WO2012052386A1 - Procédé de polymérisation d'oléfines - Google Patents

Procédé de polymérisation d'oléfines Download PDF

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Publication number
WO2012052386A1
WO2012052386A1 PCT/EP2011/068077 EP2011068077W WO2012052386A1 WO 2012052386 A1 WO2012052386 A1 WO 2012052386A1 EP 2011068077 W EP2011068077 W EP 2011068077W WO 2012052386 A1 WO2012052386 A1 WO 2012052386A1
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Prior art keywords
groups
process according
anyone
polymerization
alkyl
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PCT/EP2011/068077
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English (en)
Inventor
Joachim T. M. Pater
Simona Guidotti
Alessandro Mignogna
Giampiero Morini
Gianni Vitale
Original Assignee
Basell Poliolefine Italia S.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Basell Poliolefine Italia S.R.L. filed Critical Basell Poliolefine Italia S.R.L.
Priority to BR112013008507A priority Critical patent/BR112013008507A2/pt
Priority to EP11770437.9A priority patent/EP2630169A1/fr
Priority to CN201180050746.8A priority patent/CN103154050B/zh
Priority to US13/878,712 priority patent/US20130217844A1/en
Publication of WO2012052386A1 publication Critical patent/WO2012052386A1/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
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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 the production of polyolefins carried out at a relatively high temperature in the presence of a specific Ziegler-Natta polymerization catalyst.
  • the polymerization of olefins is an exothermic reaction and it is therefore necessary to provide means to cool the bed to remove the heat of polymerization.
  • the preferred method for removing the heat of polymerization is by supplying to the polymerization reactor a gas, the fluidising gas, which is at a temperature lower than the desired polymerization temperature, passing the gas through the fluidised bed to conduct away the heat of polymerization, removing the gas from the reactor and cooling it by passage through an external heat exchanger, and recycling it to the bed.
  • the temperature of the recycle gas can be adjusted in the heat exchanger to maintain the fluidised bed at the desired polymerization temperature.
  • the recycle gas generally comprises the monomelic olefin, optionally together with, for example, an inert diluent gas such as nitrogen and/or a gaseous chain transfer agent such as hydrogen.
  • an inert diluent gas such as nitrogen and/or a gaseous chain transfer agent such as hydrogen.
  • the recycle gas serves to supply the monomer to the bed, to fluidise the bed, and to maintain the bed at the desired temperature.
  • the production rate i.e. the space time yield in terms of weight of polymer produced per unit volume of reactor space per unit time
  • the rate of heat removal can be increased in several ways, also depending on the type of polymerization technique. For example, in gas-phase fluidized bed polymerization, heat removal can be increased by increasing the velocity of the recycle gas, reducing the temperature of the recycle gas, changing the heat capacity of the recycle gas.
  • the extent of heat removal can be increased either by lowering the temperature of the refrigerating liquid circulating in the jacketed reactor or by increasing its circulation velocity.
  • USP 7,388,061 discloses diolesters belonging to the formula R 1 -CO-O-CR 3 R 4 -A-CR 5 R 6 -O- CO-R 2 in which Ri and R 2 groups, which may be identical or different, can be substituted or unsubstituted hydrocarbyl having 1 to 20 carbon atoms, R 3 -R6 groups, which may be identical or different, can be selected from the group consisting of hydrogen, halogen or substituted or unsubstituted hydrocarbyl having 1 to 20 carbon atoms, R 1 -R6 groups optionally contain one or more hetero-atoms replacing carbon, hydrogen atom or the both, said hetero-atom is selected from the group consisting of nitrogen, oxygen, sulfur, silicon, phosphorus and halogen atom, two or more of R 3 -R6 groups can be linked to form saturated or unsaturated monocyclic or polycyclic ring; A is a single bond or bivalent linking group with chain length between two free radicals being 1-10 atoms, wherein said bi
  • R -R4 groups are hydrogen or C1-C15 hydrocarbon groups, optionally containing an heteroatom selected from halogen, P, S, N and Si, with the proviso that Ri and R4 are not simultaneously hydrogen, R groups equal to or different from each other, are selected from C1-C15 hydrocarbon groups which can be optionally linked to form a cycle and n is an integer from 0 to 5, and optionally
  • the process is carried out at a temperature ranging from 80 to 95°C more preferably from higher than 80 to 95°C and especially from higher than 80 to 90°C and very especially from higher than 80 to 88°C.
  • Ri and R4 independently are selected from C1-C15 alkyl groups, C 6 -Ci 4 aryl groups, C 3 -C15 cycloalkyl groups, and C 7 -C15 arylalkyl or alkylaryl groups. More preferably, Ri and R4 are selected from C1-C1 0 alkyl groups and even more preferably from C1-C5 alkyl groups in particular methyl.
