WO2006130953A1 - Process for the polymerization of olefins - Google Patents
Process for the polymerization of olefins Download PDFInfo
- Publication number
- WO2006130953A1 WO2006130953A1 PCT/CA2006/000757 CA2006000757W WO2006130953A1 WO 2006130953 A1 WO2006130953 A1 WO 2006130953A1 CA 2006000757 W CA2006000757 W CA 2006000757W WO 2006130953 A1 WO2006130953 A1 WO 2006130953A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- compound
- group
- polymerization
- catalyst
- Prior art date
Links
Classifications
-
- 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
- C08F110/02—Ethene
Definitions
- the present invention relates to a process for the polymerization of olefins and to the use of a cocatalyst aid in that process.
- polymerization processes to produce polymers for a wide variety of applications and products are well known in the art.
- any known polymerization catalyst systems may be utilized.
- Preferred are single-site catalyst containing systems, such as metallocenes or non-metallocene, and a more favorable system is a bimetallic catalyst system consisting of a metallocene and a Ziegler-Natta type catalyst.
- U.S. 5,283,218 is directed towards the prepolymerization of a metallocene catalyst.
- U.S. 5,332,706 and 5,473,028 disclosed to form a catalyst by "incipient impregnation”.
- EP 0 453 116 Al discloses the introduction of antistatic agents to the reactor for reducing the amount of sheets and agglomerates.
- WO 96/11961 discloses a supported catalyst system having an antistatic component for reducing fouling and sheeting in a gas, slurry or liquid pool polymerization process. Further, U.S.
- U.S. 5,410,002 discusses using a conventional Ziegler-Natta titanium/magnesium supported catalyst system where a selection of antistatic agents is added directly to the reactor to reduce fouling.
- WO 97/46599 relates to the use of soluble metallocene catalysts that are fed into a lean zone in a polymerization reactor with antifoulants or antistatic agents, such as ATMER 163 (available from ICI Specialty Chemicals, Baltimore, Md.).
- EP 811 638 A2 discusses the use of a metallocene catalyst and an activating cocatalyst in a polymerization process in the presence of a nitrogen containing antistatic agent.
- Aluminum alkyls are often used as scavengers for olefin polymerization. It is well known that an excess amount of scavenger, such as trimethylaluminum, will deactivate the single-site catalysts. It is desirable to have a reagent which has the functions of a scavenger with little effects on activated catalyst centers.
- Amine or hydroxylated amines are well known antistatic agents.
- the co-injection of such agents with catalyst(s) will reduce or even eliminate the reactor fouling/sheeting.
- the object is achieved by a process for the polymerization of olefins, comprising the steps of:
- the cocatalyst aid is a reaction product prepared separately prior to the introduction into the reactor by reacting at least one metal alkyl compound of group IIA or IIIA of the periodic system of elements and at least one compound (A) of the formula R m XR' n , wherein R is a branched, straight, or cyclic, substituted or unsubstituted, hydrocarbon group having 1 to 50 carbon atoms, R' is hydrogen or any functional group with at least one active hydrogen, X is at least one heteroatom selected from the group of O, N, P or S or a combination thereof, and wherein n and m are each at least 1 and are such that the formula has no net charge,
- compound (A) is selected from amine derivatives, imine derivatives, phenol derivatives, alcohols or hydroxy group containing alkyl amines.
- compound (A) is an amine.
- R is a hydrocarbon group having 10 to 40 carbon atoms.
- R' is a functional group of the formula -CH 2 CH 2 OH.
- the metal alkyl compound is an alkyl aluminum compound.
- the polymerization catalyst may be a single site catalyst containing catalyst system.
- the catalyst system is a metallocene containing catalyst system mixed with a Ziegler-Natta type catalyst.
- the polymerization catalyst is supported on a support selected from inorganic oxide, magnesium chloride, clay, zeolite, polymeric support, graphite, or mixtures thereof.
- the support is selected from the group consisting of silica, alumina, magnesia, titania, zirconia, polystyrene, polyethylene, polypropylene, polyvinylchloride, polycarbonate, polyketone, polyvinylalcohol, polymethylmethacrylate, cellulose, or mixtures thereof.
