US20050255264A1 - Rotomoulded articles prepared with polyethylene - Google Patents

Rotomoulded articles prepared with polyethylene Download PDF

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US20050255264A1
US20050255264A1 US10/512,388 US51238805A US2005255264A1 US 20050255264 A1 US20050255264 A1 US 20050255264A1 US 51238805 A US51238805 A US 51238805A US 2005255264 A1 US2005255264 A1 US 2005255264A1
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article
wall structure
ethylene
polyethylene resin
polymerization
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Eric Maziers
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Total Petrochemicals Research Feluy SA
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Total Petrochemicals Research Feluy SA
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Priority claimed from EP02076658A external-priority patent/EP1357135A1/en
Priority claimed from EP02027878A external-priority patent/EP1428841A1/en
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Assigned to TOTAL PETROCHEMICAL RESEARCH FELUY reassignment TOTAL PETROCHEMICAL RESEARCH FELUY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAZIERS, ERIC
Publication of US20050255264A1 publication Critical patent/US20050255264A1/en
Priority to US13/342,430 priority Critical patent/US8420194B2/en
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    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • 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
    • 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
    • C08F4/6592—Component 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
    • C08F4/65922—Component 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
    • 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]
    • 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]
    • Y10T428/1376—Foam or porous material containing

Definitions

  • This invention is concerned with rotomoulded articles having reduced shrinkage and warpage and prepared from polyethylene polymerised with a tetrahydro-indenyl catalyst.
  • Polyethylene 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.
  • 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 polyethylene, polypropylene, polycarbonate or PVC. Linear low density polyethylene is preferably used as disclosed for example in “Some new results on rotational molding of metallocene polyethyles” by D. Annechini, E. Takacs and J. Vlachopoulos in ANTEC, vol. 1, 2001.
  • Polyethylenes prepared with a Ziegler-Natta catalyst are generally used in rotomoulding, but metallocene-produced polyethylenes are desirable, because their narrow molecular distribution allows better impact properties and shorter cycle time in processing.
  • the metallocene-produced polyethylenes of the prior art suffer from high shrinkage and warpage.
  • Plastoelastomeric compositions such as described in U.S. Pat. No. 5,457,159 can also be used in rotomoulding, but they require complex processing steps of mixing and vulcanisation.
  • U.S. Pat. No. 6,124,400 discloses the use for rotomoulding of polymer alloys containing semi-crystalline polyolefin sequences with chains of different controlled microstructure prepared in a “one-pot” polymerisation process from a single monomer.
  • the polymerization of these polymer alloys requires a complex catalyst system comprising organometallic catalyst precursors, cationic forming cocatalysts and cross-over agents.
  • the present invention discloses articles produced by rotomoulding and consisting essentially of polyethylene (PE) polymerized with a metallocene catalyst system based on a bis-indenyl or on a bis-cyclopentadienyl metallocene catalyst component.
  • PE polyethylene
  • the high density polyethylene used in the present invention has a density ranking from 0.915 to 0.950 g/cm 3 , preferably from 0.925 to 0.945 g/cm 3 and a melt flow index of from 0.5 to 30 g/10 min, preferably from 2.0 to 20 g/10 min.
  • the density of the polyethylene is measured at 23° C. using the procedures of standard test ASTM D 1505.
  • the melt index M12 is measured using the procedures of standard test ASTM D 1238 at 190° C. and under a load of 2.16 kg.
  • the metallocene used to prepare the high density polyethylene can be a bis-indenyl represented by the general formula: R′′(Ind) 2 MQ 2 (I) or a bis-cyclopentadienyll represented by the formula (Cp) 2 MQ 2 (II) wherein (Ind) is an indenyl or an hydrogenated indenyl, substituted or unsubstituted, Cp is a cyclopentadienyl ring 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 to20 carbon atoms or a halogen, and M is a group IVb transition metal or Vanadium.
  • 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 IVA, 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 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.
  • each cyclopentadienyl ring may be substituted in the same way or differently from one another at one or more positions in the cyclopentadienyl ring.
