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WO2000064952A2 - Polyethene non reticule - Google Patents

Polyethene non reticule Download PDF

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Publication number
WO2000064952A2
WO2000064952A2 PCT/FI2000/000366 FI0000366W WO0064952A2 WO 2000064952 A2 WO2000064952 A2 WO 2000064952A2 FI 0000366 W FI0000366 W FI 0000366W WO 0064952 A2 WO0064952 A2 WO 0064952A2
Authority
WO
WIPO (PCT)
Prior art keywords
non crosslinked
polyethene
crosslinked polyethene
polymerisation
metallocene complex
Prior art date
Application number
PCT/FI2000/000366
Other languages
English (en)
Other versions
WO2000064952A3 (fr
Inventor
Anneli Malmberg
Barbro LÖFGREN
Original Assignee
Borealis Technology Oy
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 Borealis Technology Oy filed Critical Borealis Technology Oy
Priority to AU42992/00A priority Critical patent/AU4299200A/en
Publication of WO2000064952A2 publication Critical patent/WO2000064952A2/fr
Publication of WO2000064952A3 publication Critical patent/WO2000064952A3/fr

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
    • C08F10/02—Ethene
    • 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
    • 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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium 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
    • 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
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the object of the invention is a non-crosslinked polyethene with novel rheological properties.
  • the invention also relates to the polymerisation of said non-crosslinked polyethene.
  • Improvement of the processability can be reached by either broadening the molar mass distribution or by introducing long chain branching to the polymer. Of these two alternatives, increasing the degree of long chain branching while mamtaining the narrow molar mass and comonomer distribution is more desirable. The pseudo- plasticity (shear thinning) and melt elasticity of these polymers are improved, while maintaining the desired mechanical properties.
  • the patent application EP 676 421 describes a metallocene catalyst and polymerisation conditions leading to polyolefins having at least 0.01 long chain branches per 1000 carbon atoms along the polymer backbone and a breadth of molar mass distribution (M w /M n ) greater than 2,5.
  • a particularly preferred metallocene complex is a C 2 -bridged bis(indenyl)zirconium dichloride.
  • the polymerisation described in EP 676 421 is preferably carried out in gas-phase in the presence of a cocatalyst such as methyl aluminoxane.
  • a cocatalyst such as methyl aluminoxane.
  • the polymers according to this publication show increased shear thinning compared to other single site catalysts. Their shear thinning behaviour is conventional, i.e. the polymers show increased shear rate dependency of the viscosity.
  • the processing window is, however, still rather narrow which can cause problems like melt fracture, extruder high back pressure, bubble instability in blow film processes and sagging in blow molding.
  • the non crosslinked polyethene according to the invention is such that the value of the normalised difference between its storage modulus G' and its loss modulus G", determined by dynamic rheological measurement, is continuously below 0,5 under frequencies from 0,01 to 100 rad/s and at the temperature 190°C.
  • the curves G' and G" are thus essentially parallel in said frequency range.
  • the non crosslinked polyethene according to the invention has preferably been polymerised with a catalyst system comprising a metallocene complex.
  • Said metallocene complex is a metallocene having a sandwich bonding ligand comprising a sandwich bonding moiety having an unsaturated 5-membered ring or having a 6- membered ring fused to an unsaturated 5-membered ring which moiety is covalently substituted by an organic group via a heteroatom.
  • said moiety comprises an indenyl, dihydroindenyl or tetrahydroindenyl ring system.
  • Said moiety is also preferably substituted by a silyloxy or germyloxy group.
  • said metallocene complex is rac-ethylene bis(3-tri- isopropylsiloxy)indenyl zirconium dichloride or rac-ethylene bis(3-tert- butyldimethylsiloxy)indenyl zirconium dichloride.
  • said metallocene complex is preferably supported, the support being silica, alumina and/or magnesium dichloride.
  • the polymerisation is carried out in a slurry process, in which a C 3 -C 8 inert hydrocarbon e.g. propane, isobutane, pentane, heptane, hexane, toluene or any other aliphatic or aromatic solvent is used as polymerisation medium,.