- the polymerization catalyst is activated by at least one cocatalyst which may be selected from the group consisting of aluminum alkyls, aluminoxanes, boranes and/or borates.
- the cocatalyst is methylaluminoxane (MAO), modified methylaluminoxane (MMAO), perfluorophenylborane, perfluorophenylborate, derivatives and/or mixtures thereof.
- MAO methylaluminoxane
- MMAO modified methylaluminoxane
- perfluorophenylborane perfluorophenylborate, derivatives and/or mixtures thereof.
- the process may be carried out in gas phase, slurry phase or solvent phase.
- a modifier, a promoter and/or a electron donor reagent may be added into the reactor.
- the modifier, promoter and/or electron donor reagent are selected from the group consisting of alcohol, titanate, ether, such as tetrahydrofurane, silicon containing compound, surfactant, antistatic reagent, antioxidant and/or fluorine containing compound.
- the ratio of the metal of the metal alkyl compound and X of compound (A) is from about 2:1 to about 4:1.
- the scavenger is selected from the group of triisobutylaluminum, trihexylaluminum, triisopropylaluminum, triethylaluminum and/or trimethylaluminum.
- a cocatalyst aid being a reaction product obtained by reacting at least one metal alkyl compound of group IIA or HIA of the periodic system of elements and at least one compound (A) of the formula R m XR' n , wherein R is a branched straight, or cyclic, substituted or unsubstituted, hydrocarbon group having 1 to 30 carbon atoms, R' is hydrogen or any functional group with at least one active hydrogen, X is at least one heteroatom selected from the group of O, N, P or S or a combination thereof, and n and m are each at least 1 and are such that the formula has not net charge, may be used in a process for the polymerization of olefins.
- a cocatalyst aid as defined above may be advantageously utilized which could be used as cocatalyst/scavenger as well as antifouling agent in that process.
- cocatalyst aid refers to a compound or a reagent which could help the cocatalyst to activate the polymerization catalyst or to prevent the deactivation of that catalyst, wherein the cocatalyst aid also prevents fouling and/or sheeting.
- the cocatalyst aid is prepared separately prior to being introduced into the polymerization reaction.
- an antistatic agent and a scavenger separately into the polymerisation reactor.
- the cocatalyst aid used is a reaction product of an aluminum alkyl and an amine.
- adducts R 1 NH 2 AlR 23
- elimination products R 1 NH-AlR 22
- dimers R 1 NH-AlR ⁇ 2
- R 23 A1-NH(R ! )-A1R 22 may be possible products, wherein R 1 and R 2 are any hydrocarbon groups.
- the process for the polymerization of olefins may be utilized to prepare homopolymers or copolymers of ethylene and alpha-olefins having about 3 to about 20 carbon atoms.
- Examples of typical catalysts, especially single-site catalysts, which may be used in the process of the invention include but are not limited to: 1. Bridged or unbridged metallocenes
- Ziegler-Natta type catalysts used in the inventive process may be any traditional Ziegler- Natta catalyst or modified Ziegler-Natta catalyst.
- Ziegler-Natta catalyst shall be a general term for coordination type catalysts before the discovery of metallocene or single site catalysts, having active metals such as Ti(IV), Ti(III), Cr, Zr, V, etc..
- the polymers produced in the process of the present invention may be used in a wide variety of products and end use applications.
- the polymers include homopolymers and copolymers of ethylene and other alpha-olefins. More preferably, bimodal (co)polymers, produced in a single reactor, are produced. However, also unimodal or multi-modal (co)polymers may be obtained.
- the polyolefins of the invention can be made into films, molded articles (including pipes), sheets, wire and cable coating and the like.
- the films produced may further contain additives, such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistats, polymer processing aids, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents.
- Preferred additives include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal stearates, talc, barium sulfate, diatomaceous earth, wax, carbon black, flame retarding additives, low molecular weight resins, hydrocarbon resins, glass beads and the like.
- ES70 silica which was calcinated at 600 0 C
- 20 mL of a mixture of MAO (10% in toluene) and a specific amount of metallocene (Ia: (n-BuCp) 2 ZrCl 2 or Ib: 2,2'-bis(2- indenyl)biphenylzirconiumdichloride) were mixed under a nitrogen atmosphere in a 100 mL round-bottom flask equipped with a stir bar. After stirring for an hour at 50 0 C, the solvents were then removed under vacuum.
