suppressing clogging of pipes, without clogging of pipes, and without deterioration in quality.
- a cooling medium is supplied from the bottom and at least one side of the polymerization tank.
- the present invention provides a polyolefin gas phase characterized in that a cooling medium supply mechanism for cooling is provided.
- FIG. 1 is a schematic view showing an embodiment of a subsequent polymerization tank in an apparatus for producing a propylene-ethylene block copolymer which is an example of a polyolefin gas-phase polymerization apparatus of the present invention.
- 1 is a post-stage polymerization tank
- 2 is a monomer supply pipe
- 3 is a polymer discharge pipe
- 4 is a cooling medium supply mechanism
- 5 is a stirring blade
- 6 is a gas phase.
- the present invention is generally applicable to a method for producing polyolefin by continuous gas phase polymerization using an olefin polymerization catalyst, and is particularly preferably applicable to a method for producing a propylene block copolymer.
- the monomer used for producing the polyolefin of the present invention is not particularly limited, and ethylene, propylene, 1-butene, 11-pentene, 4-methynole-pentene-11, 1-hexene, Orefins such as 1-octene, 1-nonene and 1-decene can be exemplified.
- These ⁇ -olefins may be homopolymerized, or may be copolymerized with two or more ⁇ -olefins or produced with other copolymerizable monomers such as vinyl acetate and acrylic acid. You can also.
- the olefin polymerization catalyst used in the method for producing polyolefin of the present invention is not particularly limited, and various known catalysts can be used. These catalysts include, for example, Ziegler containing a solid catalyst component prepared using a halide or alcohol of trivalent or tetravalent titanium, an alkoxytitanium halide, magnesium chloride, an alkoxymagnesium, or the like.
- olefin polymerization catalysts used in known gas-phase processes such as solid catalysts containing a metallocene-based compound containing a titanium, zirconium, or hafnium-based compound having a cyclopentagel group, such as a titanium-based catalyst having a cyclopentagel group
- these catalyst components include organoaluminum compounds such as alkylaluminum and aluminoxane, known cocatalysts such as ionic complexes and Lewis acids, and catalysts prepared using electron donors. it can. Further, an electron donating compound can be used at the time of polymerization.
- vapor phase polymerization tank used for producing the vapor phase polyolefin of the present invention there is no particular limitation on the vapor phase polymerization tank used for producing the vapor phase polyolefin of the present invention, and various known apparatuses can be used.
- an apparatus shown in "Chemical Equipment, pp. 62-74, Vol. 41, No. 12 (1999)" can be used.
- a fluidized-bed polymerization tank for example, Japanese Patent Application Laid-Open No. Hei 4-234409
- a vertical polymerization tank having a stirring blade Japanese Patent Application Laid-Open No. Sho 53-123,487) And Japanese Patent Application Laid-Open No. Sho 544-23258
- a horizontal polymerization tank having a stirring blade Japanese Patent Application Laid-Open No. 63-232011.
- the polymerization tank may be a single-stage or single-stage polymerization tank, or one having two or more stages of a plurality of polymerization tanks.
- the solid catalyst and the monomer are continuously supplied to the polymerization tank, The offspring are extracted continuously or intermittently.
- a method is employed in which the monomer gas in the polymerization tank is cooled by an external compressor or condenser, the cooled monomer is sprayed into the polymerization tank, and the polymerization heat is removed by the latent heat of evaporation.
- the method for producing polyolefin of the present invention can be preferably applied to the production of polyolefin using two or more polymerization tanks, usually two polymerization tanks. That is, polymerization is performed in the first and second polymerization tanks to obtain polymers (copolymers) having different properties.
- polymerization is performed in the first and second polymerization tanks to obtain polymers (copolymers) having different properties.
- rubbery random copolymerization is carried out in the presence of the crystalline polyolefin polymerized in the former stage, which is suitable for producing polyolefin as a mixed composition of both polyolefins. Can be adopted.
- Examples of such two-stage polymerization include polymerization of polyolefins having different molecular weights in each polymerization tank, (co) polymerization of different monomers, copolymerization of different copolymerization compositions, (co) polymerization of different crystallinity, and the like. It is possible to select a production method corresponding to the intended polyolefin such as a combination.
