Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
  • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
  • B60K15/03—Fuel tanks
  • B60K15/03177—Fuel tanks made of non-metallic material, e.g. plastics, or of a combination of non-metallic and metallic material
• • 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
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
  • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
• • 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
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
  • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
  • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
  • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
  • B60K15/03—Fuel tanks
  • B60K2015/03032—Manufacturing of fuel tanks
  • B60K2015/03046—Manufacturing of fuel tanks made from more than one layer
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2314/00—Polymer mixtures characterised by way of preparation
  • C08L2314/02—Ziegler natta catalyst
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2314/00—Polymer mixtures characterised by way of preparation
  • C08L2314/06—Metallocene or single site catalysts
• • 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

• the present invention relates to an automobile fuel tank comprising polyethylene and to the manufacture of such a tank.
• blow moulding does not permit additional features such as pipes for transfering fuel into and out of the tank to be integrally moulded with the tank body; such pipes need to be welded onto the tank after the blow moulding process. This incurs additional cost and labour, and the there is the possibility of weld failure, leading to escape of fuel or vapours from the tank.
• Plastics automobile fuel tanks are required to exhibit high safety performance, particularly with regard to fire resistance and impact resistance. Such fuel tanks are required to meet minimum statutory industry specified performance criteria both with respect to creep resistance when the tank is subjected to a fire, and crash test resistance when the tank is subjected to an impact.
• An automobile fuel tank for use in Europe is required to have a fire resistance and an impact resistance both complying with the respective standards defined in ECE34, Annex 5.
• known blow moulded automobile fuel tanks are required by automobile manufacturers to have a minimum wall thickness of at least 3mm so as to provide sufficient impact strength and creep resistance for the fuel tank as a whole.
• An automobile fuel tank composed of polyethylene typically has a volume of up to about 100 litres, or even greater.
• EP 1063116A discloses a fuel tank made by injection moulding, which is said to satisfy the above requirements.
• the tank is required to be formed of a polyethylene having a density of from 0.930 to 0.955g/cm 3 , a polydispersity M w /Mschreib (where M w is the average molecular weight of the polyethylene by weight and M n is the average molecular weight of the polyethylene by number) of from 2 to 3, and a melt index MI 2 of from 0.2 to 2 g/lOmin.
• M w is the average molecular weight of the polyethylene by weight
• M n is the average molecular weight of the polyethylene by number
• MI 2 melt index
• EP 1063116A states that if the polydispersity is higher than 3, then as a result of the broad molecular weight distribution, the polymer chains of varying length have different relaxation characteristics during cooling following the injection of the molten resin. This can induce wa ⁇ age or shrinkage in the fuel tank wall following the injection moulding process
• the present invention provides a fuel tank for a vehicle comprising at least one component which is injection-moulded, rotomoulded or thermoformed multimodal polyethylene having a polydispersity M w M n of at least 3.
• multimodal polyethylene is meant polyethylene having at least two components of different molecular weights and compositions (ie comonomer content).
• the multimodal polyethylene is injection-moulded, and for convenience the injection-moulded, rotomoulded or thermoformed polyethylene is referred to hereinafter simply as "injection-moulded".
• the polydispersity of the injection-moulded multimodal polyethylene is preferably at least 4, with the maximum preferably being 35, more preferably 24. The most preferred range is 4-24.
• the polyethylene is preferably bimodal: by "bimodal" is meant two components of different molecular weights, one having a higher relative molecular weight than the other of the two components and compositions (ie comonomer content). In one embodiment, the polydispersity of each of the two blocks is less than 4.
• the unformulated polyethylene resin before the inco ⁇ oration of any additives, preferably has a density of from 930 to 965 kg/m 3 . If following injection moulding the density is lower than 930 kg/m 3 , then the creep resistance of the component may be insufficient for use in an automobile fuel tank. If the density is higher than 965 kg/m 3 , then the walls of the tank may be too brittle, resulting in insufficient impact resistance and toughness. In this specification, the density of the polyethylene is measured according to ISO 1183. Resins used in fuel tanks typically contain about 0.5wt% of carbon black, which increases the density compared with unformulated resin by less than 1 kg/m 3 .
• the high load melt index (HLMI) of the resin is preferably between 1 and 30, more preferably between 8 and 25 g/lOmin. HLMI is measured using the procedures of ASTM D-1238 at 190°C using a load of 21.6kg.
• an important parameter of the resin is its viscosity at high shear rate. Accordingly it is preferred that the value of ⁇ 3 , the viscosity at a shear rate of 1000 s "1 , with a die having a ratio of length to internal diameter of 15:1, is less than 7000 dPa.s, preferably less than 5000 dPa.s.
• the bimodal polyethylene preferably comprises 30-70% of a low molecular weight block, and 70-30% of a high molecular weight block. Most preferred is 45-65 % of the low molecular weight block, and 55-35 % of the high molecular weight block.
• the low molecular weight block is preferably a homopolymer of ethyl ene, but may also be a copolymer.
• the high molecular weight block is preferably a copolymer of ethylene and one or more of butene, pentene, hexene and octene.