- a mixture of 4 mL of MAO (10% in toluene) and a specific amount of metallocene (2,2'- bis(2-indenyl)biphenylzirconiumdichloride) at room temperature was added to 1 gram of Ziegler-Natta catalyst, prepared as above, and supported on silica to provide bimetallic catalyst Ha.
- the mixture was then stirred for Ih at 50 0 C. All solvents were then removed by evacuation and the residue was washed with isopentane three times followed by drying under vacuum.
- the polymerizations were carried out in a two-liter stirred autoclave, using deoxygenated isopentane as solvent. Hydrogen was added to control molecular weight, if desired, and a specific cocatalyst aid, as prepared above and disclosed in table 1, was added. Polymerizations were carried out at 88 0 C and 20 bars of total pressure, wherein ethylene gas was supplied on demand to maintain the overall pressure at 20 bars. Upon completion of the polymerization, the reactor was vented and cooled to ambient temperature to recover the polymer obtained. Details of each polymerization and characteristics of the resins produced are provided in Table 2 below. Table 2: Polymerizations with the cocatalyst aid
- the advantages of the inventive process are reducing or eliminating the poisoning effects of both the antistatic agent and aluminum alkyls while retaining scavenger functions of aluminum alkyl and antistating functions of antistatic agent in the cocatalyst aid.
- examples Cl, Ml and M2 are comparative examples, in that the catalyst was used with triisobutyl aluminium at different concentrations as scavenger only.
- example C2 is a comparative example in that the catalyst was used with triisobutyl aluminium and Atmer (ethoxylated amine, commercially available from ICI Speciality Chemicals, Baltimore, Md.), which were separately added into the reactor.
- the antistatic agent is added separately, it will reduce the electrostatic properties. However, it will act as poison to the metallocene catalyst, table 2, comparison of examples C2 and M5.
- the aluminium alkyl is used alone in a polymerization process, without antistatic agent, it will function as a cocatalyst/scavenger. It will also attack the activated catalyst. However, utilizing the inventive process, it is prevented that the aluminium alkyl attacks the catalyst, table 2, examples M2 and M5.
Landscapes
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EA200702640A EA018374B1 (en) | 2005-06-07 | 2006-05-12 | Process for the polymerization of olefins |
EP06741472.2A EP1888653B1 (en) | 2005-06-07 | 2006-05-12 | Process for the polymerization of olefins |
CN2006800199998A CN101189270B (en) | 2005-06-07 | 2006-05-12 | Process for the polymerization of olefins |
US11/921,616 US7919569B2 (en) | 2005-06-07 | 2006-05-12 | Process for the polymerizaion of olefins |
PL06741472T PL1888653T3 (en) | 2005-06-07 | 2006-05-12 | Process for the polymerization of olefins |
JP2008515007A JP5088891B2 (en) | 2005-06-07 | 2006-05-12 | Olefin polymerization method |
ES06741472.2T ES2567604T3 (en) | 2005-06-07 | 2006-05-12 | Procedure for the polymerization of olefins |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05012188.8 | 2005-06-07 | ||
EP05012188A EP1731535A1 (en) | 2005-06-07 | 2005-06-07 | Process for polymerization of olefins |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006130953A1 true WO2006130953A1 (en) | 2006-12-14 |
Family
ID=35241021
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2006/000757 WO2006130953A1 (en) | 2005-06-07 | 2006-05-12 | Process for the polymerization of olefins |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1731535A1 (en) |
JP (1) | JP5088891B2 (en) |
CN (1) | CN101189270B (en) |
EA (1) | EA018374B1 (en) |
ES (1) | ES2567604T3 (en) |