  • each substituent on the cyclopentadienyl may be independently chosen from those of formula XR* v in which X is chosen from group IVA, oxygen and nitrogen and each R* is the same or dfferent 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 and the most preferred substituent is n-butyl.
  • R′′ is preferably a C1-C4 alkylene radical (as used herein to describe a difunctional radical, also called alkylidene), most preferably an ethylene bridge (as used herein to describe a difunctional radical, also called ethylidene), which is substituted or unsubstituted.
  • the metal M is preferably zirconium, hafnium, or titanium, most preferably zirconium.
  • Each Q is the same or different and may be a hydrocarbyl or hydrocarboxy radical having 1 to 20 carbon atoms or a halogen.
  • Suitable hydrocarbyls include aryl, alkyl,alkenyl,alkylaryl or arylalkyl.
  • Each Q is preferably halogen.
  • metallocenes used in the present invention one can cite bis tetrahydro-indenyl compounds and bis indenyl compounds as disclosed for example in WO 96/35729 or bis(cyclopentadienyl) compounds.
  • the most preferred metallocene catalysts are ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and bis(n-butyl-cyclopentadienyl) zirconium dichloride.
  • 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.
  • alumoxane is used to ionise the catalyst 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: for oligomeric, linear alumoxanes And for oligomeric, cyclic alumoxanes, wherein n is 140, 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.
  • aluminiumalkyl(s) can be used as cocatalyst in the reactor.
  • An aluminiumalkyl represented by the formula AlR 3 can be 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.
  • Especially suitable aluminiumalkyl is trialkylaluminium, the most preferred being triisobutylaluminium (TIBAL).
  • the catalyst may be prepolymerised prior to introducing it in the reaction zone and/or prior to the stabilization of the reaction conditions in the reactor.
  • the polymerisation of the metallocene-produced high density polyethylene can be carried out in gas, solution or slurry phase. Slurry polymerisation is preferably used to prepare the high density polyethylene.
  • 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.
  • a continuous single loop reactor is preferably used for conducting the polymerisation under quasi steady state conditions.
  • a double loop reactor can also be used to produce either monomodal or bimodal resins, such as for examples a resin consisting of a first fraction produced in the first reactor under first polymerisation conditions and a second fraction produced in the second reactor under second polymerisation conditions, said two fractions having the same molecular weight and different densities.
  • 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, typically C3 to C20 olefins among which propylene, butene, hexene, octene, 4-methyl-pentene are preferred, the most preferred being hexene.
  • the rotomoulding machine can be any one of the machines generally used in the field such as for example the CACCIA 1400R rotational moulding machine.
  • the rotomoulded polyethylene articles according to the present invention are characterised by very low warpage and shrinkage.
  • the polyethylene structure is mainly influenced by the catalytic system used for polymerisation and said structure is responsible for the properties of the final articles. It has been observed that a n-butyl catalyst produces a linear polyethylene resin with a narrow molecular weight distribution of about 2.5, that a Ziegler-Natta catalyst produces a linear polyethylene resin with a broader molecular weight distribution of the order of 5 and that a tetrahydro-indenyl catalyst produces a polyethylene with a large amount of long chain branches and a narrow molecular weight distribution of the order of 2.5.
  • the molecular weight distribution (MWD) is completely defined by the polydispersity index D that is the ratio Mw/Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
  • the Dow Rheological Index gives a measure of the amount of long chain branches. The lower the DRI value, the lower the amount of long chain branches.
  • the DRI is determined by fitting the Rheological Dynamic Analysis (RDA) curve of the HDPE by the Cross rheological model described here-below.
  • the dynamic rheology is measured using the method of the RDA. It is a measure of the resistance to flow of material placed between two parallel plates rotating with respect to each other with an oscillatory motion.
  • the apparatus comprises a motor that transmits a sinusoidal deformation to the sample.
  • the sample then transmits the resulting constraint, said resulting constraint being also sinusoidal.
  • the material to be studied can be a solid attached between two anchoring points or it can be melted between the two plates.