• the Melt Index (MI ) of the low molecular weight block is preferably less than 1000, more preferably less than 800 and most preferably less than 200 g/10 min.
• the HLMI of the high molecular weight block is preferably between 0.001 and 2, more preferably between 0.01 and 0.7; its density is preferably less than 950, more preferably less than 940 kg/m .
• the polyethylene resin utilised in the present invention may be made using a Ziegler-Natta catalyst.
• the polydispersity of the injection-moulded multimodal polyethylene is preferably between 10 and 24.
• Ziegler-Natta catalysts typically consist of two main components. One component is an alkyl or hydride of a Group I to III metal, most commonly Al(Et) 3 or Al(iBu) 3 or Al(Et) 2 Cl but also encompassing Grignard reagents, n-butyllithium, or dialkylzinc compounds.
• the second component is a salt of a Group IN to NIII transition metal, most commonly halides of titanium or vanadium such as TiCl 4 , TiCl 3 , NC1 4 , or NOCl 3 .
• the catalyst components when mixed, usually in a hydrocarbon solvent, may form a homogeneous or heterogeneous product. Such catalysts may be impregnated on a support, if desired, by means known to those skilled in the art and so used in any any of the major processes known for co-ordination catalysis of polyolefins such as solution, slurry, and gas-phase. In addition to the two major components described above, minor amounts of other compounds (typically electron donors) may be added to further modify the polymerisation behaviour or activity of the catalyst.
• the polyethylene resin is made using a metallocene catalyst, in which case the polydispersity of the injection-moulded multimodal polyethylene is preferably between 5 and 12.
• Metallocenes may typically be represented by the general formula: Z x (C 5 R ra ) M L (4 . y .i) where (C 5 Rn) y and (C 5 R m ) are cyclopentadienyl ligands, R is hydrogen, alkyl, aryl, alkenyl, etc. M is a Group IVA metal
• Z is a bridging group
• L is an anionic ligand
• y is 0, 1 or 2
• n and m are from 1 to 5
• x is 0 or 1.
• the most preferred complexes are those wherein y is 1 and L is halide or alkyl.
• Typical examples of such complexes are bis (cyclopentadienyl) zirconium dichloride and bis (cyclopentadienyl) zirconium dimethyl.
• the cyclopentadienyl ligands may suitably be substituted by alkyl groups such as methyl, n- butyl or vinyl.
• R groups may be joined together to form a ring substituent, for example indenyl or fluorenyl.
• the cyclopentadienyl ligands may be the same or different. Typical examples of such complexes are bis(n- butylcyclopentadienyl) zirconium dichloride or bis (methylcyclopentadienyl) zirconium dichloride.
• metallocene complex is constrained geometry complexes in which the metal is in the highest oxidation state.
• Such complexes are disclosed in EP 416815 and WO 91/04257 both of which are inco ⁇ orated herein by reference.
• the complexes have the general formula:
• Cp* is a single ⁇ 5-cyclopentadienyl or ⁇ 5-substituted cyclopentadienyl group optionally covalently bonded to M through -Z-Y- and corresponding to the formula:
• each R is independently hydrogen or a moiety selected from halogen, alkyl, aryl, haloalkyl, alkoxy, aryloxy, silyl groups, and combinations thereof of up to 20 non- hydrogen atoms, or two or more R groups together form a fused ring system;
• M is zirconium, titanium or hafnium bound in an ⁇ 5 bonding mode to the cyclopentadienyl or substituted cyclopentadienyl group and is in a valency state of +3 or +4; each X is independently hydride or a moiety selected from halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof (e.g.
• Z is a divalent moiety comprising oxygen, boron, or a member of Group 14 of the Periodic Table of the Elements;
• Y is a linking group covalently bonded to the metal comprising nitrogen, phosphorus, oxygen or sulfur, or optionally Z and Y together form a fused ring system.
• M is titanium or zirconium.
• metallocene complexes are those wherein the anionic ligand represented in the above formulae is replaced with a diene moiety.
• the transition metal may be in the +2 or +4 oxidation state and a typical example of this type of complex is ethylene bis indenyl zirconium (II) 1,4-diphenyl butadiene.
• II ethylene bis indenyl zirconium
• Examples of such complexes may be found in EP 775148A and WO 95/00526 the disclosures of which are inco ⁇ orated herein by reference.
• complexes may have the general formula:
• R' each occurrence is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, and combinations thereof, said R' having up to 20 non hydrogen atoms, and optionally, two R 1 groups (where R' is not hydrogen, halo or cyano) together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring to form a fused ring structure;
• X is a neutral ⁇ 4- bonded diene group having up to 30 non-hydrogen atoms, which forms a ⁇ -complex with M;
• Y is -O-, -S-, -NR*-, -PR*-;
• M is titanium or zirconium in the +2 formal oxidation state;
• R* in each occurrence is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 10 non-hydrogen atoms, and optionally, two R* group from Z* (when R* is not hydrogen), or an R* group from Z* and an R* group from Y form a ring system.
• Fuel tanks manufactured in accordance with the invention typically comprise two or more injection-moulded components joined together, for example by welding, to form an entire fuel tank.