WO (1) | WO2006130953A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009536673A (en) * | 2006-05-11 | 2009-10-15 | バーゼル・ポリオレフィン・ゲーエムベーハー | Antistatic agent for olefin polymerization and method for producing the antistatic agent |
EP2610269A1 (en) | 2011-12-28 | 2013-07-03 | Saudi Basic Industries Corporation | Catalyst composition and method for preparing the same |
WO2020088942A1 (en) | 2018-10-31 | 2020-05-07 | Sabic Global Technologies B.V. | Process for the preparation of polyethylenes |
US11820879B2 (en) | 2018-12-28 | 2023-11-21 | Braskem S.A. | Continuous feed of antistatic agent for gas phase polymerization process |
WO2024132245A1 (en) | 2022-12-20 | 2024-06-27 | Sabic Global Technologies B.V. | Process for the production of polyethylene |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE503780T1 (en) † | 2007-05-25 | 2011-04-15 | Borealis Tech Oy | PRODUCTION PROCESS FOR AN ALPHA-OLEFIN POLYMER RESIN |
JP5667949B2 (en) * | 2011-09-08 | 2015-02-12 | 日本ポリエチレン株式会社 | Method for polymerizing olefins with improved polymer particle properties |
US9000200B2 (en) * | 2011-12-19 | 2015-04-07 | Saudi Basic Industries Corporation | Process for the preparation of metallocene complexes |
JP6454548B2 (en) * | 2011-12-19 | 2019-01-16 | サウディ ベーシック インダストリーズ コーポレイション | Process for preparing metallocene complexes |
CN103664595B (en) * | 2012-09-06 | 2015-07-22 | 中国石油化工股份有限公司 | Ether ester compound and application thereof |
JP6403230B2 (en) | 2013-05-03 | 2018-10-10 | ウポノール・イノベーション・エービーUponor Innovation Ab | Polyolefin pipe |
GB2525453A (en) | 2014-04-23 | 2015-10-28 | Uponor Innovation Ab | Polyolefin pipe |
WO2016102548A1 (en) * | 2014-12-22 | 2016-06-30 | Sabic Global Technologies B.V. | Process for transitioning between incompatible catalysts |
EP3237458B1 (en) | 2014-12-22 | 2022-06-22 | SABIC Global Technologies B.V. | Process for transitioning between incompatible catalysts |
WO2016151098A1 (en) | 2015-03-24 | 2016-09-29 | Sabic Global Technologies B.V. | Process for transitioning between incompatible catalysts |
CN107810057B (en) | 2015-06-19 | 2021-06-04 | 沙特阿拉伯石油公司 | Antifouling oligomerization catalyst system |
US11104621B2 (en) | 2016-01-07 | 2021-08-31 | Saudi Arabian Oil Company | Antifouling oligomerization catalyst systems |
WO2019060299A1 (en) | 2017-09-22 | 2019-03-28 | Saudi Arabian Oil Company | Inline process to make antifouling agent co-catalyst for ethylene oligomerization |
US11440980B2 (en) | 2020-07-22 | 2022-09-13 | Saudi Arabian Oil Company | Methods for forming ultra high molecular weight polyethylenes and methods for reducing contaminant content in such |
WO2022115748A1 (en) | 2020-11-30 | 2022-06-02 | Saudi Arabian Oil Company | Catalyst systems |
US11440857B2 (en) | 2020-11-30 | 2022-09-13 | Saudi Arabian Oil Company | Catalyst systems |
US11458462B2 (en) | 2020-11-30 | 2022-10-04 | Saudi Arabian Oil Company | Catalyst systems |
US11623208B2 (en) | 2020-11-30 | 2023-04-11 | Saudi Arabian Oil Company | Catalyst systems |
US11458463B2 (en) | 2020-11-30 | 2022-10-04 | Saudi Arabian Oil Company | Catalyst systems |
US11529622B2 (en) | 2021-03-12 | 2022-12-20 | Saudi Arabian Oil Company | Catalyst systems |
CN113087824B (en) * | 2021-03-19 | 2023-02-10 | 上海簇睿低碳能源技术有限公司 | Improved Ziegler-Natta catalyst and preparation method and application thereof |
US11484871B1 (en) | 2021-08-26 | 2022-11-01 | Saudi Arabian Oil Company | Catalyst systems |
US11623901B1 (en) | 2022-08-31 | 2023-04-11 | Saudi Arabian Oil Company | Catalyst systems that include silyl ether moieties |
US11639321B1 (en) | 2022-08-31 | 2023-05-02 | Saudi Arabian Oil Company | Catalyst systems that include meta-alkoxy substituted n-aryl bis-diphosphinoamine ligands |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997027228A1 (en) * | 1996-01-26 | 1997-07-31 | The Dow Chemical Company | Improved olefin addition polymerization catalyst composition |
