US20100069580A1 - Catalyst composition for the (co) polymerization of propylene - Google Patents
Catalyst composition for the (co) polymerization of propylene Download PDFInfo
- Publication number
- US20100069580A1 US20100069580A1 US12/305,217 US30521707A US2010069580A1 US 20100069580 A1 US20100069580 A1 US 20100069580A1 US 30521707 A US30521707 A US 30521707A US 2010069580 A1 US2010069580 A1 US 2010069580A1
- Authority
- US
- United States
- Prior art keywords
- propylene
- catalyst
- compound
- succinate
- diether
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- 0 [1*]C([2*])(C(=O)O[5*])C([3*])([4*])C(=O)O[6*] Chemical compound [1*]C([2*])(C(=O)O[5*])C([3*])([4*])C(=O)O[6*] 0.000 description 1
Classifications
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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
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
-
- 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
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
-
- 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
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
Definitions
- the present invention relates to the polymerization of propylene with one or more optional comonomers in presence of a blend of at least two Ziegler-Natta catalysts with different internal donors.
- Polypropylene has become one of the most widely used polymers due to its good combination of properties. Most of the polypropylene today is produced by polymerizing propylene and optionally one or more comonomers in presence of Ziegler-Natta catalysts, i.e. transition metal coordination catalysts, specifically titanium halide containing catalysts. Such catalysts also contain internal electron donors, with phthalates being the most widely used. Polypropylenes made with such catalysts have an acceptable balance of properties. To further improve, different catalyst compositions, and especially different internal electron donors have been developed and tested, and in some cases also commercialized.
- Ziegler-Natta catalysts i.e. transition metal coordination catalysts, specifically titanium halide containing catalysts.
- Such catalysts also contain internal electron donors, with phthalates being the most widely used.
- Polypropylenes made with such catalysts have an acceptable balance of properties. To further improve, different catalyst compositions, and especially different internal electron donors have been developed and tested, and in some cases also commercialized.
- WO 02/100904 discloses 1,3-diethers as internal electron donors, said diethers having the general formula R 1 R 2 C(CH 2 OR) 2 with R being a C 1 -C 10 alkyl group, R 1 being a linear or branched primary alkyl radical with at least three carbon atoms, and R 2 being a secondary alkyl or cycloalkyl radical, which is different from isopropyl. Both, R 1 and R 2 may optionally contain a heteroatom.
- R 1 and R 2 may optionally contain a heteroatom.
- the use of 1,3-diethers leads to polypropylenes with narrow molecular weight distribution and very high isotacticity.
- WO 00/63261 discloses substituted succinates as internal electron donors.
- Polypropylenes made with a polymerization catalyst comprising a succinate as internal electron donor are characterized by a broad molecular weight distribution and high isotacticity.
- the present invention relates to a process for the production of propylene polymers, said process comprising the step of polymerizing propylene and one or more optional comonomers in one or more polymerization reactors in presence of
- the present invention relates to a propylene polymer produced with such a process.
- the propylene polymers of the present invention can be homopolymers or copolymers of propylene and one or more comonomers, which can be ethylene or a C 4 -C 20 alpha-olefin.
- the copolymers can be random copolymers or heterophasic copolymers.
- the random copolymers of the present invention comprise at least 0.1 wt % of comonomer(s), preferably at least 0.2 wt %, more preferably at least 0.5 wt %, even more preferably at least 1 wt %, and most preferably at least 2 wt %. They comprise up to 10 wt % of comonomer(s), preferably up to 8 wt %, and most preferably up to 6 wt %.
- the random copolymers are copolymers of propylene and ethylene.
- the heterophasic copolymers of the present invention comprise a matrix, which in turn is made of propylene homopolymer or random copolymer as defined above, and a rubber phase.
- the heterophasic copolymers are copolymers of propylene and ethylene. They have an ethylene content in the range from 4 wt % to 15 wt %.
- the heterophasic copolymers comprise from 5 wt % to 35 wt % of rubber phase.
- the rubber phase is an ethylene propylene rubber.
- the polymerization of propylene and one or more optional comonomers is performed in presence of one or more Ziegler-Natta catalysts, an organo-aluminium compound and an optional external donor.
- a Ziegler-Natta catalyst comprises a titanium compound having at least one titanium-halogen bond, and an internal electron donor, both supported on magnesium halide in active form.
- the blend of Ziegler-Natta catalysts comprises at least a diether catalyst and a succinate catalyst.
- the blend of Ziegler-Natta catalysts is a blend of a diether catalyst and a succinate catalyst.
