WO2002012357A2 - Procédé de préparation d'un support de catalyseur pour la polymérisation d'alpha olefines - Google Patents
Procédé de préparation d'un support de catalyseur pour la polymérisation d'alpha olefines Download PDFInfo
- Publication number
- WO2002012357A2 WO2002012357A2 PCT/FR2001/002529 FR0102529W WO0212357A2 WO 2002012357 A2 WO2002012357 A2 WO 2002012357A2 FR 0102529 W FR0102529 W FR 0102529W WO 0212357 A2 WO0212357 A2 WO 0212357A2
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- aliphatic
- chosen
- catalyst
- carbon atoms
- monoether
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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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
-
- 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
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Definitions
- the present invention relates to a process for preparing a catalyst support for the. polymerization of ethylene and polymerization. (stereospecific) ⁇ -olefins, in particular propylene, as well as on the support thus obtained.
- the invention also relates to the corresponding catalyst (support + compound based on transition metal + if necessary electron donor or internal Lewis base) or on the corresponding catalytic system (catalyst + cocatalyst + if appropriate donor) electrons or external Lewis base), as well as on the polymerization process using this catalyst or this catalytic system.
- the polymerization of ethylene and of ⁇ -.olefins in general is carried out using Ziegler-Natta type catalysts.
- the catalytic system of the Ziegler-Natta type generally consists of two inseparable elements: a catalytic component based on transition metal deposited on a support based on magnesium chloride and a cocatalyst generally based on an aluminum compound.
- This electron donor is very often a diester of aromatic bicarboxylic acid, as described in European patent application EP-A-45 976; it can also be a diether, as described in European patent application EP-A-361,494. • -
- this electron donor and the titanium compound are brought into contact with magnesium chloride in active form.
- Ziegler-Natta type catalysts often contain phthalates as internal Lewis bases, these phthalates usually influencing the stereospecificity of the final polymer. However, phthalates are compounds suspected of being harmful to health; it is therefore interesting to be able to do without them or to find substitutes for them.
- the preparation of catalytic systems for the polymerization of olefins (propylene) is relatively complex; polymerization without external Lewis base could be a source of cost savings and would also simplify 'the process.
- the molecular weights of the polymers are adjusted during polymerization by the presence of a transfer agent, such as hydrogen. For many applications, there is a demand for products with relatively low molecular weights. Obtaining such products requires a large amount of transfer agent during polymerization. For process and cost reasons, it may be advantageous to have a catalytic system which requires less hydrogen to manufacture polymers with low molecular weights.
- the support for magnesium chloride can be produced by chlorination of an organomagnesium (alkylmagnesium) in the presence of an organic aluminum compound and an aliphatic diether, in which case it is not necessary to use an internal electron donor (or internal Lewis base) during the support activation by the transition metal compound.
- an organomagnesium alkylmagnesium
- an aliphatic diether in which case it is not necessary to use an internal electron donor (or internal Lewis base) during the support activation by the transition metal compound.
- the Applicant Company "1 has also discovered that the catalyst system of the invention requires less hydrogen to manufacture polymers with low molecular weights.
- the complexing agent is advantageously chosen from aliphatic or cyclic ethers, diisoamyl ether and sec-butyl ether being preferred.
- the method for preparing the support does not include step (ii) above, and the complexing agent is restricted to the family of di .
- aliphatic ethers which makes it possible to obtain a polymer (for example polypropylene) very isotactic unlike other complexing agents, without having to necessarily add an internal or external Lewis base.
- the aliphatic diether is not brought into contact with magnesium chloride in active form, as in the case of European patent application EP-A-0 361 494 in which the diethers are described, but it is brought into contact with the alkylmagnesium before the synthesis of the activated magnesium chloride support.
- the diether is put after production of the support and, according to the present invention, the diether is put during the preparation of the support; this provides the advantage that at a given melt flow rate, the polymerization consumes less hydrogen, which also amounts to saying that, for a given quantity of hydrogen, the polymer obtained is more fluid in the molten state.