- the method for producing polyolefin of the present invention is characterized in that, in the method for producing polyolefin by continuous gas-phase polymerization using an olefin polymerization catalyst, a circulating medium for cooling is supplied from the bottom and at least one side of the polymerization tank.
- a circulating medium for cooling is supplied from the bottom and at least one side of the polymerization tank. This is mainly applicable to a polymerization tank after the two-stage polymerization.
- the circulating medium for cooling only needs to be able to remove the heat of polymerization, and may be a liquid, a gas, or a mixture of a liquid and a gas. Liquid is preferred because of its excellent cooling effect.
- the polyolefin gas-phase polymerization apparatus of the present invention is a polyolefin gas-phase polymerization apparatus having a monomer supply pipe, a polymer discharge pipe, and a polymerization tank provided with a stirring blade in some cases. It has a structure provided with a cooling circulating medium supply mechanism for supplying a cooling circulating medium from one place.
- 'A method for producing a lock copolymer will be described as an example.
- FIG. 1 is a schematic diagram showing an embodiment of a polymerization tank at a subsequent stage in a propylene-ethylene block copolymer production apparatus which is an example of a polyolefin gas-phase polymerization apparatus of the present invention.
- the latter polymerization tank 1 is composed of a monomer supply pipe 2, a polymer discharge pipe 3, a circulating medium supply mechanism 4 for cooling, and, in some cases, a stirring blade 5, and the inside of the polymerization tank is a gas phase part (upper part) 6 and a powder part. (Lower) It is divided into seven. Its cooling circulation medium, usually, hydrogen to zero. 0 1 to 1% by weight, ethylene is 5-4 0 mass 0/0, propylene 4 0-9 0% by weight, propane 4-2 0 wt% , nitrogen 0 to 1 mass 0 I, methane from 0. 0 1 to 5 mass%.
- the circulating cooling medium not only from the bottom surface but also from the side surface to the powder portion of the polymerization tank, and the height of the powder portion is 2 or more. It is preferable to supply from.
- the supply from this side varies depending on the structure of the polymerization tank, the state of forming the powder portion, and the like, but may be supplied from a plurality of positions.
- the amount supplied from the side is usually 0.05 to 0.5 times (mass) the amount supplied from the bottom.
- the above-mentioned cooling circulating medium supply mechanism generally employs a nozzle.
- the method for producing polyolefin of the present invention is particularly useful in a polymerization having a plurality of polymerization steps, in which a propylene homopolymer or a propylene copolymer having a content of other a-olefins of 5% by mass or less is used in a first polymerization tank.
- a propylene homopolymer or a propylene copolymer having a content of other a-olefins of 5% by mass or less is used in a first polymerization tank.
- propylene and another a-olefin are randomly copolymerized in the presence of the crystalline polypropylene to form a propylene block copolymer.
- the supply of the circulating medium for cooling the second polymerization tank is preferably applied not only to the bottom but also to the method for producing block polypropylene which is supplied from the position of the side wall of the polymerization tank.
- the method for producing polyolefin and the polymerization apparatus of the present invention there is a case of producing a propylene block copolymer.
- a propylene block copolymer having excellent impact resistance, especially low-temperature impact resistance can be produced by the continuous phase composed of crystalline polypropylene and the dispersed phase composed of rubber-like particles (including polyethylene).
- a block polypropylene copolymer having desired properties can be produced.
- the monomer in the random copolymer in the second-stage polymerization tank is a combination of propylene and other ⁇ -olefins such as ethylene and 1-butene, but the copolymer of propylene and other ⁇ -olefins is used.
- the polymerization ratio (mass ratio) is usually 10 to 90 to 90, preferably 20 to 85 to 80 to 15.
- the content ratio of the random copolymer to be copolymerized in the latter stage in the propylene block copolymer is usually 3 to 60% by mass, preferably 5 to 50% by mass.
- the polymerization catalyst examples include a high stereoregularity catalyst obtained by using ( ⁇ ) a solid catalyst component containing at least a magnesium atom, a titanium atom and a halogen atom, and ( ⁇ ) an organoaluminum compound.
- a catalyst for example, a highly stereoregular catalyst obtained by using the following components (II) and (II) can be mentioned.
- a solid catalyst component obtained by using (a) a magnesium compound and (b) a titanium compound.