  • the dynamic rheometer allows the simultaneous measurement of both the elastic modulus and the viscous modulus of the material. Indeed, the resulting sinusoidal constraint is displaced by a phase angle ⁇ with respect to the imposed deformation and it is mathematically possible to decompose the resulting sinusoid into:
  • the complex viscosity is defined as G/ ⁇ .
  • G′ and G′′ can be measured for different values of ⁇ . The measurements were carried out under the following operating conditions:
  • the elastic component G′ and the viscous component G′′ can be graphed as a function of frequency ⁇ .
  • the point of intersection between the elastic and viscous curves, called the cross-over point (COP), is characterised by a frequency ⁇ c and a viscosity component G c .
  • the cross-over point is characteristic of each polymer and is a function of the molecular weight and of the molecular distribution.
  • the DRI is calculated by least squares fit of the rheological curve (complex viscosity versus frequency) as described in U.S. Pat. No.
  • the resins according to the present invention further have excellent flexural yield strength and flexural properties. They also have good impact strength both at room temperature and at low temperature Additionally, the production cycling time of the polyethylene resins produced with a bis-indenyl catalyst and preferably with a tetrahydro-indenyl catalyst is in line with that of other polyethylene resins.
  • the rotomoulded articles prepared with the polyethylene according to the present invention offer a better resistance to degradation from nitric acid.
  • the rheological properties of the polyethylene produced with a tetrahydro-indenyl catalyst are used to prepare micro-pellets having an average size of from 300 to 800 microns in a one-step procedure: it is a result the fast decrease of the viscosity with increasing shear.
  • rotomoulded articles having an inner foamed polyethylene layer and an outer normal polyethylene layer can be prepared.
  • the large elastic viscosity component G′ of the polyethylene prepared with a tetrahydro-indenyl catalyst is responsible for the better dispersion of bubbles into the foamed material.
  • the articles prepared with a catalyst component based either on tetrahydro indenyl or on bis(n-butyl-cyclopentadienyl) have a very fine microstructure, thereby improving their mechanical properties such as impact strength and their optical properties, such as gloss and their impermeability to solvents.
  • polyethylene resins of the present invention can also be cross-linked by any cross-linking agent known in the field prior to being rotomoulded.
  • the polyethylene polymerized with a bis-indenyl or a bis)cyclopentadienyl metallocene catalyst according to the present invention can be used to produce rotomoulded articles in a variety of applications such as for example tanks, containers, toys, boats, furniture, medical applications, buried tanks, sceptic tanks, fuel tanks.
  • FIG. 1 represents the viscous modulus G′′ expressed in Pa as a function of the elastic modulus G′ expressed in Pa.
  • FIG. 2 represents the elastic component G′ expressed in Pa as a function of shear rate expressed in s- 1 .
  • FIG. 3 represents containers produced respectively with resin R 3 ( FIG. 3 a ) anfdwith resin R 9 ( FIG. 3 b ).
  • FIG. 4 represents the microstructure of resins R 9 ( FIG. 4 a ), R 1 ( FIG. 4 b ), R 10 ( FIG. 4 c ) and R 3 ( FIG. 4 d ).
  • FIG. 5 is a graph representing the average permeability to fuel expressed in g/day at 40° C. for rotomoulded boffles prepared with resins R 9 , R 10 , R 1 and R 3 .
  • FIG. 6 represents the peak internal air temperature (PIAT) temperature expressed in ° C. for a normal mould as a function of time expressed in seconds.
  • PIAT peak internal air temperature
  • FIG. 7 represents the peak internal air temperature (PIAT) temperature expressed in ° C. for a pressurised mould as a function of time expressed in seconds.
  • PIAT peak internal air temperature
  • FIG. 8 represents the radius X/a as a function of time expressed in seconds in sintering experiments, wherein X is the sintering neck radius between the two spheres to be sintered and a is the radius of the spheres.
  • FIG. 9 represents the mass fraction of the powder expressed in percent as a function of particle size expressed in microns.
