US20040121098A1 - Metallocene-produced polyethylene for glossy plastic containers - Google Patents

Metallocene-produced polyethylene for glossy plastic containers Download PDF

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Publication number
US20040121098A1
US20040121098A1 US10/333,175 US33317503A US2004121098A1 US 20040121098 A1 US20040121098 A1 US 20040121098A1 US 33317503 A US33317503 A US 33317503A US 2004121098 A1 US2004121098 A1 US 2004121098A1
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Prior art keywords
polyethylene
produced
metallocene
bottles
plastic containers
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Abandoned
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US10/333,175
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Eric Maziers
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Total Petrochemicals Research Feluy SA
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Individual
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Assigned to ATOFINA RESEARCH reassignment ATOFINA RESEARCH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAZIERS, ERIC
Publication of US20040121098A1 publication Critical patent/US20040121098A1/en
Assigned to TOTAL PETROCHEMICALS RESEARCH FELUY reassignment TOTAL PETROCHEMICALS RESEARCH FELUY CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: ATOFINA RESEARCH
Priority to US13/285,261 priority Critical patent/US20120068385A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/60—Bottles
    • 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
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • This invention is related to plastic containers having a glossy outer surface and in particular to the production high gloss bottles, jars, etc. formed of polyethylene.
  • High gloss high density polyethylene has been used: it is characterised by a very narrow molecular weight distribution that is typically inferior to 8.
  • the molecular weight distribution can be completely defined by means of a curve obtained by gel permeation chromatography.
  • the molecular weight distribution is more simply defined by a parameter, known as the dispersion index D, which is the ratio between the average molecular weight by weight (Mw) and the average molecular weight by number (Mn).
  • the dispersion index constitutes a measure of the width of the molecular weight distribution. It is known that a resin of narrow molecular weight distribution will produce plastic containers of very high gloss but simultaneously, that such resin will be very difficult to process and will be characterised by very poor mechanical properties. It has also been observed that said resins have poor mechanical properties, particularly, a very low environmental stress crack resistance (Modern Plastic International, August 1993, p. 45).
  • HDPE high density polyethylene
  • polyamide polyamide
  • high gloss plastic containers comprise an internal layer including a polyolefin and an external layer including a styrenic component containing from 40 to 85 wt % of styrene, based on the weight of the external layer.
  • An aim of the present invention is to produce plastic containers that offer simultaneously the desired glossy appearance, a good resistance to scratching and very low swell.
  • the present invention provides single layer or multi-layer plastic containers, for which the external layer consists essentially of a metallocene-produced polyethylene having a density of from 0.930 to 0.966 g/cm 3 and a melt index MI2 of from 0.5 to 2.5 g/10min.
  • the density of the polyethylene is measured at 23 ° C. using the procedures of ASTM D 1505.
  • the melt index MI2 is measured using the procedures of ASTM D 1238 at 190° C. using a load of 2.16 kg.
  • the high load melt index HLMI is measured using the procedures of ASTM D 1238 at 190 ° C. using a load of 21.6 kg.
  • the external layer is prepared with a metallocene-produced polyethylene resin
  • the inner layer(s) is(are) prepared with any one of the known catalysts, such as a chromium or a Ziegler-Natta or a metallocene catalyst, said metallocene catalyst being either the same as or different from the metallocene catalyst used to prepare the external layer.
  • a number of different catalyst systems have been disclosed for the manufacture of polyethylene, in particular medium-density polyethylene (MDPE) and high-density polyethylene (HDPE) suitable for blow moulding. It is known in the art that the physical properties, in particular the mechanical properties, of a polyethylene product vary depending on what catalytic system was employed to make the polyethylene. This is because different catalyst systems tend to yield different molecular weight distributions in the polyethylene produced
  • EP-A-0,291,824, EP-A-0,591,968 and U.S. Pat. No. 5,310,834 each disclose mixed catalyst compositions, incorporating chromium-based catalysts, for the polymerisation of polyethylene.
  • the HDPE can be produced using a conventional Ziegler-Natta catalyst or a supported Ziegler-Natta catalyst comprising metallocene sites such as described in EP-A-0,585,512.