- the present invention therefore firstly relates to a process for the preparation of a catalyst support for the homopolymerization of olefins and ethylene, in particular for the homopolymerization of propylene or for the copolymerization of ethylene and ⁇ -olefins, characterized in that one reacts, ' in the presence of at least one aliphatic diether as electron donor, at least one chlorinated organic compound and a preliminary mixture of at least one alkylmagnesium and at least one organic aluminum compound chosen from aluminoxanes, aluminosiloxanes and alkylaluminums.
- the aliphatic diether acts as an agent for controlling the morphology of the support, which means that: a) the SPAN (measurement defined precisely below which characterizes the particle size distribution width of the support) is low, in general less than 5; b) the polymer particles obtained by the suspension polymerization processes, gas phase in the liquid monomer, exhibit a good morphological replica of the solid catalytic component obtained from the support and therefore from the support itself. At least one monoether chosen from aliphatic monoethers and cyclic monoethers may have been associated with the aliphatic diether (s).
- aliphatic diether as electron donor
- monoether chosen from aliphatic monoethers and cyclic monoether may also have been associated with this or these aliphatic diethers .
- the aliphatic diethers are especially chosen from: 2, 2-diisobutyl-1,3-dimethoxypropane; 2,2-diisobutyl-1,3-diethoxypropane;
- the aliphatic diether is . 2, 2 '-dicyclopentyl-1, 3-dimethoxypropane or 9,9-bis (methoxymethyl) fluorene.
- the aliphatic monoether (s) are chosen in particular from diisoamyl ether and di-sec-butyl ether; and the cyclic monoetheres are in particular chosen from tetrahydrofuran and dioxane.
- the diethers and - and the monoether (s) associated with the pre-mixing and those put. used during the reaction of the chlorinated organic compound (s) and the aluminum compound (s) can be respectively identical or different.
- the chlorinated organic compound (s) are chosen in particular from: 'alkyl chlorides in which the alkyl radical is primary, secondary or tertiary and optionally comprises a heteroatom, said radical comprising up to 12 carbon atoms; polyalkyl halides; and acid chlorides.
- alkylmagnesium (s) are in particular chosen by those of formula (I):
- R and R each independently represent an alkyl radical having from 1 to 12 carbon atoms.
- a particularly preferred alkylmagnesium is butylethylmagnesium.
- aluminoxane (s) are chosen in particular from the compounds of formula (II):
- - R 3 represents an alkyl radical in - ⁇ - C ⁇ g
- R 4 ' together form a radical -0- or each represent a radical R 3 ;
- - n is 0 or is an integer from 1 to '20.
- aluminosiloxane (s) are chosen in particular from the compounds of formula (III):
- R 5 , R 6 , R 7 , R 8 and R 9 identical or different, each represent an alkyl radical in preferably in - ⁇ - Cg, or a hydrogen atom, provided that there are not more than 3 hydrogen atoms per mole of compound, or a chlorine atom, at the provided that there are not more than 3 chlorine atoms per mole of compound.
- alkyl aluminum (s) are in particular chosen from the compounds of formula (IV):
- Ri ⁇ , Ri x i -and R1 identical or different, each represent an alkyl radical having from 1 to
- the Mg / Al molar ratio is advantageously between 5 and 200, and preferably between 10 and 80. Even elsewhere, the concentration of chlorinated organic compound (s) is advantageously such that the Cd / Mg molar ratio is between 2 and 4.
- the molar ratio of the total amount of the aliphatic diether (s) and the monoether (s) to the magnesium is advantageously at least 0.01, being in particular from 0.01 to 5, the aliphatic diethers being those used with the one or more chlorinated organic compounds and optionally with the premix, and the monoether being those optionally used with the chlorinated organic compound (s) and / or with the premix.
- the molar ratio of the total amount of the Al or aliphatic diethers, excluding monoether, to the magnesium is at least 0.01, being in particular from 0.01 to 5, the aliphatic diethers being those used with the chlorinated organic compound (s) and possibly with the premixing, and the monoether being those possibly engaged with the chlorinated organic compound (s) and / or with the premix.
