US20080287618A1 - Solid State Properties Of Polyethylene Prepared With Tetrahydroindenyl-Based Catalyst System - Google Patents

Solid State Properties Of Polyethylene Prepared With Tetrahydroindenyl-Based Catalyst System Download PDF

Info

Publication number
US20080287618A1
US20080287618A1 US11/667,792 US66779205A US2008287618A1 US 20080287618 A1 US20080287618 A1 US 20080287618A1 US 66779205 A US66779205 A US 66779205A US 2008287618 A1 US2008287618 A1 US 2008287618A1
Authority
US
United States
Prior art keywords
less
unsubstituted
reactor
indenyls
injecting
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
Application number
US11/667,792
Other languages
English (en)
Inventor
Eric Maziers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies One Tech Belgium SA
Original Assignee
Total Petrochemicals Research Feluy SA
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.)
Filing date
Publication date
Application filed by Total Petrochemicals Research Feluy SA filed Critical Total Petrochemicals Research Feluy SA
Assigned to TOTAL PETROCHEMICALS RESEARCH FELUY reassignment TOTAL PETROCHEMICALS RESEARCH FELUY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAZIERS, ERIC
Publication of US20080287618A1 publication Critical patent/US20080287618A1/en
Priority to US12/876,523 priority Critical patent/US8822611B2/en
Assigned to TOTAL RESEARCH & TECHNOLOGY FELUY reassignment TOTAL RESEARCH & TECHNOLOGY FELUY CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: TOTAL PETROCHEMICALS RESEARCH FELUY
Priority to US14/327,700 priority patent/US9255161B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/74Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
    • C08F4/76Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit

Definitions

  • This invention relates to the field of polyethylene prepared with a catalyst system based on a tetrahydroindenyl catalyst component and to their solid state properties.
  • Rotomoulding is used for the manufacture of simple to complex, hollow plastic products. It can be used to mould a variety of materials such as for example polyethylene, polypropylene, polycarbonate or polyvinyl chloride (PVC).
  • Polyethylene (PE) represents more than 80% of the polymers used in the rotomoulding market. This is due to the outstanding resistance of polyethylene to thermal degradation during processing, to its easy grinding, good flowability, and low temperature impact properties.
  • Polyethylenes prepared with a Ziegler-Natta catalyst are generally used in rotomoulding, but metallocene-produced polyethylenes are desirable, because their narrow molecular weight distribution allows better impact properties and shorter cycle time in processing.
  • the present invention discloses a method for preparing a homopolymer or a copolymer of ethylene that comprises the steps of:
  • (Ind) is an indenyl or an hydrogenated indenyl, substituted or unsubstituted
  • R′′ is a structural bridge between the two indenyls to impart stereorigidity that comprises a C 1 -C 4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical, which bridge is substituted or unsubstituted
  • Q is a hydrocarbyl radical having from 1 to 20 carbon atoms or a halogen
  • M is a transition metal Group 4 of the Periodic Table or Vanadium
  • ii) an activating agent and iii) optionally a support b) injecting into the reactor ethylene monomer at a concentration of at least 6.5 wt %, c) injecting an amount of hydrogen such that the ratio H 2 /C 2 in the feed is of less than 85 g/10 6 g; d) maintaining under polymerisation conditions at a temperature of less than 90
  • Each indenyl or hydrogenated indenyl compound may be substituted in the same way or differently from one another at one or more positions in the cyclopentadienyl ring, the cyclohexenyl ring and the bridge.
  • Each substituent on the indenyl may be independently chosen from those of formula XR v in which X is chosen from Group 14 of the Periodic Table, oxygen and nitrogen and each R is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms and v+1 is the valence of X.
  • X is preferably C.
  • the cyclopentadienyl ring is substituted, its substituent groups must not be so bulky as to affect coordination of the olefin monomer to the metal M.
  • Substituents on the cyclopentadienyl ring preferably have R as hydrogen or CH 3 . More preferably, at least one and most preferably both cyclopentadienyl rings are unsubstituted.
  • both indenyls are unsubstituted, and most preferably they are unsubstituted hydrogenated indenyls.
  • the active catalyst system used for polymerising ethylene comprises the above-described catalyst component and a suitable activating agent having an ionising action.
  • Suitable activating agents are well known in the art.
  • the catalyst component can be supported on a support.
  • the polymerisation conditions necessary to obtain the desired polyethylene resin comprise a high concentration of ethylene, little or no hydrogen and a low polymerisation temperature.
  • the concentration of ethylene is of at least 6.5 wt %, preferably of at least 7 wt %.
  • the amount of hydrogen is selected to give a H 2 /C 2 in the feed of at most 85 g/10 6 g, preferably of at most 60 g/10 6 g, more preferably there is no hydrogen.
  • the polymerisation temperature is of less than 90° C., preferably of less than 88° C., more preferably of from 80 to 85° C.
  • the PE resins prepared with the metallocene catalyst system of the present invention may be homo- or co-polymers of ethylene with densities ranging from 0.930 to 0.965 g/cc.
  • the density is measured following the method of standard test ASTM 1505 at a temperature of 23° C.
  • the melt index is typically of at least 0.5, preferably of at least 3, as measured following the method of standard test ASTM D 1238 under a load of 2.16 kg and at a temperature of 190° C. They are characterised by a narrow molecular weight distribution, typically with a polydispersity index (D) lower than 3.
  • the polydispersity index is defined as the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn.
  • the long Chain Branching Index (LCBI) is superior to 0, indicating the presence of long chain branching. It is surprisingly observed that the long chain branching (LCB) initiates an auto-nucleation process. The magnitude of this nucleation process increases with increasing long chain branching and LCB itself can be tailored by modifying the polymerisation conditions. This auto-nucleation process suppresses or reduces the need for external nucleating agents for polyethylene resins.
  • polyethylene resins can be used to prepare articles by all methods generally used in the field, such as for example rotomoulding, injection moulding, blow moulding or extrusion. They are particularly advantageous in rotomoulding applications.
  • the finished articles according to the present invention have several attractive properties.
  • the barrier properties of articles prepared with the resins according to the invention are of less than 1 g/day, preferably of less than 0.5 g/day.
  • FIG. 1A to 1J represent the microstructure measured on 700 mL rotomoulded bottles prepared respectively with resins R1 to R10.
  • FIG. 2 represents the true deformation expressed in cm as a function of time expressed in weeks for resins R7, R8 and R9.
  • the star for resin R8 indicates breakage.