- Such catalysts are known in the art and can for example be obtained by reaction of an anhydrous magnesium halide with an alcohol, followed by titanation with a titanium halide and reaction with a diether compound resp. a succinate compound as internal electron donor according to the methods described in patent applications WO 00/63261 and WO 02/100904.
- Such a catalyst comprises 2.5-7.5 wt % of titanium, about 10-20 wt % of magnesium and about 5-30 wt % of internal donor with chlorine and solvent making up the remainder.
- Particularly suited diether compounds are 1,3-diethers of formula
- diethers are 2-methyl-2-isopropyl-1,3-dimethoxypropane; 2,2-diisobutyl-1,3-dimethoxypropane; 2-isopropyl-2-cyclo-pentyl-1,3-dimethoxypropane; 2-isopropyl-2-isoamyl-1,3-dimethoxypropane; 9,9-bis(methoxymethyl)fluorene.
- Suitable succinate compounds have the formula
- the organoaluminium compound is advantageously an Al-alkyl compound of the Al-trialkyls family, such as Al-triethyl, Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO 4 or SO 3 groups.
- Al-triethyl is preferred.
- the Al-trialkyl has a hydride content, expressed as AlH 3 , of less than 1.0 wt % with respect to the Al-trialkyl. More preferably, the hydride content is less than 0.5 wt %, and most preferably the hydride content is less than 0.1 wt %.
- the organoaluminium compound is used in such an amount as to have a molar ratio Al/Ti in the range from 1 to 1000.
- the upper limit is 500. More preferably, the upper limit is 400.
- the lower limit is preferably 10, more preferably 20, and most preferably 50.
- Suitable external donors include certain silanes, ethers, esters, amines, ketones and heterocyclic compounds. It is preferred to use a 1,3-diether as described above or a silane. It is most preferred to use silanes of the general formula
- the molar ratio of organo-aluminium compound to external donor ranges advantageously between 1 and 1000.
- the upper limit of the AI/ED ratio preferably is at most 800, more preferably at most 600 and most preferably at most 400.
- the lower limit of the AI/ED ratio preferably is at least 5, more preferably at least 10, even more preferably at least 20 and most preferably at least 30.
- the molar ratio of organo-aluminium compound to external donor ranges from 1 to 200.
- the upper limit of the AI/ED ratio preferably is at most 150, more preferably at most 100, even more preferably at most 80 and most preferably at most 65.
- the lower limit of the AI/ED ratio preferably is at least 3 and more preferably at least 5.
- the weight ratio of diether catalyst to succinate catalyst ranges from 0.01 to 100.
- the upper limit of the weight ratio is preferably at most 10, more preferably at most 5, even more preferably at most 3, and most preferably at most 1.5.
- the lower limit of the weight ratio is preferably at least 0.02, more preferably at least 0.05, even more preferably at least 0.1 and most preferably at least 0.2.
- Such a blend of catalysts can be supplied to a polymerization plant either in pre-prepared form or can be prepared directly at the polymerization plant. Alternatively, it is also possible to introduce the catalysts separately into the polymerization reactor, possibly also at different places. If the production of the propylene polymer is conducted in more than one polymerization reactor it is also possible to introduce the catalysts into different polymerization reactors.
- the polymerization of propylene and one or more optional comonomers can be carried out according to known techniques.
- the polymerization can for example be carried out in liquid propylene as reaction medium. It can also be carried out in a diluent, such as an inert hydrocarbon (slurry polymerization) or in the gas phase.
- a diluent such as an inert hydrocarbon (slurry polymerization) or in the gas phase.
- the polymerization is preferably carried out in one or more polymerization reactors in series, employing liquid propylene as reaction medium and then in one or more gas phase reactors in series, as is done for example in a propylene polymer production line based on Spheripol technology. It is preferred to produce a heterophasic propylene copolymer sequentially in (a) one or more loop reactors and (b) one or more gas phase reactors. It is most preferred to employ only one gas phase reactor.
- propylene homopolymers and random copolymers are preferably produced by polymerization in liquid propylene at temperatures in the range from 20° C. to 100° C. Preferably, temperatures are in the range from 60° C. to 80° C.
- the pressure can be atmospheric or higher. It is preferably between 25 and 50 bar.
- the molecular weight of the polymer chains, and in consequence of the melt flow of the propylene polymer, is regulated by adding hydrogen.
- Propylene polymers produced according to the present invention are characterized by a broad molecular weight distribution and a high isotacticity index.
- the present invention allows the production of bimodal propylene polymers in one single polymerization reactor.