• each injection moulded polyethylene resin component comprises a fuel tank half and the two halves are welded together to form an entire fuel tank. Further components may be inco ⁇ orated into the tank, either made of injection-moulded polyethylene in accordance with the invention, or made of other materials.
• the polymerisation was then started by flushing the solid catalyst A, ethylene bis (4,5,6,7-tetrahydro-l-indenyl) zirconium dichloride (prepared in accordance with the method of Brintzinger as published in the Journal of Organometallic Chemistry 288 (1995) pages 63 to 67), into the autoclave with 200 ml of isobutane.
• the temperature, partial pressure of ethylene, and the H 2 /C 2 ratio were kept constant over the polymerisation period.
• the reaction was stopped by cooling and then venting the reactor.
• the low molecular weight polyethylene was then collected from the reactor.
• the process for preparing the high molecular weight fraction was the same as that for preparing the low molecular weight fraction specified above in Example A, except that instead of adding hydrogen after raising the temperature to 80°C, varying amounts of 1-hexene comonomer were added and a different amount of ethylene was introduced, in order to obtain the desired ethylene partial pressure and C 6 C 2 ratio.
• the high molecular weight ethylene-hexene copolymer obtained was collected from the reactor.
• the detailed polymerisation conditions are specified in Table 1A.
• the desired quantity of the low molecular weight polyethylene fraction obtained in Example A above was blended with the desired quantity of the high molecular weight ethylene-hexene copolymer obtained in Example B together with Irganox B225 antioxidant commercially available from CIBA Speciality Chemicals.
• the resulting blend was pelletised in an extruder (APV Baker under the trade name MP19TC25). The details of the blending recipes are specified in Table 2.
• the manufacture of a polyethylene resin comprising a blend of low molecular weight and high molecular weight ethylene polymers was carried out in suspension in isobutane in two loop reactors connected in series.
• Isobutane, ethylene, hydrogen, triisobutyl aluminium (TIBAL) and catalyst A were continuously introduced into the first loop reactor and the polymerisation of ethylene was carried out in this mixture in order to form the low molecular weight homopolymer.
• the polymerisation conditions are specified in Table IB.
• the mixture, additionally comprising the low molecular weight homopolymer was continuously withdrawn from the first loop reactor and was subjected to a reduction in pressure, so as to remove the hydrogen.
• the resulting mixture was then continuously introduced into a second loop reactor serially connected to the first loop reactor together with ethylene, 1- hexene and isobutane.
• the polymerisation of the ethylene and 1-hexene was carried out therein in order to form the high molecular weight copolymer.
• the suspension comprising the polyethylene resin blend of the low molecular weight and high molecular weight ethylene polymer fractions was continuously withdrawn from the second loop reactor.
• the suspension was subjected to a final reduction in pressure, so as to evaporate the isobutane and the remaining reactants present (ethylene, 1-hexene and hydrogen) and to recover the polyethylene resin in the form of a powder, which was subject to drying in order to complete the degassing of the isobutane.
• the polymerisation conditions in the second reactor are also specified in Table IB.
• molecular weights in the above Table are calculated. W&have found that at low molecular weights (below 100,000) the polydispersity of the resin is approximately 3, increasing to a value of approximately 3.25 at higher molecular weights up to 700,000. The spread of polydispersities around these values is approximately +/- 0.5.
• ⁇ O Viscosity at shear rate of Is "1 with a 30/2 ratio die.
• ⁇ 2 Viscosity at shear rate of 100 s "1 with a 30/2 ratio die.
• ⁇ 3 Viscosity at shear rate of 1000 s "1 with a 30/2 ratio die.
• compressed plates of varying thicknesses were formed as follows. Polymer flake prepared as in Examples 1-8 was loaded into a picture-frame mould and brought in contact with the plates of a hot press, which were rapidly heated up to 190°C at a pressure of 20 bar. The sample was held at those conditions for approximately 5 minutes. The pressure was increased to 80 bar in order to force the polymer to flow out through the shape of the frame. After 5 minutes, pressure was released and the temperature was decreased at a rate of 15°C/min down to 35°C. The plates thus obtained were stored at room temperature for at least 7 days before being submitted to any mechanical tests.

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• Chemical & Material Sciences (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Transportation (AREA)
• Sustainable Development (AREA)
• Mechanical Engineering (AREA)
• Combustion & Propulsion (AREA)
• Life Sciences & Earth Sciences (AREA)
• Sustainable Energy (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)

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• 2002
  • 2002-04-29 EP EP02076956A patent/EP1359191A1/de not_active Withdrawn
• 2003
  • 2003-04-10 AU AU2003229649A patent/AU2003229649A1/en not_active Abandoned
  • 2003-04-10 US US10/512,979 patent/US20050170112A1/en not_active Abandoned
  • 2003-04-10 JP JP2004501500A patent/JP2005523842A/ja active Pending
  • 2003-04-10 EP EP03722454A patent/EP1499673A1/de not_active Withdrawn
  • 2003-04-10 WO PCT/EP2003/003792 patent/WO2003093362A1/en active Application Filing

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