EP0811638A2 (en) | 1996-06-06 | 1997-12-10 | Union Carbide Chemicals & Plastics Technology Corporation | Process for controlling static in polymerizations utilizing metallocene catalysts |
US6140432A (en) * | 1995-07-13 | 2000-10-31 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
US6245868B1 (en) * | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1316773A (en) * | 1961-02-21 | 1963-02-01 | Ethylene Plastique Sa | Polyaddition polymerization process |
JPH0343406A (en) * | 1989-07-12 | 1991-02-25 | Tosoh Corp | Production of stereoregular polyolefin |
FR2660926B1 (en) * | 1990-04-11 | 1992-07-31 | Bp Chemicals Snc | ALPHA-OLEFIN PREPOLYMER CONTAINING A TRANSITIONAL METAL AND PROCESS FOR THE POLYMERIZATION OF ALPHA-OLEFIN IN THE GAS PHASE USING THE PREPOLYMER. |
IT1262935B (en) * | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
ES2132744T3 (en) * | 1994-10-13 | 1999-08-16 | Exxon Chemical Patents Inc | CATALYTIC POLYMERIZATION SYSTEMS, THEIR PRODUCTION AND USE. |
JP3670163B2 (en) * | 1999-05-24 | 2005-07-13 | 三井化学株式会社 | Olefin slurry polymerization method |
US7205363B2 (en) * | 2003-06-11 | 2007-04-17 | Exxon Mobil Chemical Patents Inc. | Polymerization processes using antistatic agents |
-
2005
- 2005-06-07 EP EP05012188A patent/EP1731535A1/en not_active Withdrawn
-
2006
- 2006-05-12 CN CN2006800199998A patent/CN101189270B/en not_active Expired - Fee Related
- 2006-05-12 ES ES06741472.2T patent/ES2567604T3/en active Active
- 2006-05-12 JP JP2008515007A patent/JP5088891B2/en not_active Expired - Fee Related
- 2006-05-12 EA EA200702640A patent/EA018374B1/en not_active IP Right Cessation
- 2006-05-12 WO PCT/CA2006/000757 patent/WO2006130953A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6140432A (en) * | 1995-07-13 | 2000-10-31 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
WO1997027228A1 (en) * | 1996-01-26 | 1997-07-31 | The Dow Chemical Company | Improved olefin addition polymerization catalyst composition |
EP0811638A2 (en) | 1996-06-06 | 1997-12-10 | Union Carbide Chemicals & Plastics Technology Corporation | Process for controlling static in polymerizations utilizing metallocene catalysts |
US6245868B1 (en) * | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
Non-Patent Citations (6)
Title |
---|
HEALY M.D. ET AL.: "Sterically Crowded Aryloxide Compounds of Aluminum", ORGANOMETALLICS, vol. 7, 1988, pages 2543 - 2548, XP003004882 * |
KASKEL S. ET AL.: "Synthesis, Structure, and Characterization of [Ral(mu-NHEt)(mu-NEt)2Si(NHEt)]2(R=M,Et)", EUR. J. INORG. CHEM., vol. 6, 2003, pages 1193 - 1196, XP003004884 * |
MOHAMMED M. ET AL.: "Counterion Effects on Propylene Polymerization Using Two-State ansa-Metallocene Complexes", J. AM. CHEM. SOC., vol. 125, 2003, pages 7930 - 7941, XP003004881 * |
See also references of EP1888653A4 * |
SIEDLE A.R. ET AL.: "Exchange Reactions Between Dialkylzirconocene and Alkylaluminum Compounds", POLYHEDRON, vol. 9, 1999, pages 301 - 308, XP002298976 * |
WAGGONER K.M. AND POWER P.P.: "Reactions of Trimethylaluminum or Trimethylgallium with Bulky Amines: Structural Characterization of Thermolysis Products", J. AM. CHEM. SOC., vol. 113, 1991, pages 3385 - 3393, XP003004883 * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009536673A (en) * | 2006-05-11 | 2009-10-15 | バーゼル・ポリオレフィン・ゲーエムベーハー | Antistatic agent for olefin polymerization and method for producing the antistatic agent |
EP2610269A1 (en) | 2011-12-28 | 2013-07-03 | Saudi Basic Industries Corporation | Catalyst composition and method for preparing the same |
WO2013097936A1 (en) | 2011-12-28 | 2013-07-04 | Saudi Basic Industries Corporation | Catalyst composition and method for preparing the same |
WO2013097937A1 (en) | 2011-12-28 | 2013-07-04 | Saudi Basic Industries Corporation (Sabic) | Catalyst composition and method for preparing the same |