  • FIG. 10 represents the number of bubbles per mm 2 remaining in the molten resin as a function of temperature expressed in ° C.
  • FIG. 11 represents the mass fraction of the micropellets expressed in percent as a function of particle size expressed in microns.
  • FIG. 12 represents a photograph of the micropellets produced on machine 2 for resin R 9 , under the conditions described in Table VII.
  • FIG. 13 represents the mass fraction of powders and micropellets expressed in percent as a function of particle size expressed in microns for resin R 7 .
  • FIG. 14 represents the number of bubbles per mm 2 remaining in the molten resin as a function of temperature expressed in ° C. for several powder and micropellet samples of various granulometries.
  • Resin R 1 is a polyethylene resin prepared with a metallocene catalyst and sold by Borealis under the name Borocene® RM8343.
  • Resins R 2 , R 5 and R 6 have been prepared with ethylene bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride.
  • Resin R 3 is a commercial Ziegler-Natta resin sold by BP under the name Rigidex® 3560
  • Resins R 7 and R 8 were prepared with di(n-butyl-cyclopentadieny) zirconium dichloride.
  • Resin R 9 was prepared with ethylene bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride.
  • Resin R 10 was prepared with di(n-butyl-cyclopentadieny) zirconium dichloride.
  • Resins R 11 and R 12 were prepared with ethylene bis(4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and had a very low melt index.
  • the main difference between resins R 1 , R 7 , R 8 and R 10 on the one hand and resins R 2 , R 5 , R 6 and R 9 on the other hand lies in the values for the Dow Rheological index (DRI), said values being extremely low for the resins prepared with the n-butyl catalyst.
  • DRI Dow Rheological index
  • resins R 11 and R 12 have melt flow indices of 0.9 and 0.7 g/10 min, well below the minimum value of about 2 g/10 min generally recommended in the field of rotomoulding.
  • FIG. 1 The elastic component of the various resins is displayed in FIG. 1 that represents the viscous modulus G′′ expressed in Pa graphed as a function of the elastic modulus G′ expressed in Pa. It can be deduced from that gragh that resins R 2 and R 3 prepared respectively with a tetrahydro-indenyl catalyst and with a Ziegler-Natta catalyst have the largest elastic component, resin R 6 , prepared with a tetrahydro-indenyl catalyst has an intermediate elastic component and resin R 7 prepared with the n-butyl catalyst has the lowest elastic component.
  • R 2 presents a higher elastic component G′ than R 6 because it has a higher molecular weight than R 6 .
  • FIG. 2 represents the elastic component G′ expressed in Pa as a function of shear rate expressed in s-1. It is observed on that graph that resin R 7 prepared with a n-butyl metallocene catalyst has the lowest elastic component which is favourable to sintering. These rotomoulded articles prepared from these resins however suffer from high shrinkage and warpage. Resin R 3 , prepared with a Ziegler-Natta catalyst has a higher elastic component than R 7 , thus less favourable for sintering. Resin R 6 prepared according to the present invention has an intermediate position between resins R 7 and R 3 and offers the advantage of very small shrinkage and warpage.
  • a first set of rotational moulding trials were carried out on the polyethylene powders, R 2 , R 3 , R 6 and R 7 micronised on the WEDCO® machine.
  • Each grade polymer was exposed to three peak internal air temperatures (PIAT) that were respectively of 180, 190 and 210° C.
  • PIAT is defined as the maximum temperature that the mould reached within the oven before it was removed to the cooling bay of the rotational moulding machine.
  • the parts were moulded using an oven set temperature of 300° C.
  • the ROTOLOG® temperature measuring system was used to record the temperature profiles of the internal air, material, and mould as well as that of the oven.
  • the system consists of an insulated radio transmitter, which is attached to the mould and travels with it in the oven and in the cooler bay.
  • the transmitter sends a signal to a receiver, which in turn is connected to a computer that uses the ROTOLOG® software to graph real-time temperature/time data.
  • the mould used to produce the test mouldings was an aluminium cube mould of base 300 mm ⁇ 300 mm with a central vent port and with a draft angle of 3° included to facilitate demoulding.