- propylene polymers with high melt flow index, i.e. low viscosity show increased melt strength due to tailing in the high molecular weight fraction, thus allowing for better processability e.g. in extrusion applications.
- a bimodal propylene polymer i.e. a propylene polymer having a bimodal molecular weight distribution, comprises two propylene polymer fractions whose molecular weights are different enough to be reproducibly separated by a suitable analytical method, for example by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- Heterophasic propylene copolymers produced according to the present invention have a homo- or random copolymer matrix of broad or bimodal molecular weight distribution and, if applicable, a bimodal distribution of comonomer insertion and a rubber phase with a broad or bimodal molecular weight distribution and a bimodal distribution of comonomer insertion.
- the rubber phase can for example be an ethylene propylene rubber (EPR).
- EPR ethylene propylene rubber
- the present invention avoids having to use two gas-phase reactors, as is currently the case if a succinate compound is used as sole internal electron donor, for the production of an EPR phase so as to give a heterophasic copolymer with good stiffness/impact balance.
- the propylene polymers made according to the present invention show improved flow, shrinkage and processing behavior.
- the propylene polymer may contain additives such as, by way of example, antioxidants, light stabilizers, acid scavengers, lubricants, antistatic additives, nucleating/clarifying agents, colorants.
- additives such as, by way of example, antioxidants, light stabilizers, acid scavengers, lubricants, antistatic additives, nucleating/clarifying agents, colorants.
- the propylene polymers of the present invention can be used in extrusion applications and injection molding applications, particularly in film extrusion, fiber extrusion, sheet, injection molding, blow molding, extrusion stretch blow molding, thermoforming, etc.
- Melt flow is measured according to norm ASTM D 1238, condition L.
- Xylene solubles are determined as follows: Between 4.5 and 5.5 g of propylene polymer are weighed into a flask and 300 ml xylene are added. The xylene is heated under stirring to reflux for 45 minutes. Stirring is continued for 15 minutes exactly without heating. The flask is then placed in a thermostat bath set to 25° C. ⁇ 1° C. for 1 hour. The solution is filtered through Whatman n° 4 filter paper and exactly 100 ml of solvent are collected. The solvent is then evaporated and the residue dried and weighed. The percentage of xylene solubles (“XS”) is then calculated according to
- Molecular weights and molecular weight distribution have been measured by GPC with trichlorobenzene as solvent. Calibration is done via commercially available polystyrene standards.
- the polymerizations were conducted in an autoclave bench reactor having a volume of 3 l.
- the reactor was first charged with liquid propylene and an appropriate amount of hydrogen for melt flow control.
- a mix of polymerization catalyst(s), aluminium triethyl, and (cyclopentyl) 2 Si(OCH 3 ) 2 (generally referred to as “D-donor”) as external donor was flushed into the reactor with liquid propylene.
- Total volume of liquid propylene in the reactor was 2 l.
- the reactor was then heated to 70° C.
- the polymerization was run for 60 minutes and then stopped by flashing of the propylene.
- the retrieved propylene polymer fluff was worked up by standard procedures.
- Avant ZN 126 and Avant ZN 168 were employed as polymerization catalysts.
- Avant ZN 126 is a Ziegler-Natta catalyst with 3.5 wt % titanium and a diether compound as internal electron donor, which is commercially available from Basell.
- Avant ZN 168 is a Ziegler-Natta catalyst with 2.6 wt % titanium and a succinate compound as internal electron donor, which is commercially available from Basell.