  • R 2 -R3 groups independently are selected from hydrogen, C1-C15 alkyl groups, C 6 -Ci 4 aryl groups, C 3 -C15 cycloalkyl groups, and C 7 -C15 arylalkyl or alkylaryl groups. More preferably, R 2 and R 3 are selected from hydrogen or C1-C1 0 alkyl groups and even more preferably from hydrogen or C1-C5 alkyl groups in particular methyl. In one preferred embodiment, hydrogen and methyl are preferred. In one particular embodiment both R 2 and R 3 are hydrogen.
  • R groups are selected from C1-C15 alkyl groups, C 6 -Ci 4 aryl groups, C 3 -C15 cycloalkyl groups, and C 7 -C15 arylalkyl or alkylaryl groups. More preferably, R are selected from Ci-Cio alkyl groups and even more preferably from C 1 -C5 alkyl groups. Among them particularly preferred are methyl, ethyl, n-propyl and n-butyl.
  • the index n can vary from 0 to 5 inclusive, preferably it ranges from 1 to 3 and more preferably is 1. When n is i, the substituent R is preferably in position 4 of the benzoate ring.
  • preferred structures are those in which simultaneously Ri and R4 are methyl, R 2 and R 3 are hydrogen and n is 1 and the R groups, which are in position 4 of the benzene ring are methyl, ethyl, n-propyl or n-butyl.
  • Non limiting examples of structures (A) are the following: 2,4-pentanediol dibenzoate, 3-methyl-
  • the catalyst components of the invention comprise, in addition to the above electron donors, Ti, Mg and halogen.
  • the catalyst components comprise a titanium compound, having at least a Ti-halogen bond and the above mentioned electron donor compounds supported on a Mg halide.
  • the magnesium halide is preferably MgCl 2 in active form which is widely known from the patent literature as a support for Ziegler-Natta catalysts.
  • Patents USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler- Natta catalysis.
  • magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line.
  • the preferred titanium compounds used in the catalyst component of the present invention are TiCl 4 and TiCl 3 ; furthermore, also Ti-haloalcoholates of formula Ti(OR) m-y X y can be used, where m is the valence of titanium, y is a number between 1 and m-1, X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms.
  • the preparation of the solid catalyst component can be carried out according to several methods.
  • One method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to USP 4,220,554) and an excess of TiCl 4 in the presence of the electron donor compounds at a temperature of about 80 to 135°C.
  • the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR) m-y X y , where m is the valence of titanium and y is a number between 1 and m, preferably TiCl 4 , with a magnesium chloride deriving from an adduct of formula MgCl 2 *pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
  • the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648.
  • the so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl 4 (generally 0°C); the mixture is heated up to 80- 135°C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiCl 4 can be carried out one or more times.
  • the electron donor compound is preferably added during the treatment with TiCl 4 .
  • the preparation of catalyst components in spherical form are described for example in European Patent Applications EP-A-395083, EP-A-553805, EP-A-553806, EPA601525 and WO98/44001.
  • the solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) generally between 20 and 500 m 2 /g and preferably between 50 and 400 m 2 /g, and a total porosity (by B.E.T. method) higher than 0.2 cm 3 /g preferably between 0.2 and 0.6 cm 3 /g.
  • the porosity (Hg method) due to pores with radius up to 10.000 A generally ranges from 0.3 to 1.5 cm 3 /g, preferably from 0.45 to 1 cm 3 /g.
  • the solid catalyst component has an average particle size ranging from 5 to 120 ⁇ and more preferably from 10 to 100 ⁇ .
  • the desired electron donor compounds can be added as such or, in an alternative way, it can be obtained in situ by using an appropriate precursor capable to be transformed in the desired electron donor compound by means, for example, of known chemical reactions such as etherification, alkylation, esterification, etc.
  • the final amount of electron donor compounds is such that the molar ratio with respect to the MgCl 2 is from 0.01 to 1, preferably from 0.05 to 0.5.
  • the amount of Ti atoms in the catalyst component preferably ranges from 1 to 10%wt, more preferably from 1.5 to 8% and especially from 2 to 5% with respect to the total weight of said catalyst component.
  • the organo aluminum compound is preferably an alkyl-Al compound. It is preferably selected from the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n- butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum.
  • Suitable external electron-donor compounds include silicon compounds, ethers, esters, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine and ketones.
  • Another class of preferred external donor compounds is that of silicon compounds of formula (R 7 )a(3 ⁇ 4)bSi(C)R9)c, where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4;
  • R 7 , Rg, and R 9 are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
  • Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t- butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), (2-ethylpiperidinyl)t- butyldimethoxy silane, (2-ethylpiperidinyl)thexyldimethoxy silane, (3,3,3 -trifluoro-n-propyl)(2- ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane.
  • C donor methylcyclohexyldimethoxysilane
  • D donor dicyclopentyldimethoxysilane