  • the shot weight was set at 1.8 kg to produce 3 mm thick mouldings.
  • the mould was removed from the oven at peak internal temperatures of 180° C., 190° C. and 210° C.
  • the cooling medium for all the materials was forced air and the moulding conditions for the trials were as follows:
  • Mould shrinkage factors are measured by recording how much a moulded article dimension reduces after the moulding has cooled.
  • the reduced dimension is related to a reference dimension taken from the actual mould.
  • the mould had a grid machined into the bottom of its cavity.
  • the distance selected as the reference value was the hypothenuse distance of the grid at the bottom of the mould: it was measured to be 169.9 mm.
  • the distance between the same two reference points was recorded on the cooled moulding and the percentage of shrinkage was then determined.
  • the measuring apparatus consisted of a milling machine bed upon which the moulded article was placed. An electronic microscope was fixed onto movable axes positioned above the milling bed.
  • the amount of warpage on a moulded article was measured by using a dial gauge in conjonction with the apparatus described here-above for measuring the shrinkage.
  • the dial gauge pointer was placed above the centre of the grid and the milling machine bed was raised vertically so that a datum value could be set on the gauge.
  • the milling bed was then moved so that the dial gauge sat on a point of the grid and a reading was made of how much the pointer rose or fell with respect to the datum value. This was repeated for all the points on the grid and the maximum warpage was defined as the largest deviation from the datum.
  • Table IV TABLE IV Maximum warpage in mm Material PIAT of 180° C. PIAT of 190° C.
  • brittle and ductile Modes of failure during impact testing fall into two categories: brittle and ductile.
  • brittle failure a crack initiates and propagates prior to any bulk yielding of the specimen and hence the point of failure lies on the initial rising portion of the load/deformation curve.
  • ductile failure considerable yielding takes place and the failure occurs well after the maximum on the load/deformation curve.
  • the area under the load/deformation curve is a measure of the fracture energy, it follows that brittle failure is associated with very low absorbed energy as compared to ductile failure.
  • the samples used for impact tests were all taken from the same side of each trial moulding so that the results were made comparable to the moulding conditions. They were cut with a bandsaw into squares of 60 mm ⁇ 60 mm, the edges were cleaned of burrs and the thickness at the centre of each sample was noted. The machine used was the CEAST Fractovis and depending upon the thickness and the expected strength of the sample under test, the sensitivity and the working range of the load cell were appropriately set up to sense the sample failure.
  • the microstructure of resins R 9 and R 10 according to the invention and of reference resins R 1 and R 3 was also studied following the method described in Oliveira and Cramez (Oliveira M. J., and Cramez M. C.; J. Macrom. Sci.-Physics, B40, 457, 2001.), wherein the size of the spherulites is schematicised by microscopy.
  • the spherulites of reins R 9 and R 10 have a much smaller size than those of the reference resins R 1 and R 3 as can be seen in FIG. 4 a to 4 d. It can be seen that the resins according to the invention have a structure that differes that of polymers compounded with nucleating additives.
  • the resins according to the invention have an improved impermeability to solvents as can be seen in FIG. 5 .
  • FIG. 5 represents the permeability to fuels expressed in g/day at 40° C. measured on rotomoulded 700 ml bottles having a weight of 150 g and prepared at a PIAT of 190° C. with resins R 1 , R 3 , R 9 and R 10 . They also have improved mechanical properties such as for example impact strength and stress crack resistance and improved optical properties, such as gloss.
  • the cycle time was measured for rotomoulded articles prepared with resins R 1 , R 3 and R 9 at a PIAT of about 190° C.
  • the results are displayed in FIG. 6 representing for the three resins the PIAT temperature expressed in ° C. as a function of time expressed in seconds. It can be observed that resin R 9 , although it has a PIAT higher (by about 8° C.) than that of the other resins, crystallises faster than resins R 1 and R 3 .