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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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06115777A EP1857476A1 (fr) | 2006-04-24 | 2006-06-21 | Composition catalytique pour la (co)polymérisation de propylène |
EP06115777.2 | 2006-06-21 | ||
PCT/EP2007/056173 WO2007147864A2 (fr) | 2006-06-21 | 2007-06-21 | Composition de catalyseur pour la (co)polymérisation du propylène |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/056173 A-371-Of-International WO2007147864A2 (fr) | 2006-06-21 | 2007-06-21 | Composition de catalyseur pour la (co)polymérisation du propylène |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/215,235 Continuation US9206267B2 (en) | 2006-06-21 | 2014-03-17 | Catalyst composition for the (co)polymerization of propylene |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100069580A1 true US20100069580A1 (en) | 2010-03-18 |
Family
ID=38669147
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/305,217 Abandoned US20100069580A1 (en) | 2006-06-21 | 2007-06-21 | Catalyst composition for the (co) polymerization of propylene |
US14/215,235 Active US9206267B2 (en) | 2006-06-21 | 2014-03-17 | Catalyst composition for the (co)polymerization of propylene |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/215,235 Active US9206267B2 (en) | 2006-06-21 | 2014-03-17 | Catalyst composition for the (co)polymerization of propylene |
Country Status (9)
Country | Link |
---|---|
US (2) | US20100069580A1 (fr) |
EP (1) | EP2029637B1 (fr) |
JP (1) | JP2009541515A (fr) |
KR (1) | KR101414916B1 (fr) |
CN (1) | CN101479304B (fr) |
AT (1) | ATE465184T1 (fr) |
DE (1) | DE602007006011D1 (fr) |
PL (1) | PL2029637T3 (fr) |
WO (1) | WO2007147864A2 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012139897A1 (fr) * | 2011-04-12 | 2012-10-18 | Basell Poliolefine Italia S.R.L. | Composants catalytiques pour la polymérisation d'oléfines |
US9187586B2 (en) | 2009-10-01 | 2015-11-17 | Total Research & Technology Feluy | Propylene polymer with improved processability in thermoforming |
US9611340B2 (en) | 2013-06-03 | 2017-04-04 | Lummus Novolen Technology Gmbh | High performance Ziegler-Natta catalyst systems, processes for producing such catalyst systems, and use thereof |
US10221261B2 (en) * | 2011-09-23 | 2019-03-05 | Basell Poliolefine Italia S.R.L. | Process for the preparation of high purity propylene polymers |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1849807A1 (fr) * | 2006-04-24 | 2007-10-31 | Total Petrochemicals Research Feluy | Composition catalytique pour la coplymerisation de propylène |
EP2077286A1 (fr) * | 2008-01-07 | 2009-07-08 | Total Petrochemicals Research Feluy | Copolymère de propylène hétérophasique avec comportement de fluage amélioré |
CN107043491A (zh) | 2009-06-19 | 2017-08-15 | 巴塞尔聚烯烃意大利有限责任公司 | 制备抗冲击性丙烯聚合物组合物的方法 |
US9068029B2 (en) | 2009-11-19 | 2015-06-30 | Basell Poliolefine Italia S.R.L. | Process for the preparation of impact resistant propylene polymer compositions |
CN102453149B (zh) * | 2010-10-21 | 2013-06-05 | 中国石油化工股份有限公司 | 烯烃聚合催化剂组分和烯烃聚合催化剂以及烯烃聚合方法 |
CN102453147B (zh) * | 2010-10-21 | 2013-06-05 | 中国石油化工股份有限公司 | 烯烃聚合催化剂组分和烯烃聚合催化剂以及烯烃聚合方法 |
CN103635495B (zh) * | 2011-07-01 | 2016-06-22 | 巴塞尔聚烯烃意大利有限责任公司 | 聚丙烯膜和片材 |
EP2594593A1 (fr) | 2011-11-17 | 2013-05-22 | Basell Poliolefine Italia S.r.l. | Procédé de préparation de compositions à base de polymère de propylène hétérophase |
EP2682505A1 (fr) * | 2012-07-06 | 2014-01-08 | Basell Poliolefine Italia S.r.l. | Fibres de polypropylène |
ES2765401T3 (es) | 2015-12-21 | 2020-06-09 | Borealis Ag | Artículos con propiedades ópticas mejoradas |
JP7466306B2 (ja) | 2016-08-19 | 2024-04-12 | 中国科学院化学研究所 | 超高分子量超微粒子径ポリエチレン及びその製造方法と応用 |
EP3510060A1 (fr) | 2016-09-08 | 2019-07-17 | Total Research & Technology Feluy | Procédé de préparation de polypropylène |
Citations (11)
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US4071674A (en) * | 1972-09-14 | 1978-01-31 | Mitsui Petrochemical Industries Ltd. | Process for polymerization or copolymerization of olefin and catalyst compositions used therefor |