  • a C 3 -C 8 inert hydrocarbon e.g. propane, isobutane, pentane, heptane, hexane, toluene or any other aliphatic or aromatic solvent is used as polymerisation medium,.
  • the reaction temperature is preferably from 60 to 110°C, more preferably from 75 to 100°C.
  • the polymerisation conditions are preferably such that the ethene partial pressure is from 0,25 to 40,0 bar, preferably from 5,0 to 15,0 bar.
  • Hydrogen is optionally used, preferably in an amount from 0,1 to 10 mol, more preferably from 0,5 to 2 mol per 1000 mol of ethene.
  • Comonomer can also be used in the polymerisation and preferably the comonomer is an ⁇ -olef ⁇ n, preferably a C -C 8 ⁇ -olef ⁇ n.
  • the amount of comonomer is such that the comonomer content of the final product is from 1,0 to 10,0 wt-%, preferably from 3,0 to 10,0 wt-%, most preferably from 5,0 to 8,0 wt-%.
  • an alkyl aluminoxane is preferably used, and most preferably said alkyl aluminoxane is methyl aluminoxane, hexaisobutyl aluminox- ane and/or tetraisobutyl aluminoxane.
  • the amount of alkyl aluminoxane used is such that Al/Metal-ratio is from 50 to 2500, preferably from 100 to 1500.
  • the non crosslinked polyethene according to the invention has the desirable mechanical properties characteristic of metallocene polymers associated to good processability due to long chain branching.
  • the polymerisations were performed in a 3 L semiflow stainless steel autoclave reactor equipped with a paddle stirrer and an external glycol jacket for temperature control. The reactor was dried and degassed thoroughly prior to use.
  • Heterogenoeous catalyst was prepared by mixing 34,2 mg of rac-ethylene bis(3-tri- isopropylsiloxy)indenyl zirconium dichloride with 1,98 mL of 30 wt-% methyl aluminoxane and further diluting the mixture with 0,55 mL of toluene. After 1 hour reaction time 1,48 mL of the complex solution obtained was slowly impregnated on activated silica (0,987 g Sylopol 55SJ, activated at 600°C). Impregnation time was 1 hour after which the catalyst was dried by nitrogen purging.
  • Comparative examples 6-8 are examples of polymers catalysed with metallocenes and containing some long chain branching.
  • Comparative examples 9 and 10 are examples of linear polymers catalysed with metallocenes.
  • - polymer sample appropriately stabilised prior to testing e.g. containing 2000 ppm of a thermal/oxidative stabiliser, e.g. Irganox B 215 commercially available from Ciba-Geigy
  • a thermal/oxidative stabiliser e.g. Irganox B 215 commercially available from Ciba-Geigy
  • the samples tested were those prepared in examples 1-10 as well as three reference materials, that were commercial low density polyethene (PE-LD, Figure 11), high density polyethene (PE-HD, ( Figure 12) and linear low density polyethene (PE- LLD, ( Figure 13).
  • PE-LD commercial low density polyethene
  • PE-HD high density polyethene
  • PE- LLD linear low density polyethene
  • the PE-LD reference sample was characterised by high molar mass, broad molar mass distribution and a flow activation energy of 50 kJ/mol, typical for low density polyethene.
  • the PE-LLD sample was a conventional Ziegler-Natta catalysed film grade linear low density polyethene, Mw 80 000 g/mol and MMD 4,0, yielding 33 kJ/mol for flow activation energy.
  • the PE-HD sample was a chromium catalysed high density polyethene with few or no long chain branches, characterised by high molar mass (Mw 300 000 g/mol) and broad MMD (15). The flow activation energy of this material was 31 kJ/mol. Table 1. Polymer properties
  • FIGS. 1-13 The frequency dependency of the dynamic moduli of the samples are shown in figures 1-13.
  • Figures 1-5 show the corresponding curves for samples prepared in examples 1-4, according to the invention.
  • Figures 6-10 show the curves for the comparative samples prepared in examples 6-10 and figures 11-13 show the curves for the reference materials PE-LD, PE-HD and PE-LLD.
  • the curve representing the storage modulus G'( ⁇ ) is parallel to that of loss modulus G"( ⁇ ) over the whole measured frequency region, four decades (0,01-100 rad/s).
  • the two curves are essentially parallel over the frequency region from 0,3 or 0,4 to 100 rad/s.
  • the storage modulus G' ( ⁇ ) is not parallel to the loss modulus G"( ⁇ ) over any part of the frequency region studied. Such is the case also in figures 11-13.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Silicon Polymers (AREA)