  • Further tests on the cycle time were carried out using a pressurised mould as described by Crawford (Crawford R. presented at “Advanced seminar in rotational moulding.” held in Minneapolis on Sep. 23, 2001.). The results are presented in FIG. 7 and clearly show a dramatic reduction in crystallisation time and cycle time for resin R 9 .
  • Resins R 9 and R 10 were ground to powder on state of the art grinding equipment: they exhibited outstanding performances in terms of productivity.
  • Polyethylene resins prepared with a bis-indenyl metallocene catalyst system, and having densities in the range of from 0.910 to 0.940 g/cm 3 and a M12 in the range of from 0.1 to 2 g/ 10 min are not suitable, as such, for rotomoulding applications. They can however be used as impact modidfiers in blends for rotational moulding applications. Up to 50 wt % of resins having densities in the range of from 0.910 to 0.940 g/cm 3 and M12 in the range of from 0.1 to 2 g/ 10 min can be blended with polyethylene or with polypropylene for use in rotomoulding, blow moulding, injection blow mouldind or injection moulding applications.
  • Resin R 9 was also tested under various grinding conditions, using either different grinding machines, or using the same grinder to produce powders of different granulometry.
  • the standard pellets were ground into powders having an average size of about 300 microns and the particle size distribution analysis was carried out using the method of standard test ASTM D 1921 and further described in McDaid and Crawford (J. McDaid and R. J. Crawford, in “The grinding of polyethylene for use in rotational moulding.” In Rotation, Spring 1997, 27.).
  • the samples were produced on the following machines:
  • Resins R 1 , R 7 , R 9 , R 11 and R 12 were tested for micropellets production. Three types of machines were used (Gala, BKG, Black Clawson) and the pelletisation conditions for each machine are summarised in Table VII. TABLE VII Machine 1 Machine 2 Machine 3 Resin R9 R1 R12 R9 R1 R11 R9 R7 Micropellets ⁇ D eg > ( ⁇ m) 700 600 650 525 525 470 600 550 Throughput (kg/h) 60 80 60 100 100 100 3 4 Yield (%) 65 95 95 95 95 95 ⁇ 50 ⁇ 50 Residual water no no No yes yes yes Yes yes Pelletisation Extruder type Twin screw: 60 mm Twin screw: 75 mm Twin screw: 50.8 mm Melt pump yes yes Yes yes yes yes No no Number of holes 300 300 300 2200 2200 2200 520 520 Hole diameter ( ⁇ m) 400 400 400 300 300 350 350 Hole length (mm) 3 3 3 — — — 1.5 1.5 Number of knives 18 18 18 6 6 6
  • FIG. 13 A comparison of granulometry analysis for powders and micropellets is displayed in FIG. 13 representing the mass fraction of powders and micropellets expressed in percent as a function of particle size expressed in microns for resin R 7 and showing clearly that the average size of the micropellets is substantially larger than that of powders.
  • micropellets exhibit a better bubble removal as a function of temperature than do the ground products.
  • resins R 11 and R 12 have a high molecular weight and thus excellent mechanical properties: they are excellent candidates to replace the cross-linked polyethylene (XLPE) resins generally recommended in the field of rotational moulding.
  • XLPE cross-linked polyethylene

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US20070037937A1 (en) * 2004-02-13 2007-02-15 Eric Damme Process for improving the co-polymerization of ethylene and an olefin co-monomer in a polymerization loop reactor
EP1862288A1 (en) * 2006-05-29 2007-12-05 Total Petrochemicals Research Feluy Optimisation in rotomoulded applications.