  • the HDPE can further be polymerised with a metallocene catalyst capable of producing a mono- or bi- or multimodal distribution, either in a two step process such as described for example in EP-A-0,881,237, or as a dual or multiple site catalyst in a single reactor such as described for example in EP-A-0,619,325.
  • a metallocene catalyst capable of producing a mono- or bi- or multimodal distribution, either in a two step process such as described for example in EP-A-0,881,237, or as a dual or multiple site catalyst in a single reactor such as described for example in EP-A-0,619,325.
  • Any metallocene catalyst known in the art can be used in the present invention. It is represented by the general formula:
  • Cp is a cyclopentadienyl ring
  • M is a group 4 b , 5 b or 6 b transition metal
  • R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms
  • X is a halogen
  • (C 5 R′ k ) is a cyclopentadienyl or substituted cyclopentadienyl
  • each R′ is the same or different and is hydrogen or a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms are joined together to form a C 4 -C 6 ring
  • R′′ is a C 1 -C 4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical bridging two (C 5 R′ k ) rings
  • Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having 1-20 carbon atoms or halogen and can be the same or different from each other
  • Q′ is
  • metallocenes used in the present invention one can cite among others ethylene bis-(tetrahydroindenyl) zirconium dichloride and ethylene bis-(indenyl) zirconium dichloride as disclosed for example in WO 96/35729.
  • the metallocene may be supported according to any method known in the art.
  • the support used in the present invention can be any organic or inorganic solids, particularly porous supports such as talc, inorganic oxides, and resinous support material such as polyolefin.
  • the support material is an inorganic oxide in its finely divided form.
  • An active site must be created by adding a cocatalyst having an ionising action.
  • alumoxane is used as cocatalyst during the polymerization procedure, and any alumoxane known in the art is suitable.
  • the preferred alumoxanes comprise oligomeric linear and/or cyclic alkyl alumoxanes represented by the formula:
  • n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C 1 -C 8 alkyl group and preferably methyl.
  • Methylalumoxane is preferably used.
  • AIR x When alumoxane is not used as a cocatalyst, one or more aluminiumalkyl represented by the formula AIR x are used wherein each R is the same or different and is selected from halides or from alkoxy or alkyl groups having from 1 to 12 carbon atoms and x is from 1 to 3.
  • Especially suitable aluminiumalkyl are trialkylaluminium, the most preferred being triisobutylaluminium (TIBAL).
  • the metallocene catalyst utilised to produce a polyethylene can be used in gas, solution or slurry polymerisation.
  • the polymerization process is conducted under slurry phase polymerization conditions.
  • the polymerisation temperature ranges from 20 to 125° C., preferably from 60 to 95° C. and the pressure ranges from 0.1 to 5.6 Mpa, preferably from 2 to 4 Mpa, for a time ranging from 10 minutes to 4 hours, preferably from 1 and 2.5 hours).
  • the polymerization reaction be run in a diluent at a temperature at which the polymer remains as a suspended solid in the diluent.
  • a continuous loop reactor is preferably used for conducting the polymerisation.
  • the average molecular weight is controlled by adding hydrogen during polymerisation.
  • the relative amounts of hydrogen and olefin introduced into the polymerisation reactor are from 0.001 to 15 mole percent hydrogen and from 99.999 to 85 mole percent olefin based on total hydrogen and olefin present, preferably from 0.2 to 3 mole percent hydrogen and from 99.8 to 97 mole percent olefin.
  • the density of the polyethylene is regulated by the amount of comonomer injected into the reactor; examples of comonomer which can be used include 1-olefins butene, hexene, octene, 4-methyl-pentene, and the like, the most preferred being hexene.
  • the densities of the polyethylenes required for preparing the plastic containers of the present invention range from 0.930 g/cm 3 to 0.966 g/cm 3 .
  • the melt index of polyethylene is regulated by the amount of hydrogen injected into the reactor.
  • the melt indexes useful in the present invention range from 0.5 g/10′ to 2.5 g/10′.
  • the polyethylene resin used in the present invention can be prepared with either a single site metallocene catalyst or with a multiple site metallocene catalyst and it has therefore either a monomodal or a bimodal molecular weight distribution.
  • the molecular weight distribution is of from 2 to 20, preferably, of from 2 to 7 and more preferably of from 2 to 5.
  • polyethylene resins produced in accordance with the above-described processes have physical properties making them particularly suitable for use as blow moulding grade polyethylenes.
  • the polyethylene resins of the present invention are used preferably for producing containers of a capacity ranging from 0.005 to 5 l. They are more preferably used for producing food packaging, particularly milk bottles and juice bottles, cosmetic packaging and household packaging such as detergent packaging.