- the alkylmagnesium (s) is mixed with the organic compound (s) of aluminum in the presence of the aliphatic diethers (s) and, the where appropriate, aliphatic or aromatic monoether (s), this reaction advantageously being able to be carried out in an inert solvent such as a hydrocarbon containing from 6 to 30 carbon atoms, which can be chosen from linear or cyclic hydrocarbons, saturated or unsaturated, such as heptane, cyclohexane, toluene, benzene or their derivatives such as durene or xylene and any mixture of these compounds;
- an inert solvent such as a hydrocarbon containing from 6 to 30 carbon atoms, which can be chosen from linear or cyclic hydrocarbons, saturated or unsaturated, such as heptane, cyclohexane, toluene, benzene or their derivatives such as durene or xylene and any mixture of these compounds;
- an inert liquid which can be chosen from the inert solvents identified above, the support thus formed in suspension in the reaction medium.
- a support is then obtained, the particle diameter of which is between 5 and 150 ⁇ m, more generally between 5 and 100 ⁇ m.
- the particle size distribution width of the support, and therefore of the subsequent catalyst, is very narrow, generally less than 5.
- the present invention also relates to a catalyst support for the homopolymerization or the copolymerization of ethylene and of the ⁇ -olefins, capable of being obtained by the process as defined above.
- the present invention also relates to a Ziegler-Natta catalyst for the omopolymerization of a- olefins and ethylene, in particular for the homopolymerization of propylene, or for the copolymerization of ethylene and ⁇ -olefins, comprising- the catalyst support prepared or capable of being obtained by the process as defined above above and at least one Group IV transition metal halide.
- the group IV transition metal halide is in particular a titanium halide of formula (V);
- R - * - 3 is an alkyl radical in C- j ⁇ C- j ⁇ ;
- - p represents an integer between 0 and 4.
- the titanium halide is TiC ⁇ ⁇ .
- the catalyst may also comprise at least one electron donor (called an impregnation donor) advantageously chosen from organic compounds containing one or more nitrogen, sulfur or phosphorus atoms.
- an impregnation donor advantageously chosen from organic compounds containing one or more nitrogen, sulfur or phosphorus atoms.
- the association of one or more electron donors above can be carried out. More specifically, the electron donors containing one or more commonly used oxygen atoms can be organic acid esters or ethers. More specifically, they may be esters of aromatic mono- or dicarboxylic acid or diethers.
- the aromatic esters can be phthalates such as dialkylphthalates, but the invention also relates to a catalyst such as defined above from which phthalates are excluded, as well as on a catalyst as defined. above from which, in general, non-ether internal Lewis bases are excluded.
- the present invention also relates to a process for the preparation of a catalyst as defined above, characterized in that it comprises the impregnation of the support prepared or capable of being prepared by the process as defined above above, with at
- Impregnation can thus be done in a way
- transition metal halide optionally in an inert solvent to form a homogeneous suspension,. and possibly in the presence of the electron donor.
- the support can possibly undergo two impregnations
- aliphatic hydrocarbons such as hexane, heptane and decane can be used; alicyclic hydrocarbons such as
- Cyclohexane and ethylcyclohexane aromatic hydrocarbons such as toluene, xylene, chlorobenzene and durene and their mixtures.
- the catalyst thus prepared is combined with a cocatalyst to carry out the polymerization of olefins.
- the present invention therefore also relates to a catalytic system for the homopolymerization or the copolymerization of ethylene and of the ⁇ -olefins, characterized in that it comprises a catalyst as defined above and at least one cocatalyst, and if applicable, at least one
- the cocatalyst is generally chosen from group III metal alkyls, among which mention may be made of aluminum alkyls such as trimethylaluminum, triethylaluminium, triisobutylaluminium 'and their combinations.
- cocatalyst electron donor (s) which can be used to modify the catalytic performance can advantageously be chosen from: •. aliphatic silanes of general formula (VI):
- R represent 'each independent alkoxy -OR 1 ⁇
- R liD representing a C - ⁇ - C20 alkyl group
- n may be cited as examples, dicyclopentyldimethoxysilane, cyclohexyl ethyldimethoxy-silane and diisobutyldimethoxysilane); arylalkoxysilanes such as diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane;
- silacycloalkanes such as 2,6-diethylsilacyclohexane; the diethers of general formula (VII):
- R 21 N represents a polycyclic amino group
- the number of carbon atoms is between 7 and 40 and forming a cyclic skeleton including the nitrogen atom.