  • FIG. 3 represents the true deformation expressed in cm as a function of time expressed in weeks for resins R3, R4 and R6.
  • FIG. 4 represents the true longitudinal deformation expressed in mm as a function of time expressed in seconds in traction creep tests carried out at a temperature of 80° C. with applied stresses of 14 to 18 MPa on rotomoulded parts prepared respectively with resins R4 and R6.
  • FIG. 5 represents the true longitudinal deformation expressed in mm as a function of time expressed in seconds in traction creep tests carried out at room temperature with an applied stress of 16 MPa on rotomoulded parts prepared respectively with resins R3 and R6.
  • FIG. 6 represents the long branching index LCBI as a function of spherulite size expressed in ⁇ m.
  • FIG. 7 represents the spherulite size expressed in ⁇ m as a function of melt index MI 2 expressed in dg/min.
  • FIG. 8 represents the LCBI as a function of melt index MI 2 expressed in dg/min.
  • FIGS. 9 a , 9 b and 9 c represent the load displacement curves at a temperature of ⁇ 40° C. for 4.5 mm thick rotomoulded articles prepared respectively with resins R6, R3 and R4.
  • the load is expressed in Newtons and the displacement in mm.
  • Resin R1 is a Ziegler-Natta (ZN) PE resin sold by Exxon Mobill Chemicals under the name LX0210.
  • Resin R2 is a ZN PE resin sold by Matrix under the name N307.
  • Resin R3 is a ZN PE resin sold by Dow Chemicals under the name NG2432.
  • Resin R4 is a metallocene-prepared PE resin sold by Borealis under the name
  • Resin R5 is a ZN PE resin sold by Borealis under the name RG7403.
  • Resin R6 is a resin according to the present invention prepared with a bridged bis(tetrahydroindenyl)-based catalyst system.
  • Resin R7 is a metallocene-prepared PE sold by Borealis under the name RM8403.
  • Resin R8 is a ZNPE resin sold by Dow Chemicals under the name NG2431.
  • Resin R9 is a resin according to the present invention prepared with a bridged bis(tetrahydroindenyl)-based catalyst system.
  • Resin R10 is a resin according to the present invention prepared with a bridged bis(tetrahydroindenyl)-based catalyst system.
  • Resin R11 is a homopolymer of ethylene according to the present invention prepared with a bridged bis(tetrahydroindenyl)-based catalyst system.
  • the melt flow index MI 2 was measured following the method of standard test ASTM D 1238, under a load of 2.16 kg and at a temperature of 190° C.
  • the density was measured following the method of standard test ASTM D 1505 at a temperature of 23° C.
  • the spherulite size is measured by Small Angle Light Scattering (SALS).
  • SALS Small Angle Light Scattering
  • a beam of light passes through a thin slice of a semi-crystalline polymer, which is positioned between two crossed polarisers, the spherulites of the polymer diffuse the light and a four-leaf pattern is projected onto a screen positioned after the second polariser.
  • the size of the pattern is inversely related to the spherulite diameter and may be used for its determination.
  • the Young modulus was measured on compression-moulded samples following the method of standard test ASTM D 790 on samples R3 and R6 having an identical density.
  • the Young modulus of resin R6 was higher than that of prior art resin R3 with values respectively of 575 MPa for resin R3 and of 615 Mpa for resin R6.
  • the resistance to impact was tested by the falling weight method on rotomoulded tanks and by the drop test on 10 L rotomoulded bottles having a 6 mm wall thickness.
  • the resins according to the present invention were all less brittle than the prior art resins.
  • the drop test was carried out at a temperature of ⁇ 18° C., on 10 L rotomoulded bottles having a wall thickness of 6 mm and prepared with a proprietary mould. The bottles were dropped from increasing heights until failure occurred.
  • Resin R6, according to the present invention did not fail up to a height of 6.5 m both at a temperature of ⁇ 18° C. and at a temperature of ⁇ 40° C.
  • broken means that, at least 50% of the tested samples, broke during the test.
  • FIG. 2 The stacking test performed at a temperature of 40° C. on 700 mL rotomoulded bottles having a 2.5 mm wall thickness, prepared with resins R7, R8 and R9 with a proprietary mould, filled with a wetting agent (Huperol at 5% in water) and placed under a load of 40 kg are displayed in FIG. 2 representing the deflection expressed in cm as a function of time expressed in days.
  • FIG. 6 shows a linear correlation between the LCBI and the spherulite size.
  • the spherulite size decreased linearly with increasing LCBI for resins R6, R9 and R10 whereas it remained unchanged for prior art resins.
  • FIG. 7 shows a correlation between LCBI and melt index MI 2 for the resins according to the present invention.
  • the melt index increased with decreasing LCBI.
  • the LCB content could thus be tailored by modifying the melt index.
  • FIG. 8 shows a linear correlation between the melt index and the spherulite size. The melt index increased linearly with increasing spherulite size.
  • Resin R6 according to the present invention outperforms the other resins at all tested temperatures.
  • FIGS. 9 a , 9 b and 9 c The load displacement curves, at a temperature of ⁇ 40° C., are presented on FIGS. 9 a , 9 b and 9 c for the 4.5 mm rotomoulded samples prepared respectively with resins R6, R3 and R4.
  • Resin R6 exhibits a pure ductile behaviour at all tested temperatures, contrary to the other tested resins.
  • the polyethylene resin according to the present invention proved at least as good as and in most instances far better than all the prior art resins.