  • the blow moulding machine incorporating a coextrusion die for extruding a parison to be blow moulded, can be any one of the machines generally used for blow moulding. The following have been used for processing the polyethylene:
  • a Battenfeld Fisher VK1-4 available from Battenfeld this is a continuous extrusion or co-extrusion blow moulding machine with up to 6 extruders for the production of polyethylene bottles of 0.5 litre capacity, the bottles being either single layer or multi-layer with up to 6 layers;
  • the plastic containers of the present invention are characterised by a very high gloss, as measured using the ASTM D 2457-90 test, a low haze as measured by ASTM D 1003-92, a very low swell and a outstanding resistance to drop.
  • the swell is measured with the Gottfert 2002 capillary rheometer: it measures the diameter of the extruded product for different shear velocities.
  • the capillary selection corresponds to a die having an effective length of 10 mm, a diameter of 2 mm and an aperture of 180 °.
  • the temperature is 210 ° C.
  • Shear velocities range from 7 to 725 sec ⁇ 1 , selected in decreasing order in order to reduce the time spent in the cylinder; 7 velocities are usually tested.
  • the extruded product has a length of about 7cm, it is cut, after the pressure has been stabilised and the next velocity is selected.
  • the extruded product (sample) is allowed to cool down in a rectilinear position.
  • the diameter of the extruded product is then measured with an accuracy of 0.01 mm using a vernier, at 2.5 cm (d 2.5 ) and at 5 cm (d 5 ) from one end of the sample, making at each position d 2.5 and d 5 two measurements separated by an angle of 90 °.
  • the swell G is determined as
  • the swell value is measured for each of the selected shear velocities and a graph representing the swell as a function of shear velocity can be obtained.
  • the drop resistance test is performed on one-litre bottles prepared in accordance with the present invention.
  • the drop resistance is measured using the following procedure:
  • the bottles had a fairly homogeneous thickness
  • the empty bottles were stored at room temperature for about 20 hrs;
  • the bottles were then filled with fluid, closed and brought to the desired conditioning as follows: 1) room temperature, water, 24+ ⁇ 3 hrs;
  • a test run on a sample of 20 bottles included the following steps:
  • H F H o +[ ⁇ H ( A/N ⁇ 0.5)]
  • H o is the minimum height
  • ⁇ H is the step distance
  • A is given by the product (i*n i ) wherein n i represents the number of ruptures at each height considering only the last 7 ruptures and i is an integer 0,1,2, . . . indicating the number of steps above the minimum height H o ,
  • N is the total number of ruptures.
  • the typical weight of the container can be reduced by as much as 50% if so desired.
  • the external layer is a metallocene-produced polyethylene and the internal layer is a polyethylene produced by any conventional method.
  • the external layer represents from 5 to 14%, preferably about 10%, of the total wall thickness.
  • the transformation temperatures are higher than on the VK1-4 machine, they range from 170 to 190 ° C.
  • the polyethylene resin was obtained by continuous polymerisation in a loop slurry reactor with a supported and ionised metallocene catalyst prepared in two steps by first reacting SiO 2 with MAO to produce SiO 2 .MAO and then reacting 94 wt % of the SiO 2 .MAO produced in the first step with 6 wt % of ethylene bis-(tetrahydroindenyl) zirconium dichloride.
  • the dry catalyst was slurried in isobutane and pre-contacted with triisobutylaluminium (TIBAI, 10 wt % in hexane) before injection in the reactor.
  • TIBAI triisobutylaluminium
  • the polyethylene resin was obtained by continuous polymerisation in a loop slurry reactor with a supported and ionised metallocene catalyst prepared in two steps by first reacting SiO 2 with MAO to produce SiO 2 .MAO and then reacting 96 wt % of the SiO 2 .MAO produced in the first step with 4 wt % of ethylene bis-(indenyl) zirconium.
  • the dry catalyst was slurried in isobutane and pre-contacted with triisobutylaluminium (TiBAI, 10 wt % in hexane) before injection in the reactor. The reaction was conducted in a 70 l capacity loop reactor during ?
  • RPM 1 is the number of rotations per minute.
  • Nb*/min is the number of bottles produced per minute
  • FIG. 1 displays the bottle's weight for the five resins tested.
  • FIG. 2 represents the swell in % as a function of shear rate.
  • FIG. 3 represents the production rate for the five resins tested.
  • FIG. 4 represents the gloss in % for resins R4 and R1 when used as external layer or as internal layer.
  • FIGURES show unambiguously the improved qualities of swell and gloss of the plastic containers obtained with metallocene-produced polyethylene.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Laminated Bodies (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (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)
US10/333,175 2000-03-30 2001-03-28 Metallocene-produced polyethylene for glossy plastic containers Abandoned US20040121098A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/285,261 US20120068385A1 (en) 2000-03-30 2011-10-31 Metallocene-Produced Polyethylene For Glossy Plastic Containers