- the present invention also relates to a process for homopolymerization of ⁇ -olefins and - ethylene, in particular for the homopolymerization of propylene, or of copolymerization of ethylene and ⁇ -olefins, comprising contacting ethylene and / or. at least one ⁇ -olefin and / or at least one other comonomer representing less than 50% by mass, with a catalytic system as defined above, said process being carried out in suspension or in gas phase or in a liquid ⁇ -olefin.
- the invention therefore applies to. the polymerization of ethylene and the stereospecific polymerization of ⁇ -olefins and more particularly propylene, as well as the copolymerization of ethylene and ⁇ -olefins.
- Copolymerization also includes terpolymerization. In the copolymerization, it is possible to copolymerize the ethylene and the ⁇ olefins together; it is also possible to operate with another comonomer, in which case it represents less than 50% by mass of all the monomers.
- ⁇ -olefin as used in '
- olefins comprising from 3 to 20 carbon atoms,. preferably 3 to 8 carbon atoms.
- the preferred ⁇ -olefin is propylene.
- the comonomer generally represents less than 30% by mass.
- this also allows the production, with high productivity, of non-stereo-specific polymers such as random polymers of ⁇ -olefin with high comonomer content such as ethylene.
- the polymerization of ⁇ -olefins can be carried out according to known methods, in suspension in a diluent, in the liquid monomer, in the gas phase.
- a chain transfer agent can be used to control the melt index of the polymer to be produced.
- chain transfer agent hydrogen can be used, which is introduced in an amount which can range up to 90% and which is generally between 0.01 and 60 mol% of the olefin group and hydrogen brought to the reactor.
- This chain transfer agent makes it possible to obtain a given melt index, knowing that the melt index increases when the quantity of chain transfer agent increases.
- the invention offers the advantage of consuming little chain transfer agent for a given melt index.
- DCPDMP 2,2-dicyclopentyl-1,3-dimethoxypropane
- TiBAO tetraisobutylalumin xane
- EDIA • diisoamyl ether
- THF tetrahydrofuran
- TEA Durene triethylaluminium. : tetramethylbenzene
- melt index (melt index or MFI) is defined according to ASTM-D 1238.
- The% mm measured by high resolution NMR - * - C, defines the percentage of meso triads of the polymer obtained.
- DCPDMP DCPDMP and 9.16 g (0.006 mole) of a 20% by weight TiBAO solution in hexane. This mixture is stirred for
- Example 2 The procedure is as in Example 1, except that the 10 g of DCPDMP is replaced by 3.9 g of diisoamyl ether, 10% of which is used with BEM and 90% with tert-butyl chloride. 10 5 Pa (1 bar) of hydrogen and 3.5 liters of propylene are introduced into a 4.5 liter metal reactor, fitted with a double jacket and mechanical stirring, previously placed under an inert atmosphere. Under. stirring, 24 mmol of triethylaluminum and 15 mg of catalyst B1 are introduced at ambient temperature. The temperature is raised to 70 ° C. in ten minutes, then maintained at this value for 1 hour.
- the residual propylene is then degassed and 21 g of polypropylene are recovered - that is to say 1273 g of polypropylene / g of catalyst B1.
- the melt index cannot be measured because of the excessive fluidity of the polymer.
- The% of mm is 70.1.
- 100 g are introduced into a 1 liter reactor, fitted with a double jacket, with mechanical stirring and a tube allowing the introduction of reagents.
- This mixture is stirred for 1 hour.
- the temperature is raised to 50 ° C, stirring is maintained at 250 rpm.
- the solid After filtration, the solid is dried for 2 hours at 70 ° C. 8 g of a B2 catalyst containing "12.0% of DCPDMP, 1.4% Ti and 18.5% Mg.
- the D50 is 17.0 ⁇ m for a SPAN of 1.6.