- (B) an organoaluminum compound Preferably, the following components (A), (B) and (C) And high stereoregularity catalysts obtained by using
- the magnesium compound is not particularly limited. Magnesium oxide, magnesium hydroxide, dianolequinolemagnesium, anolequinolemagnesium halide, magnesium halide, magnesium dialkoxide, etc., specifically, magnesium chloride, magnesium Jetoxide, magnesium dimethoxide and the like can be mentioned.
- the magnesium compound a known solid product obtained by reacting a metal magnesium, a halogen, and an alcohol can be suitably used.
- examples of the alcohol include methanol and ethanol, and those having a water content of 200 ppm or less are easy to obtain a solid product having good morphology.
- the halogen chlorine, bromine, iodine, particularly iodine is preferably used.
- titanium compound any titanium compound can be used.
- the general formula (1) is the general formula (1)
- X 1 is a halogen atom, particularly a chlorine atom
- R 1 is a hydrocarbon group having 1 to 10 carbon atoms, particularly a linear or branched alkyl group, and a plurality of groups R 1 are present. In some cases, they may be the same or different from each other, and n is an integer from 0 to 4.
- any electron-donating compound (c) can be used if necessary.
- These electron donating compounds are usually organic compounds containing oxygen, nitrogen, phosphorus or sulfur.
- amines, amides, ketones, nitriles, phosphines, esters, ethers, thioethers, alcohols, thioesters, acid anhydrides, acid halides, aldehydes, organic Acids and organic silicon compounds having a Si—O—C bond can be exemplified.
- aromatic diesterol phthalates such as getyl phthalate, dibutyl phthalate, diisobutyl phthalate, and dihexyl phthalate, dimethyl dimethyl silane, getyl ethoxy silane, diphenyl dimethyl silane, and cyclohexymethyl
- organic silicon compounds such as dimethyoxysilane, di-butinoresimethoxysilane, diisobutyldimethyoxysilane, diisopropyldimethyoxysilane, dicyclohexyldimethyoxysilane, and dicyclopentyl / resimethoxysilane.
- the solid catalyst component (A) can be prepared by a known method using a magnesium compound (a), a titanium compound (b) and, if necessary, an electron-donating compound (c).
- a magnesium compound (a) is brought into contact with an electron-donating compound (c), and then brought into contact with a titanium compound (b).
- the contact condition is not particularly limited, and is usually 0.01 to 10 mol, preferably 0.05 to 5 mol of the electron donating compound (c) per mol of the magnesium compound (a) in terms of magnesium atom.
- a mole is added, and the mixture is contacted at 0 to 200 ° C for 5 minutes to 10 hours, preferably at 30 to 150 ° C for 30 minutes to 3 hours.
- an inert hydrocarbon such as pentane, hexane and heptane may be added to this preparation. it can.
- the conditions for contacting the titanium compound (b) with the magnesium compound (a) or the contact product thereof with the electron-donating compound (c) are not particularly limited.
- the titanium compound (b) is added in an amount of 1 to 50 mol, preferably 2 to 20 mol, and is added at 0 to 200 ° C for 5 minutes to 10 hours, preferably at 30 to 150 ° C for 30 minutes to 5 minutes. Contact for time.
- the contact with the titanium compound (b) can be carried out in a state where the liquid titanium compound (for example, titanium tetrachloride) is used alone, and the other titanium compounds are dissolved in any inert hydrocarbon. .
- halogenated hydrocarbons for example, halogenated silicon compounds, halogen gas, hydrogen chloride, iodine, etc. Hydrogen or the like can be brought into contact with the magnesium compound (a). After completion of the contact, it is preferable to wash the product with an inert hydrocarbon.
- the organoaluminum compound (B) is not particularly limited, and has the following general formula (2)
- R 2 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, m is an integer of 1 to 3, and X 2 is an octogen atom (a chlorine or bromine atom) Is.)
- trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dialkylaluminum monochloride such as getylaluminum monochloride, dipropylaluminum monochloride, etc. Can be mentioned.
- an electron donating compound (C) can be used in combination, if necessary.
- the electron donating compound (C) in this case, the same electron donating compound (c) as used in the preparation of the solid catalyst component (A) can be used. In this case, it may be the same as or different from that used in the preparation of the solid catalyst component.
- the preferred electron donating compound (C) is a silane compound having a SiO 2 —C bond, particularly a compound represented by the following formula (3).