CN1042547A (zh) * | 1988-09-30 | 1990-05-30 | 希蒙特公司 | 烯烃聚合成分及催化剂 |
EP0782587B1 (fr) * | 1995-07-20 | 1999-02-24 | Montell Technology Company bv | Procede et appareil de polymerisation en phase gazeuse d'alpha-olefines |
WO2000063261A1 (fr) * | 1999-04-15 | 2000-10-26 | Basell Technology Company B.V. | Constituants et catalyseurs de polymerisation d'olefines |
US6489411B1 (en) * | 1993-06-30 | 2002-12-03 | Fina Technology, Inc. | Catalyst formulation and polymerization processes |
US20040014597A1 (en) * | 2001-06-13 | 2004-01-22 | Giampiero Morini | Components and catalysts for the (co) polymerization of olefins |
WO2005014713A1 (fr) * | 2003-08-05 | 2005-02-17 | Basell Poliolefine Italia S.R.L. | Articles a base de polyolefines |
CN1597714A (zh) * | 2003-09-18 | 2005-03-23 | 中国石油化工股份有限公司 | 一种生产烯烃聚合物的方法及其聚合物 |
US20060167192A1 (en) * | 2002-06-24 | 2006-07-27 | Jari Aarila | Process for the production of linear low-density polyethlene composition |
US20070270556A1 (en) * | 2004-12-20 | 2007-11-22 | Basell Poliolefine Italia S.R.L. | Process and Apparatus for the Polymerization of Propylene |
US20070287813A1 (en) * | 2006-06-01 | 2007-12-13 | Craig Meverden | High crystallinity, high melt flow rate polypropylene |
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JP2825909B2 (ja) * | 1989-03-02 | 1998-11-18 | 三井化学株式会社 | オレフィンの重合方法およびオレフィン重合用触媒 |
JP2005187651A (ja) * | 2003-12-25 | 2005-07-14 | Toho Catalyst Co Ltd | オレフィン類重合用固体触媒成分及び触媒 |
US7022797B2 (en) * | 2004-02-20 | 2006-04-04 | Fina Technology, Inc. | Polymerization process |
CN101065437B (zh) * | 2004-10-04 | 2010-12-08 | 巴塞尔聚烯烃意大利有限责任公司 | 弹性体聚烯烃组合物 |
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2007
- 2007-06-21 CN CN2007800224551A patent/CN101479304B/zh not_active Expired - Fee Related
- 2007-06-21 JP JP2009515880A patent/JP2009541515A/ja active Pending
- 2007-06-21 EP EP07786781A patent/EP2029637B1/fr active Active
- 2007-06-21 WO PCT/EP2007/056173 patent/WO2007147864A2/fr active Application Filing
- 2007-06-21 PL PL07786781T patent/PL2029637T3/pl unknown
- 2007-06-21 US US12/305,217 patent/US20100069580A1/en not_active Abandoned
- 2007-06-21 DE DE602007006011T patent/DE602007006011D1/de active Active
- 2007-06-21 KR KR1020087030466A patent/KR101414916B1/ko active IP Right Grant
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Cited By (7)
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US9187586B2 (en) | 2009-10-01 | 2015-11-17 | Total Research & Technology Feluy | Propylene polymer with improved processability in thermoforming |
WO2012139897A1 (fr) * | 2011-04-12 | 2012-10-18 | Basell Poliolefine Italia S.R.L. | Composants catalytiques pour la polymérisation d'oléfines |
RU2598073C2 (ru) * | 2011-04-12 | 2016-09-20 | Базелль Полиолефин Италия С.Р.Л. | Компоненты катализатора для полимеризации олефинов |
US9593171B2 (en) | 2011-04-12 | 2017-03-14 | Basell Poliolefine Italia S.R.L. | Catalyst components for the polymerization of olefins |
US10221261B2 (en) * | 2011-09-23 | 2019-03-05 | Basell Poliolefine Italia S.R.L. | Process for the preparation of high purity propylene polymers |
US9611340B2 (en) | 2013-06-03 | 2017-04-04 | Lummus Novolen Technology Gmbh | High performance Ziegler-Natta catalyst systems, processes for producing such catalyst systems, and use thereof |
US10273319B2 (en) * | 2013-06-03 | 2019-04-30 | Lummus Novolen Technology Gmbh | High performance Ziegler-Natta catalyst systems, processes for producing such catalyst systems, and use thereof |
Also Published As
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WO2007147864A3 (fr) | 2008-02-21 |
US20140200316A1 (en) | 2014-07-17 |
KR20090031357A (ko) | 2009-03-25 |
EP2029637A2 (fr) | 2009-03-04 |
DE602007006011D1 (de) | 2010-06-02 |
ATE465184T1 (de) | 2010-05-15 |
WO2007147864A2 (fr) | 2007-12-27 |
JP2009541515A (ja) | 2009-11-26 |
EP2029637B1 (fr) | 2010-04-21 |
CN101479304B (zh) | 2012-03-21 |
KR101414916B1 (ko) | 2014-07-04 |
CN101479304A (zh) | 2009-07-08 |
PL2029637T3 (pl) | 2010-08-31 |
US9206267B2 (en) | 2015-12-08 |
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