- the propylene is then degassed and 468 g of polymer are recovered - ie 23,400 g of polypropylene / g of catalyst B2 - having a melt index of 22.3 g / 10 minutes.
- The% mm is 96.0.
- This mixture is stirred for 1 hour. At the same time, the temperature is raised to 50 ° C, stirring is maintained at 250 rpm.
- the synthesis of the catalyst is identical to that of Example 4, replacing support A2 with support A3. 7.7 g of catalyst B3 containing 15.4% of./ DCPDMP, 2.5% of Ti are recovered. and 17.0% Mg.
- the D50 is 20.0 ⁇ m - for a SPAN of 0.9.
- the polymerization of propylene is identical to that of Example 4, replacing the catalyst B2 with the catalyst B3. 535 g of polymer are recovered - ie 26,800 g of polypropylene / g of catalyst B3 - having a melt index of 25.8 g / 10 minutes. The% mm is 92.7.
- This mixture is stirred for 1 hour at room temperature at 400 rpm; the temperature of the reaction medium is then raised to 50 ° C. Under the same stirring conditions and at 50 ° C., a mixture consisting of 84.4 g of tert-butyl chloride and 23.3 g of diisoamyl ether is introduced using a syringe at a flow rate of 60 ml. / h. After this introduction, the temperature is brought back to 40 ° C. and the stirring speed lowered to 250 revolutions / minute. 50.9 g of THF are introduced using a syringe at a flow rate of 60 ml / h. After this addition, the medium is kept at 40 ° C with stirring for 15 minutes. The suspension is then filtered, and the solid recovered, washed three times with 200 ml of hexane each time. Filtration is carried out after each wash. A solid A4 is obtained.
- Catalyst B4 is obtained.
- Catalyst B4 contains 2.9% Ti, 14.4%
- the polymerization of propylene was conducted in the same manner as' Example 4 using the solid B4 instead of solid B2. 767 g of polymer are recovered - ie 38,400 g of polypropylene / g of catalyst B4 - having a melt index of 10.1 g / 10 minutes. The% mm is 91.3.
- the solid obtained is suspended in 23 ml of toluene at 40 ° C with stirring (250 rpm). 70 ml of TiCl 4 are added . The temperature is raised in 5 minutes to 100 ° C to be maintained there for 2 hours. After filtration, 94 ml of toluene, 5 ml of TiCl 4 are added and the mixture is stirred at 100 ° C. for 1 hour. This operation is repeated 4 times. After the last filtration, 90 ml of hexane are added and the mixture is stirred for 15 minutes at 70 ° C. This last operation is repeated 2 times. After filtration, the solid is dried for 2 hours at 70 ° C. 5.5 g of catalyst B5 are obtained containing 12.8% of dicyclopentyl-1, 3-dimethoxypropane, 2.2% of Ti and 19.2% of Mg. The DP50 is 19.9 ⁇ m for a SPAN of 0.91.
- the polymerization of propylene is equivalent to that of Example 1, replacing catalyst B1 with 30 mg of catalyst B5 and using 12.5 millimoles of TEA instead of 21.
- the amount of hydrogen used is 7 ⁇ 10 4 Pa (0.7 bar) instead of 4 x 10 4 Pa (0.4 bar).
- 1455 g of polypropylene are recovered - ie 48 500 g of polypropylene per gram of catalyst B5 - having a melt index of 13.4 g / 10 minutes and a.% Mm of 93.6.