US20090233099A1 (en) * 2005-05-09 2009-09-17 Eric Maziers Bi-layer rotomoulding applications
US20090306274A1 (en) * 2006-05-09 2009-12-10 Total Petrochemicals Research Feluy Coloured Rotomoulded Articles
US20110059278A1 (en) * 2004-11-19 2011-03-10 Total Petrochemicals Research Feluy Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
US20110251303A1 (en) * 2008-12-22 2011-10-13 Merck Patent Gmbh Pigment granules
US20140329979A1 (en) * 2011-12-14 2014-11-06 Ineos Europe Ag Novel polymers
US9709529B2 (en) 2006-05-31 2017-07-18 Semmelweis Egyetem Method and device for in vivo desorption ionization of biological tissue
US10242858B2 (en) 2011-12-28 2019-03-26 Micromass Uk Limited Collision ion generator and separator
US10335123B2 (en) 2009-05-27 2019-07-02 Micromass Uk Limited System and method for identification of biological tissues
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RU2011135979A (ru) 2009-01-30 2013-03-10 ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи Композиции полиэтилена высокой плотности, способ их получения, изготовленные из них укупоривающие изделия и способ изготовления таких укупоривающих изделий
CN102574314B (zh) 2009-08-28 2016-09-28 陶氏环球技术有限责任公司 旋转模塑制品及其制备方法
KR101309389B1 (ko) * 2011-06-28 2013-09-17 삼성토탈 주식회사 열수축 필름용 폴리에틸렌 수지 조성물 및 열수축 필름
US10995203B2 (en) * 2016-07-21 2021-05-04 Exxonmobil Chemical Patents Inc. Rotomolded compositions, articles, and processes for making the same
KR101862928B1 (ko) 2016-09-05 2018-05-30 한화토탈 주식회사 선형 중밀도 폴리에틸렌 수지 조성물 및 이로부터 제조된 성형품
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Cited By (20)

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US20070037937A1 (en) * 2004-02-13 2007-02-15 Eric Damme Process for improving the co-polymerization of ethylene and an olefin co-monomer in a polymerization loop reactor
US20140349050A1 (en) * 2004-11-19 2014-11-27 Total Research & Technology Feluy Solid State Properties of Polyethylene Prepared with Tetrahydroindenyl-based Catalyst System
US20110059278A1 (en) * 2004-11-19 2011-03-10 Total Petrochemicals Research Feluy Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
US8822611B2 (en) * 2004-11-19 2014-09-02 Total Research & Technology Feluy Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
US9255161B2 (en) * 2004-11-19 2016-02-09 Fina Technology, Inc. Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
US20090233099A1 (en) * 2005-05-09 2009-09-17 Eric Maziers Bi-layer rotomoulding applications
US20090306274A1 (en) * 2006-05-09 2009-12-10 Total Petrochemicals Research Feluy Coloured Rotomoulded Articles
EP1862288A1 (en) * 2006-05-29 2007-12-05 Total Petrochemicals Research Feluy Optimisation in rotomoulded applications.
WO2007137908A1 (en) * 2006-05-29 2007-12-06 Total Petrochemicals Research Feluy Optimisation in rotomoulded applications
AU2007267236B2 (en) * 2006-05-29 2010-08-05 Total Petrochemicals Research Feluy Optimisation in rotomoulded applications
US20100213638A1 (en) * 2006-05-29 2010-08-26 Total Petrochemicals Research Feluy Optimisation in Rotomoulded Applications
US9709529B2 (en) 2006-05-31 2017-07-18 Semmelweis Egyetem Method and device for in vivo desorption ionization of biological tissue
US8846783B2 (en) * 2008-12-22 2014-09-30 Merck Patent Gmbh Pigment granules
US20110251303A1 (en) * 2008-12-22 2011-10-13 Merck Patent Gmbh Pigment granules
US10335123B2 (en) 2009-05-27 2019-07-02 Micromass Uk Limited System and method for identification of biological tissues
US20140329979A1 (en) * 2011-12-14 2014-11-06 Ineos Europe Ag Novel polymers
US9175119B2 (en) * 2011-12-14 2015-11-03 Ineos Europe Ag Polymers
US10242858B2 (en) 2011-12-28 2019-03-26 Micromass Uk Limited Collision ion generator and separator
US20210147589A1 (en) * 2019-11-14 2021-05-20 Exxonmobil Chemical Patents Inc. Gas Phase Polyethylene Copolymers
US11767384B2 (en) * 2019-11-14 2023-09-26 Exxonmobil Chemical Patents Inc. Gas phase polyethylene copolymers

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KR101011168B1 (ko) 2011-01-26

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