  • (2-ethylpiperidinyl)t- butyldimethoxy silane (2-ethylpiperidinyl
  • examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.
  • the external electron donor compound is used in such an amount to give a molar ratio between the organoaluminum compound and said external electron donor compound of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.
  • the liquid phase polymerization can be carried out for example in slurry using as diluent a liquid inert hydrocarbon, or in bulk using the liquid monomer (propylene) as a reaction medium, or in solution using either monomers or inert hydrocarbons as solvent for the nascent polymer.
  • the liquid phase polymerization can be carried out in various types of reactors such as continuous stirred tank reactors, loop reactors or plug-flow ones.
  • the gas-phase polymerization can be carried out operating in one or more fluidized or mechanically agitated bed reactors. Also, it can be carried out in a gas-phase reactor comprising two interconnected polymerization zones one of which, working under fast fluidization conditions and the other in which the polymer flows under the action of gravity.
  • the operating pressure is generally between 0.5 and 10 MPa, preferably between 1 and 5 MPa. In the bulk polymerization the operating pressure is generally between 1 and 6 MPa preferably between 1.5 and 4 MPa.
  • the catalyst of the present invention can be used as such in the polymerization process by introducing it directly into the reactor.
  • the catalyst can be pre-polymerized before being introduced into the first polymerization reactor.
  • pre-polymerized means a catalyst which has been subject to a polymerization step at a low conversion degree.
  • a catalyst is considered to be pre- polymerized when the amount the polymer produced is from about 0.1 up to about 1000 g per gram of solid catalyst component.
  • the pre-polymerization can be carried out with propylene or other olefins.
  • it is especially preferred pre-polymerizing ethylene or mixtures thereof with one or more a-olefins in an amount up to 20% by mole.
  • the conversion of the pre-polymerized catalyst component is from about 0.2 g up to about 500 g per gram of solid catalyst component.
  • the pre-polymerization step can be carried out at temperatures from 0 to 60°C preferably from 5 to 50 °C in liquid or gas-phase.
  • the pre-polymerization step can be performed in-line as a part of a continuous polymerization process or separately in a batch process.
  • the process is for the (co)polymerization of propylene optionally in mixture with other olefins. It can be used for the production of crystalline propylene homo or copolymers containing up to 10 % of comonomer such as ethylene, butane- 1, or hexane-1, or for the production of impact resistant propylene polymer compositions comprising a relatively high crystalline propylene polymer fraction insoluble in xylene at 25°C, and a relatively low crystallinity copolymer fraction being soluble in xylene at 25°C.
  • melt flow rate MIL of the polymer was determined according to ISO 1133 (230°C, 2.16 Kg) EXAMPLES
  • Adduct A An initial amount of microspheroidal MgCl 2 -2.8C 2 H 5 OH was prepared according to the method described in Example 2 of WO98/44009, but operating on larger scale.
  • the solid adduct so obtained is called Adduct A.
  • Part of this solid was then subject to thermal dealcoholation at increasing temperatures from 30 to 130°C and operating in nitrogen flow until reaching an alcohol content of 50%wt.
  • Adduct B A part of this solid is further dealcoholated under nitrogen flow, until reaching 46%wt of ethanol. This solid is called Adduct C.
  • a solid catalyst component was prepared, following the description of catalyst component 1, with the following differences.
  • a solid catalyst component was prepared, following the description of catalyst component 1, with the following differences.
  • the three titanation steps were done at 100°C, 110°C and
  • the obtained solid contained 4.4%wt Ti and 13.2%wt of internal donor.
  • a solid catalyst component was prepared, following the description of catalyst component 1, with the following differences.
  • the magnesium precursor used was the Adduct C.
  • the three titanation steps were done at 110°C, 120°C and 120°C respectively.
  • the obtained solid contained 2.7%wt Ti and 10.5%wt of internal donor.
  • C donor cyclohexylmethyldimethoxysilane
  • the temperature was raised in five minutes to the desired temperature, and the polymerization was carried out at this temperature for two hours.
  • the non- reacted propylene was removed; the polymer was recovered and dried at 70°C under vacuum for three hours. Then the polymer was weighed and fractionated with o-xylene to determine the amount of the xylene insoluble (X.I.) fraction.
  • a lab-scale fluidized bed reactor equipped with recirculation gas compressor, recirculation heat exchanger, and automated temperature controller was used to polymerize propylene in gas phase.
  • the fluidized bed reactor is prepared at the desired temperature, pressure and composition, such to reach the targets values after discharging the prepolymerized catalyst into it.
  • Target values for the polymerization are pressure of 20 barg, composed of 93.8%mole of propylene, 5%mole of propane, and 1.2%mole of hydrogen.