Landscapes

  • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Moulding By Coating Moulds (AREA)
  • Laminated Bodies (AREA)
US11/667,792 2004-11-19 2005-11-18 Solid State Properties Of Polyethylene Prepared With Tetrahydroindenyl-Based Catalyst System Abandoned US20080287618A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/876,523 US8822611B2 (en) 2004-11-19 2010-09-07 Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
US14/327,700 US9255161B2 (en) 2004-11-19 2014-07-10 Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP04105942.9 2004-11-19
EP04105942A EP1659136A1 (fr) 2004-11-19 2004-11-19 Propriété à l'état solide de polyethylène préparé par un catalyseur ayant des ligands tetrahydroindényle
PCT/EP2005/056071 WO2006053900A1 (fr) 2004-11-19 2005-11-18 Proprietes a l'etat solide de polyethylene prepare au moyen d'un systeme de catalyseur a base de tetrahydroindenyle

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/056071 A-371-Of-International WO2006053900A1 (fr) 2004-11-19 2005-11-18 Proprietes a l'etat solide de polyethylene prepare au moyen d'un systeme de catalyseur a base de tetrahydroindenyle

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/876,523 Division US8822611B2 (en) 2004-11-19 2010-09-07 Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system

Publications (1)

Publication Number Publication Date
US20080287618A1 true US20080287618A1 (en) 2008-11-20

Family

ID=34929901

Family Applications (3)

Application Number Title Priority Date Filing Date
US11/667,792 Abandoned US20080287618A1 (en) 2004-11-19 2005-11-18 Solid State Properties Of Polyethylene Prepared With Tetrahydroindenyl-Based Catalyst System
US12/876,523 Expired - Fee Related US8822611B2 (en) 2004-11-19 2010-09-07 Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
US14/327,700 Expired - Fee Related US9255161B2 (en) 2004-11-19 2014-07-10 Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system

Family Applications After (2)

Application Number Title Priority Date Filing Date
US12/876,523 Expired - Fee Related US8822611B2 (en) 2004-11-19 2010-09-07 Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
US14/327,700 Expired - Fee Related US9255161B2 (en) 2004-11-19 2014-07-10 Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system

Country Status (13)

Country Link
US (3) US20080287618A1 (fr)
EP (2) EP1659136A1 (fr)
JP (1) JP5575367B2 (fr)
KR (1) KR101299439B1 (fr)
CN (2) CN101061143A (fr)
AT (1) ATE504606T1 (fr)
DE (1) DE602005027390D1 (fr)
DK (1) DK1831264T3 (fr)
EA (1) EA011520B1 (fr)
ES (1) ES2361848T3 (fr)
PL (1) PL1831264T3 (fr)
PT (1) PT1831264E (fr)
WO (1) WO2006053900A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8796409B2 (en) 2011-10-04 2014-08-05 Exxonmobil Chemical Patents Inc. Use of temperature and ethylene partial pressure to introduce long chain branching in high density polyethylene
WO2013052273A2 (fr) * 2011-10-04 2013-04-11 Exxonmobil Chemical Patents Inc. Utilisation de la température et de la pression partielle d'éthylène pour introduire des ramifications à longue chaîne dans un polyéthylène haute densité
KR101831418B1 (ko) 2015-04-13 2018-02-22 주식회사 엘지화학 가공성 및 표면 특성이 우수한 에틸렌/알파-올레핀 공중합체

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020132944A1 (en) * 1999-12-15 2002-09-19 Agapiou Agapios K. Polymerization Process
US20020132945A1 (en) * 1998-10-23 2002-09-19 Feng-Jung Wu Compositions formed from hydroxyaluminoxane and their use as catalyst components
US6734265B1 (en) * 2000-10-06 2004-05-11 Univation Technologies, Llc. Linear low density polyethylenes with high melt strength and high melt index ratio
US20040121098A1 (en) * 2000-03-30 2004-06-24 Eric Maziers Metallocene-produced polyethylene for glossy plastic containers
US20040241362A1 (en) * 2001-07-04 2004-12-02 Philippe Marechal Glossy tubes and pipes