- R 3 is a linear or branched hydrocarbon group, an aromatic hydrocarbon group or a cyclic saturated hydrocarbon group, and when p ⁇ 2, it is a combination of any of the above compounds.
- R 4 is a linear or branched hydrocarbon group, and p is an integer of 0 to 3).
- Specific examples of the compound represented by the formula (3) include t-butylcyclohexyl, ⁇ registoxysilane, methylcyclohexyldimethoxysilane, di-t-butylinolemethyoxysilane, dicyclohexinoresimethoxysilane, dipheninoresimethoxysilane, dimethyljetoxysilane, trimethyl Ethoxysilane, methylphenyldimethoxysilane and the like can be mentioned.
- a catalyst activity inhibitor may be used to stabilize the polymerization in the polymerization tank. Specifically, it can be selected from alcohols, phenols, carboxylic acids, sulfonic acids, amines, amides, esters, ethers, phosphines, water, carbon monoxide and carbon dioxide. Preferred examples of the catalyst activity inhibitor include compounds containing active hydrogen.
- Examples of the active hydrogen-containing compounds include methanol, ethanol, n -propanol, isopropanol, n-ptananol, t-butanol, n-hexanol, phenols such as phenol, cresol, and xylenol, formic acid, Acetic acid, propionic acid, benzoic acid
- Examples thereof include carboxylic acids, sulfonic acids such as snolefonic acid, benzenesnolefonic acid, and tonoleensnolefonic acid, amines such as ethylamine and isopropylamine, and water.
- active hydrogen-containing compounds there can be mentioned, for example, methanolone, ethanol, n-propanol, and isopropanol which are linear or branched alcohols having 1 to 20, preferably 1 to 10 carbon atoms.
- methanolone, ethanol, n-propanol, and isopropanol which are linear or branched alcohols having 1 to 20, preferably 1 to 10 carbon atoms.
- a plurality of these catalyst activity inhibitors can be used.
- catalyst activity inhibitors can be used alone, but can also be supplied together with a monomer, an inert hydrocarbon solvent such as heptane, or a carrier fluid such as hydrogen or nitrogen.
- the limiting viscosity [77] measured in tetralin at 135 ° C at a polymerization temperature of 40 to 100 ° C, preferably 50 to 90 ° C, and a polymerization pressure of about 0.1 to 10 MPa at 135 ° C is i to i od iZg, preferably :!
- the molecular weight is adjusted using hydrogen or the like so as to be about eZig.
- a polymerization tank is added without adding a third component, and without providing mechanical adhesion preventing equipment.
- the polymer can be prevented from adhering to the wall and the stirring blade, and polyolefin can be produced without quality deterioration.
- a glass reactor equipped with a stirrer (with an internal volume of about 12 liters) was sufficiently replaced with nitrogen gas, and about 4,860 g of ethanol, 32 g of iodine, and 320 g of metal magnesium were added.
- the reaction was carried out under heating until hydrogen gas was no longer generated from the inside of the system, thereby obtaining a solid reaction product.
- the magnesium compound [solid product] (a) was obtained by drying the solid reaction product under reduced pressure.
- the treated solid catalyst component was converted into Ti atoms in the component in a 200-liter internal volume polymerization tank with stirring blades (homopolymerization tank), and the triethyl was converted into 3 mmol Z hours.
- Aluminum was supplied at 600 mmol / hr and diphenyldimethoxysilane was supplied at 15 mmol / hr, and the polymerization temperature The reaction was carried out at a temperature of 70 ° C and a propylene pressure of 2.7 MPa (Gauge). At this time, the molecular weight was adjusted using hydrogen to a predetermined molecular weight.
- the powder is continuously extracted from the first polymerization tank and transferred to the second (random copolymerization tank).
- the second polymerization tank random copolymerization tank
- propylene and ethylene were supplied at a polymerization temperature of 55 ° C to perform random copolymerization. At this time, the supply ratio of propylene and ethylene was adjusted so that the content of the ethylene unit became a predetermined value.
- the total cooling circulation medium amount (composition:. Hydrogen 0.3 mass ./, ethylene 38 mass 0/0, propylene 58 wt 0/0, propane 3.7 wt 0/0) is 1 60 kghr, 110 kgZhr was supplied from the bottom of the polymerization tank, and 50 kgZhr was supplied from the surface of the polymerization tank.