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

Abstract

Procédé de (co)polymérisation de propylène mis en œuvre à une température allant de 77 à 95°C en présence d'un catalyseur comprenant le produit obtenu par réaction - d'un composé organoaluminium avec - un composant de catalyseur solide comprenant du Mg, du Ti, et un composé donneur d'électrons choisi parmi des diol esters spécifiques.
PCT/EP2011/068077 2010-10-19 2011-10-17 Procédé de polymérisation d'oléfines WO2012052386A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR112013008507A BR112013008507A2 (pt) 2010-10-19 2011-10-17 processo para a polimerização de olefinas
EP11770437.9A EP2630169A1 (fr) 2010-10-19 2011-10-17 Procédé de polymérisation d'oléfines
CN201180050746.8A CN103154050B (zh) 2010-10-19 2011-10-17 烯烃聚合方法
US13/878,712 US20130217844A1 (en) 2010-10-19 2011-10-17 Process for the polymerization of olefins

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP10187985.6 2010-10-19
EP10187985 2010-10-19
US40537410P 2010-10-21 2010-10-21
US61/405,374 2010-10-21

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WO2012052386A1 true WO2012052386A1 (fr) 2012-04-26

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CN (1) CN103154050B (fr)
BR (1) BR112013008507A2 (fr)
WO (1) WO2012052386A1 (fr)

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CN104761664A (zh) * 2015-03-13 2015-07-08 北京肯佰恩科技发展有限公司 用于烯烃聚合的催化剂组合物及其应用

Citations (14)