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3916555A1 (de) * 1989-05-20 1990-11-22 Hoechst Ag Verfahren zur herstellung von ethylenpolymeren
EP0926169B1 (fr) * 1997-12-25 2005-02-23 Mitsui Chemicals, Inc. Copolymére d'éthylène/alpha-oléfine et procédé pour sa préparation
DE69925723T2 (de) * 1998-04-07 2006-03-16 Exxonmobil Chemical Patents Inc., Baytown Polymerisationsverfahren
US6462212B1 (en) * 1998-10-23 2002-10-08 Albemarle Corporation Transition metal compounds having conjugate aluminoxate anions and their use as catalyst components
EP1357136A1 (fr) * 2002-04-26 2003-10-29 ATOFINA Research Objet en polyethylene haute densité preparé par injection moulage
JP2005523954A (ja) * 2002-04-26 2005-08-11 アトフイナ・リサーチ ポリエチレンを用いて作られた回転成形品
EP1428841A1 (fr) * 2002-12-12 2004-06-16 ATOFINA Research Articles rotomoulés ayant une stabilité dimensionnelle
EP1469104A1 (fr) * 2003-04-16 2004-10-20 ATOFINA Research Société Anonyme Polyéthylène pour fibres obtenu avec un catalyseur métallocène
EP1495861A1 (fr) * 2003-07-10 2005-01-12 Total Petrochemicals Research Feluy Containers ayant une haute transparence et une résistance au choc élevée
US7119153B2 (en) * 2004-01-21 2006-10-10 Jensen Michael D Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020132945A1 (en) * 1998-10-23 2002-09-19 Feng-Jung Wu Compositions formed from hydroxyaluminoxane and their use as catalyst components
US20020132944A1 (en) * 1999-12-15 2002-09-19 Agapiou Agapios K. Polymerization Process
US20040121098A1 (en) * 2000-03-30 2004-06-24 Eric Maziers Metallocene-produced polyethylene for glossy plastic containers
US6734265B1 (en) * 2000-10-06 2004-05-11 Univation Technologies, Llc. Linear low density polyethylenes with high melt strength and high melt index ratio
US20040241362A1 (en) * 2001-07-04 2004-12-02 Philippe Marechal Glossy tubes and pipes

Also Published As

Publication number Publication date
KR101299439B1 (ko) 2013-08-29
WO2006053900A1 (fr) 2006-05-26
JP5575367B2 (ja) 2014-08-20
PT1831264E (pt) 2011-05-31
EP1831264B1 (fr) 2011-04-06
JP2008520788A (ja) 2008-06-19
ATE504606T1 (de) 2011-04-15
ES2361848T3 (es) 2011-06-22
EP1659136A1 (fr) 2006-05-24
US9255161B2 (en) 2016-02-09
CN104877053A (zh) 2015-09-02
US8822611B2 (en) 2014-09-02
DE602005027390D1 (de) 2011-05-19
DK1831264T3 (da) 2011-06-06
EA200700995A1 (ru) 2007-10-26
CN101061143A (zh) 2007-10-24
PL1831264T3 (pl) 2011-09-30
KR20070093057A (ko) 2007-09-17
US20140349050A1 (en) 2014-11-27
US20110059278A1 (en) 2011-03-10
EA011520B1 (ru) 2009-04-28
EP1831264A1 (fr) 2007-09-12

Similar Documents

Publication Publication Date Title
EP1833908B1 (fr) Capsules et fermetures
EP1578862B1 (fr) Composition de moulage par soufflage de polyethylene pour la production de bidons
US7427649B2 (en) Polyethylene blow molding composition for producing small containers
US8420194B2 (en) Rotomoulded articles prepared with polyethylene
EP1576048B1 (fr) Composition de moulage par soufflage a base de polyethylene destinee a la production de grands contenants
US20120068385A1 (en) Metallocene-Produced Polyethylene For Glossy Plastic Containers
US20060052542A1 (en) Polyethylene composition for producing l-ring drums
US9255161B2 (en) Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
EP1805224B1 (fr) Composant catalytique comprenant au moins trois composés métallocènes bisindényl pontés
EP1300240A1 (fr) Récipient en plastique brillant à haute résistance à la corrosion fissurante
US20120289668A1 (en) LDPE-Like Polymers With Bisindenyl-Based Ligands Having Different Rings
US11208504B2 (en) Injection-molded articles comprising metallocene-catalyzed polyethylene resin

Legal Events

Date Code Title Description
AS Assignment

Owner name: TOTAL PETROCHEMICALS RESEARCH FELUY, BELGIUM

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MAZIERS, ERIC;REEL/FRAME:020570/0580

Effective date: 20071125

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: TOTAL RESEARCH & TECHNOLOGY FELUY, BELGIUM

Free format text: CHANGE OF NAME;ASSIGNOR:TOTAL PETROCHEMICALS RESEARCH FELUY;REEL/FRAME:032835/0542

Effective date: 20120716