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01960862A EP1317493A2 (fr) | 2000-08-03 | 2001-08-02 | Procede de preparation d'un support de catalyseur pour la polymerisation d'alpha olefines |
US10/343,239 US20040054101A1 (en) | 2000-08-03 | 2001-08-02 | Method for preparing a catalyst support for polymerising ethylene and a-olefins, resulting support and corresponding catalyst |
AU2001282258A AU2001282258A1 (en) | 2000-08-03 | 2001-08-02 | Method for preparing a catalyst support for polymerising ethylene and alpha-olefins, resulting support and corresponding catalyst |
KR10-2003-7001460A KR20030064739A (ko) | 2000-08-03 | 2001-08-02 | 에틸렌 및 α-올레핀 중합용 촉매 지지체의 제조 방법,생성 지지체 및 해당 촉매 |
JP2002518327A JP2004519530A (ja) | 2000-08-03 | 2001-08-02 | エチレンおよびα−オレフィン類を重合するための触媒担体の製造方法、得られる担体並びに対応する触媒 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0010264A FR2812642B1 (fr) | 2000-08-03 | 2000-08-03 | Procede de preparation d'un support de catalyseur pour la poymerisation de l'ethylene et des alpha-olefines, le support ainsi obtenu et le catalyseur correspondant |
FR00/10264 | 2000-08-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002012357A2 true WO2002012357A2 (fr) | 2002-02-14 |
WO2002012357A3 WO2002012357A3 (fr) | 2002-04-11 |
Family
ID=8853274
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2001/002529 WO2002012357A2 (fr) | 2000-08-03 | 2001-08-02 | Procédé de préparation d'un support de catalyseur pour la polymérisation d'alpha olefines |
Country Status (8)
Country | Link |
---|---|
US (1) | US20040054101A1 (fr) |
EP (1) | EP1317493A2 (fr) |
JP (1) | JP2004519530A (fr) |
KR (1) | KR20030064739A (fr) |
CN (1) | CN1636023A (fr) |
AU (1) | AU2001282258A1 (fr) |
FR (1) | FR2812642B1 (fr) |
WO (1) | WO2002012357A2 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003076480A1 (fr) * | 2002-03-08 | 2003-09-18 | Basell Poliolefine Italia S.P.A. | Procede de preparation d'un composant catalytique a base de diether |
WO2007133140A1 (fr) * | 2006-05-16 | 2007-11-22 | Mcneil Ab | Produit pharmaceutique destiné à une administration intrabuccale de nicotine comprenant du trométamol servant d'agent tampon |
WO2009085649A1 (fr) * | 2007-12-21 | 2009-07-09 | Dow Global Technologies Inc. | Composition de catalyseur auto-limitant contenant un donneur interne bidentate |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1958621B (zh) * | 2005-10-31 | 2010-12-22 | 中国石油化工股份有限公司 | 用于烯烃聚合的固体催化剂组分及其催化剂和催化剂应用 |
KR101373775B1 (ko) | 2012-11-23 | 2014-03-13 | 롯데케미칼 주식회사 | 폴리올레핀 합성용 촉매의 제조방법 및 이를 이용한 폴리올레핀의 제조방법 |
KR101705851B1 (ko) * | 2015-09-23 | 2017-02-10 | 롯데케미칼 주식회사 | 담체 입자의 제조 방법 |
BR112018011647B1 (pt) * | 2015-12-09 | 2022-12-27 | Nova Chemicals (International) S.A. | Método de fabricar forma desordenada de dicloreto de magnésio e métodos para fabricar um (pro)catalisador de ziegler natta e para fabricar polímeros e copolímeros de polietileno |
CN111295399B (zh) | 2017-11-06 | 2022-09-06 | 埃克森美孚化学专利公司 | 基于丙烯的抗冲共聚物及生产方法和设备 |
WO2022114910A1 (fr) * | 2020-11-30 | 2022-06-02 | 주식회사 엘지화학 | Procédé de préparation d'un catalyseur métallocène supporté |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0232643A1 (fr) * | 1985-12-18 | 1987-08-19 | Elf Atochem S.A. | Procédé de traitement de catalyseurs sphériques de polymérisation des oléfines. Application du catalyseur obtenu à la polymérisation des oléfines |
EP0361494A2 (fr) * | 1988-09-30 | 1990-04-04 | Montell North America Inc. | Composants et catalyseurs pour la polymérisation d'oléfines |
EP0434082A2 (fr) * | 1989-12-22 | 1991-06-26 | Montell North America Inc. | Composants et catalyseurs de polymérisation d'oléfines |