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US4220554A (en) 1977-05-25 1980-09-02 Montedison S.P.A. Components of catalysts for polymerizing alpha-olefins and the catalysts formed from the components
US4298718A (en) 1968-11-25 1981-11-03 Montecatini Edison S.P.A. Catalysts for the polymerization of olefins
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
US4495338A (en) 1968-11-21 1985-01-22 Montecatini Edison S.P.A. Components of catalysts for the polymerization of olefins
EP0395083A2 (fr) 1989-04-28 1990-10-31 Montell North America Inc. Composant et catalyseur pour polymérisation d'oléfines
EP0553805A1 (fr) 1992-01-31 1993-08-04 Montell Technology Company bv Composants et catalyseur pour la polymérisation d'oléfines
EP0553806A1 (fr) 1992-01-31 1993-08-04 Montell Technology Company bv Composants et catalyseur pour la polymérisation d'oléfines
EP0601525A1 (fr) 1992-12-11 1994-06-15 Montell Technology Company bv Composants et catalyseurs pour la polymerisation d'oléfines
WO1998044001A1 (fr) 1997-03-27 1998-10-08 Commonwealth Scientific And Industrial Research Organisation Reactifs polyvalents presentant une avidite elevee et une specificite multiple
WO1998044009A1 (fr) 1997-03-29 1998-10-08 Montell Technology Company B.V. Produits d'addition dichlorure de magnesium/alcool, leur procede de preparation et constituants pour catalyseurs obtenus a partir de ceux-ci
EP1666505A1 (fr) * 2003-09-18 2006-06-07 China Petroleum & Chemical Corporation Composants catalyseurs, catalyseurs pour polymerisation olefinique, et utilisation correspondante
US7388061B2 (en) 2002-02-07 2008-06-17 China Petroleum & Chemical Corporation Solid catalyst component for polymerization of olefins, catalyst comprising the same and use thereof
WO2009085649A1 (fr) 2007-12-21 2009-07-09 Dow Global Technologies Inc. Composition de catalyseur auto-limitant contenant un donneur interne bidentate

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CN100441561C (zh) * 2002-02-07 2008-12-10 中国石油化工股份有限公司 用于制备烯烃聚合催化剂的多酯化合物
CN1213080C (zh) * 2003-04-21 2005-08-03 中国石油化工股份有限公司 用于烯烃聚合反应的催化剂组分及其催化剂

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4495338A (en) 1968-11-21 1985-01-22 Montecatini Edison S.P.A. Components of catalysts for the polymerization of olefins
US4298718A (en) 1968-11-25 1981-11-03 Montecatini Edison S.P.A. Catalysts for the polymerization of olefins
US4220554A (en) 1977-05-25 1980-09-02 Montedison S.P.A. Components of catalysts for polymerizing alpha-olefins and the catalysts formed from the components
US4469648A (en) 1978-06-13 1984-09-04 Montedison S.P.A. Process for preparing spheroidally shaped products, solid at room temperature
US4399054A (en) 1978-08-22 1983-08-16 Montedison S.P.A. Catalyst components and catalysts for the polymerization of alpha-olefins
EP0395083A2 (fr) 1989-04-28 1990-10-31 Montell North America Inc. Composant et catalyseur pour polymérisation d'oléfines
EP0553805A1 (fr) 1992-01-31 1993-08-04 Montell Technology Company bv Composants et catalyseur pour la polymérisation d'oléfines
EP0553806A1 (fr) 1992-01-31 1993-08-04 Montell Technology Company bv Composants et catalyseur pour la polymérisation d'oléfines
EP0601525A1 (fr) 1992-12-11 1994-06-15 Montell Technology Company bv Composants et catalyseurs pour la polymerisation d'oléfines
WO1998044001A1 (fr) 1997-03-27 1998-10-08 Commonwealth Scientific And Industrial Research Organisation Reactifs polyvalents presentant une avidite elevee et une specificite multiple
WO1998044009A1 (fr) 1997-03-29 1998-10-08 Montell Technology Company B.V. Produits d'addition dichlorure de magnesium/alcool, leur procede de preparation et constituants pour catalyseurs obtenus a partir de ceux-ci
US7388061B2 (en) 2002-02-07 2008-06-17 China Petroleum & Chemical Corporation Solid catalyst component for polymerization of olefins, catalyst comprising the same and use thereof
EP1666505A1 (fr) * 2003-09-18 2006-06-07 China Petroleum & Chemical Corporation Composants catalyseurs, catalyseurs pour polymerisation olefinique, et utilisation correspondante
WO2009085649A1 (fr) 2007-12-21 2009-07-09 Dow Global Technologies Inc. Composition de catalyseur auto-limitant contenant un donneur interne bidentate

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CN103154050B (zh) 2016-11-16
CN103154050A (zh) 2013-06-12
BR112013008507A2 (pt) 2017-10-31
EP2630169A1 (fr) 2013-08-28

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