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP00201154.2 2000-03-30
EP00201154A EP1138702A1 (de) 2000-03-30 2000-03-30 Mit Metallocenkatalysatoren hergestelltes Polyethylen für glänzende Plastikbehälter
PCT/EP2001/003525 WO2001072856A1 (en) 2000-03-30 2001-03-28 Metallocene-produced polyethylene for glossy plastic containers

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US13/285,261 Abandoned US20120068385A1 (en) 2000-03-30 2011-10-31 Metallocene-Produced Polyethylene For Glossy Plastic Containers

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US (2) US20040121098A1 (de)
EP (3) EP1138702A1 (de)
AT (2) ATE319752T1 (de)
AU (1) AU2001254749A1 (de)
DE (1) DE60117774T2 (de)
ES (1) ES2259027T3 (de)
WO (1) WO2001072856A1 (de)

Cited By (10)

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US20050255264A1 (en) * 2002-04-26 2005-11-17 Eric Maziers Rotomoulded articles prepared with polyethylene
US20060051538A1 (en) * 2001-10-02 2006-03-09 Eric Maziers High escr glossy plastic containers
US20070042149A1 (en) * 2005-08-16 2007-02-22 S.C. Johnson & Son, Inc. Bottles made from metallocene polypropylene for delivery of fragrances
US20070129518A1 (en) * 2002-04-26 2007-06-07 Eric Maziers High dimension stability and high processability polyethylene in injection molding
US20080287618A1 (en) * 2004-11-19 2008-11-20 Total Petrochemicals Research Feluy Solid State Properties Of Polyethylene Prepared With Tetrahydroindenyl-Based Catalyst System
US20090081397A1 (en) * 2007-09-26 2009-03-26 Carvell Lee A System and method for creating high gloss plastic items via the use of styrenic copolymers as a coextruded layer
US9827705B2 (en) 2015-04-16 2017-11-28 The Procter & Gamble Company High gloss high density polyethylene containers
WO2023192846A1 (en) 2022-03-31 2023-10-05 Exxonmobil Chemical Patents Inc. Linear low density polyethylenes, polymerizations thereof, and films thereof
WO2024044423A1 (en) 2022-08-22 2024-02-29 Exxonmobil Chemical Patents, Inc. Polyethylene compositions and films made therefrom
WO2024054736A1 (en) 2022-09-07 2024-03-14 Exxonmobil Chemical Patents Inc. Polyethylenes and articles thereof

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EP1287969A1 (de) * 2001-08-24 2003-03-05 Atofina Research S.A. Spritzblasgeformter Behälter aus metallocen-Polyethylen
US20040043165A1 (en) * 2002-08-27 2004-03-04 Van Hulle Keith Eugene Lidding components for containers
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US8797540B2 (en) * 2010-09-08 2014-08-05 The Board Of Trustees Of The Leland Stanford Junior University Slow-light fiber Bragg grating sensor
US20130059140A1 (en) * 2011-09-02 2013-03-07 Chevron Phillips Chemical Company Lp Multilayer Polymer Films Having Improved Barrier Properties
US9018329B2 (en) 2011-09-02 2015-04-28 Chevron Phillips Chemical Company Lp Polymer compositions having improved barrier properties
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BR112017005188A2 (pt) 2014-10-03 2017-12-12 Exxonmobil Chemical Patents Inc polímeros de polietileno, filmes fabricados a partir dos mesmos e métodos para fabricar os mesmos

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US20120068385A1 (en) 2012-03-22
EP1593696A2 (de) 2005-11-09
ATE520722T1 (de) 2011-09-15
WO2001072856A1 (en) 2001-10-04
EP1593696B1 (de) 2011-08-17
ES2259027T3 (es) 2006-09-16
AU2001254749A1 (en) 2001-10-08
ATE319752T1 (de) 2006-03-15
EP1138702A1 (de) 2001-10-04
EP1593696A3 (de) 2006-01-04
EP1268576A1 (de) 2003-01-02
DE60117774T2 (de) 2006-11-16
EP1268576B1 (de) 2006-03-08
DE60117774D1 (de) 2006-05-04

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