Abstract

La présente invention concerne un polyéthène non réticulé dont la valeur de la différence normalisée entre son module de stockage G' et son module de perte G'', déterminée par mesure rhéologique dynamique, est continuellement inférieure à 0,5 sous des fréquences allant de 0,01 à 100 rad/s et à une température de 190 °C. Cette différence est de préférence sensiblement constante sous lesdites fréquences. On prépare de préférence ces polyéthènes en utilisant des catalyseurs métallocènes, et dans un mode de réalisation préférée ces catalyseurs sont à base de rac-éthylène bis(3-tri-isopropylsiloxy)indenyl zirconium dichloride ou de rac-éthylène bis(3-tert-butyldiméthylsiloxy)indenyl zirconium dichloride.
PCT/FI2000/000366 1999-04-27 2000-04-27 Polyethene non reticule WO2000064952A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU42992/00A AU4299200A (en) 1999-04-27 2000-04-27 Non-crosslinked polyethene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI990948 1999-04-27
FI990948A FI990948A0 (fi) 1999-04-27 1999-04-27 Ei-ristisilloitettu polyeteeni

Publications (2)

Publication Number Publication Date
WO2000064952A2 true WO2000064952A2 (fr) 2000-11-02
WO2000064952A3 WO2000064952A3 (fr) 2001-02-01

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AU (1) AU4299200A (fr)
FI (1) FI990948A0 (fr)
WO (1) WO2000064952A2 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7319125B2 (en) 2002-09-20 2008-01-15 Exxonmobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
US7910679B2 (en) 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
US7928162B2 (en) 2007-09-13 2011-04-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
US20110172354A1 (en) * 2010-01-04 2011-07-14 Dow Global Technologies Inc. Ethylene-based polymer compositions for use in fiber applications
US7994237B2 (en) 2007-12-20 2011-08-09 Exxonmobil Research And Engineering Company In-line process to produce pellet-stable polyolefins
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US8138269B2 (en) 2007-12-20 2012-03-20 Exxonmobil Research And Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7601666B2 (en) 2004-07-08 2009-10-13 Exxonmobil Chemical Patents Inc. Olefin polymerization catalyst system and process for use thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5710224A (en) * 1991-07-23 1998-01-20 Phillips Petroleum Company Method for producing polymer of ethylene
EP0676421B1 (fr) * 1994-04-07 2006-02-15 Innovene Europe Limited Procédé de polymérisation et polyoléfines ainsi obtenues
ES2157342T3 (es) * 1994-09-07 2001-08-16 Dow Chemical Co Polietileno lineal plastico de baja densidad.
JP3071145B2 (ja) * 1995-05-16 2000-07-31 ユニベーション・テクノロジーズ・エルエルシー 立体異性型メタロセンを用いるポリエチレンの製造
US6114477A (en) * 1996-02-09 2000-09-05 Exxon Chemical Patents Inc. Polymerization process
SK284880B6 (sk) * 1996-05-17 2006-01-05 Bp Chemicals Limited Polyolefínový kopolymérny prostriedok, fólia alebo iný priemyselný výrobok a zmes s jeho obsahom

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7319125B2 (en) 2002-09-20 2008-01-15 Exxonmobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
US7354979B2 (en) 2002-09-20 2008-04-08 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
US7928162B2 (en) 2007-09-13 2011-04-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
US7910679B2 (en) 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
US7994237B2 (en) 2007-12-20 2011-08-09 Exxonmobil Research And Engineering Company In-line process to produce pellet-stable polyolefins
US8138269B2 (en) 2007-12-20 2012-03-20 Exxonmobil Research And Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
US20110172354A1 (en) * 2010-01-04 2011-07-14 Dow Global Technologies Inc. Ethylene-based polymer compositions for use in fiber applications

Also Published As

Publication number Publication date
AU4299200A (en) 2000-11-10
FI990948A0 (fi) 1999-04-27
WO2000064952A3 (fr) 2001-02-01

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