- the height of the powder supplied from the side was 0.55 m, while the height of the powder tank was 0.8 m. After 6 days of operation, the inside of the polymerization tank was checked, and no polymer adhesion was observed on the stirring blade surface.
- Example 1 the supply amount of the circulating medium for cooling was changed from a supply amount of 110 kg / hr from the bottom of the polymerization tank to 160 kg / hr, and a supply amount of 50 kgZhr from the side of the polymerization tank was set to O kg / Except for hr (supplied only from the bottom), the procedure was the same as in Example 1. After six days of operation, the inside of the polymerization tank was checked, and adhesion of the polymer was observed on the stirring blade surface and the polymerization tank surface. Industrial applicability
- the polyolefin without a quality fall can be provided.
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Abstract
Description
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DE112004001586T DE112004001586T5 (de) | 2003-09-11 | 2004-09-01 | Verfahren zur Herstellung von Polyolefin und Gasphasen-Polymerisationsapparatur dafür |
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JP2003-319239 | 2003-09-11 | ||
JP2003319239A JP4843188B2 (ja) | 2003-09-11 | 2003-09-11 | ポリオレフィンの製造方法及び気相重合装置 |
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JP (1) | JP4843188B2 (ja) |
CN (1) | CN100528907C (ja) |
DE (1) | DE112004001586T5 (ja) |
WO (1) | WO2005026215A1 (ja) |
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WO2005095465A1 (en) * | 2004-03-03 | 2005-10-13 | Basell Poliolefine Italia S.R.L. | Method for controlling the polymer flow in a polymerization process |
EP2350143B1 (en) * | 2008-11-25 | 2016-02-17 | W.R. Grace & CO. - CONN. | Procatalyst composition multiple internal donor having silyl ester and method |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS646209B2 (ja) * | 1981-02-19 | 1989-02-02 | Chisso Corp | |
JPH06206917A (ja) * | 1993-01-12 | 1994-07-26 | Mitsui Petrochem Ind Ltd | オレフィンの重合方法 |
JP2000072802A (ja) * | 1998-08-28 | 2000-03-07 | Mitsui Chemicals Inc | 気相重合装置 |
JP2000302807A (ja) * | 1999-04-02 | 2000-10-31 | Union Carbide Chem & Plast Technol Corp | 重合法 |
JP2002535455A (ja) * | 1999-01-29 | 2002-10-22 | ユニオン・カーバイド・ケミカルズ・アンド・プラスチツクス・テクノロジー・コーポレーシヨン | 重合方法 |
JP2002544333A (ja) * | 1999-05-18 | 2002-12-24 | ディーエスエム エヌ.ブイ. | 流動床重合 |
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2003
- 2003-09-11 JP JP2003319239A patent/JP4843188B2/ja not_active Expired - Fee Related
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2004
- 2004-09-01 DE DE112004001586T patent/DE112004001586T5/de not_active Withdrawn
- 2004-09-01 CN CNB2004800258573A patent/CN100528907C/zh not_active Expired - Fee Related
- 2004-09-01 WO PCT/JP2004/013080 patent/WO2005026215A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS646209B2 (ja) * | 1981-02-19 | 1989-02-02 | Chisso Corp | |
JPH06206917A (ja) * | 1993-01-12 | 1994-07-26 | Mitsui Petrochem Ind Ltd | オレフィンの重合方法 |
JP2000072802A (ja) * | 1998-08-28 | 2000-03-07 | Mitsui Chemicals Inc | 気相重合装置 |
JP2002535455A (ja) * | 1999-01-29 | 2002-10-22 | ユニオン・カーバイド・ケミカルズ・アンド・プラスチツクス・テクノロジー・コーポレーシヨン | 重合方法 |
JP2000302807A (ja) * | 1999-04-02 | 2000-10-31 | Union Carbide Chem & Plast Technol Corp | 重合法 |
JP2002544333A (ja) * | 1999-05-18 | 2002-12-24 | ディーエスエム エヌ.ブイ. | 流動床重合 |
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JP4843188B2 (ja) | 2011-12-21 |
CN1849342A (zh) | 2006-10-18 |
JP2005082773A (ja) | 2005-03-31 |
CN100528907C (zh) | 2009-08-19 |
DE112004001586T5 (de) | 2006-07-27 |
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