JP2015503644A (en) * | 2011-12-28 | 2015-02-02 | サウディ ベーシック インダストリーズ コーポレイション | Catalyst composition and method for preparing the same |
US9321864B2 (en) | 2011-12-28 | 2016-04-26 | Saudi Basic Industries Corporation | Catalyst composition and method for preparing the same |
US9902845B2 (en) | 2011-12-28 | 2018-02-27 | Saudi Basic Industries Corporation | Catalyst composition and method for preparing the same |
WO2020088942A1 (en) | 2018-10-31 | 2020-05-07 | Sabic Global Technologies B.V. | Process for the preparation of polyethylenes |
US11952440B2 (en) | 2018-10-31 | 2024-04-09 | Sabic Global Technologies B.V. | Process for the preparation of polyethylenes |
US11820879B2 (en) | 2018-12-28 | 2023-11-21 | Braskem S.A. | Continuous feed of antistatic agent for gas phase polymerization process |
WO2024132245A1 (en) | 2022-12-20 | 2024-06-27 | Sabic Global Technologies B.V. | Process for the production of polyethylene |
Also Published As
Publication number | Publication date |
---|---|
EA018374B1 (en) | 2013-07-30 |
EA200702640A1 (en) | 2008-06-30 |
CN101189270B (en) | 2011-11-16 |
CN101189270A (en) | 2008-05-28 |
JP5088891B2 (en) | 2012-12-05 |
ES2567604T3 (en) | 2016-04-25 |
EP1731535A1 (en) | 2006-12-13 |
JP2008542507A (en) | 2008-11-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7919569B2 (en) | Process for the polymerizaion of olefins | |
WO2006130953A1 (en) | Process for the polymerization of olefins | |
JP3631679B2 (en) | Polymerization method | |
US5767031A (en) | Ziegler-Natta catalysts modified with metallocenes | |
EP1764378B1 (en) | Catalyst composition for polymerization of olefins, polymerization process using the same, and method for its preparation | |
US6420298B1 (en) | Metallocene catalyst compositions, processes for making polyolefin resins using such catalyst compositions, and products produced thereby | |
MXPA02006571A (en) | Mixed zieglermetallocene catalysts for the production of bimodal polyolefins. | |
US6683016B1 (en) | Supported metallocene catalyst, its preparation method and olefin polymerization therewith | |
EP1339726B1 (en) | Catalyst composition and method of polymerization | |
KR101058282B1 (en) | Method for preparing metallocene supported catalyst for polyolefin polymerization and polyolefin polymerization method using metallocene supported catalyst prepared thereby | |
CA2425588C (en) | A method for preparing a catalyst system and its use in a polymerization process | |
AU2002231225A1 (en) | Catalyst composition and method of polymerization | |
US6765074B2 (en) | Olefin polymerization process | |
AU760357B2 (en) | Catalyst modifier and its use in the polymerization of olefin(s) | |
EP1574525A1 (en) | Catalyst composition for polymerization of olefins and polymerization process using the same | |
RU2454430C2 (en) | Continuity additives and use thereof in polymerisation processes | |
US20040077807A1 (en) | Supported catalysts which reduce sheeting in olefin polymerization, process for the preparation and the use thereof | |
US5739073A (en) | Addition of lithium compounds to ziegler-natta catalysts for increased molecular weight in polyolefins | |
JPH10298226A (en) | Production of ethylene polymer, olefin polymerization catalyst used therein, and solid catalyst component for the catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 200680019999.8 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008515007 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006741472 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200702640 Country of ref document: EA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 98/DELNP/2008 Country of ref document: IN |
|
WWP | Wipo information: published in national office |
Ref document number: 2006741472 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11921616 Country of ref document: US |