FR2697526A1 (fr) * | 1992-10-30 | 1994-05-06 | Bp Chemicals Snc | Procédé de préparation d'un catalyseur de type Ziegler-Natta pour la polymérisation des oléfines. |
EP0749983A1 (fr) * | 1995-06-21 | 1996-12-27 | Elf Atochem S.A. | Particules comprenant du chlorure de magnésium, leur procédé d'obtention et particules de polyoléfine |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2529207A1 (fr) * | 1982-06-24 | 1983-12-30 | Bp Chimie Sa | Procede pour la preparation de supports de catalyseurs pour la polymerisation des alpha-olefines et supports obtenus |
EP1072619A1 (fr) * | 1999-07-28 | 2001-01-31 | Atofina | Procédé de préparation de support de catalyseur pour la polymérisation des alpha-olefines, et support ainsi obtenu |
CN1137155C (zh) * | 1999-12-06 | 2004-02-04 | 中国石油化工集团公司 | 用于烯烃聚合或共聚合的催化剂体系 |
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2000
- 2000-08-03 FR FR0010264A patent/FR2812642B1/fr not_active Expired - Fee Related
-
2001
- 2001-08-02 AU AU2001282258A patent/AU2001282258A1/en not_active Abandoned
- 2001-08-02 EP EP01960862A patent/EP1317493A2/fr not_active Withdrawn
- 2001-08-02 CN CNA018168124A patent/CN1636023A/zh active Pending
- 2001-08-02 US US10/343,239 patent/US20040054101A1/en not_active Abandoned
- 2001-08-02 WO PCT/FR2001/002529 patent/WO2002012357A2/fr not_active Application Discontinuation
- 2001-08-02 JP JP2002518327A patent/JP2004519530A/ja not_active Withdrawn
- 2001-08-02 KR KR10-2003-7001460A patent/KR20030064739A/ko not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0232643A1 (fr) * | 1985-12-18 | 1987-08-19 | Elf Atochem S.A. | Procédé de traitement de catalyseurs sphériques de polymérisation des oléfines. Application du catalyseur obtenu à la polymérisation des oléfines |
EP0361494A2 (fr) * | 1988-09-30 | 1990-04-04 | Montell North America Inc. | Composants et catalyseurs pour la polymérisation d'oléfines |
EP0434082A2 (fr) * | 1989-12-22 | 1991-06-26 | Montell North America Inc. | Composants et catalyseurs de polymérisation d'oléfines |
FR2697526A1 (fr) * | 1992-10-30 | 1994-05-06 | Bp Chemicals Snc | Procédé de préparation d'un catalyseur de type Ziegler-Natta pour la polymérisation des oléfines. |
EP0749983A1 (fr) * | 1995-06-21 | 1996-12-27 | Elf Atochem S.A. | Particules comprenant du chlorure de magnésium, leur procédé d'obtention et particules de polyoléfine |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003076480A1 (fr) * | 2002-03-08 | 2003-09-18 | Basell Poliolefine Italia S.P.A. | Procede de preparation d'un composant catalytique a base de diether |
US7033970B2 (en) | 2002-03-08 | 2006-04-25 | Basell Poliolefine Italia S.R.L. | Process for preparing a diether-based catalyst component |
WO2007133140A1 (fr) * | 2006-05-16 | 2007-11-22 | Mcneil Ab | Produit pharmaceutique destiné à une administration intrabuccale de nicotine comprenant du trométamol servant d'agent tampon |
WO2009085649A1 (fr) * | 2007-12-21 | 2009-07-09 | Dow Global Technologies Inc. | Composition de catalyseur auto-limitant contenant un donneur interne bidentate |
RU2489447C2 (ru) * | 2007-12-21 | 2013-08-10 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Самоограничивающаяся композиция катализатора с бидентатным внутренним донором |
Also Published As
Publication number | Publication date |
---|---|
WO2002012357A3 (fr) | 2002-04-11 |
CN1636023A (zh) | 2005-07-06 |
KR20030064739A (ko) | 2003-08-02 |
AU2001282258A1 (en) | 2002-02-18 |
FR2812642B1 (fr) | 2003-08-01 |
FR2812642A1 (fr) | 2002-02-08 |
US20040054101A1 (en) | 2004-03-18 |
EP1317493A2 (fr) | 2003-06-11 |
JP2004519530A (ja) | 2004-07-02 |
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