WO2002055566A2 - Polyolefine de poids moleculaire eleve, catalyseur et procede de polymerisation de ladite polyolefine - Google Patents

Polyolefine de poids moleculaire eleve, catalyseur et procede de polymerisation de ladite polyolefine Download PDF

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Publication number
WO2002055566A2
WO2002055566A2 PCT/US2001/044467 US0144467W WO02055566A2 WO 2002055566 A2 WO2002055566 A2 WO 2002055566A2 US 0144467 W US0144467 W US 0144467W WO 02055566 A2 WO02055566 A2 WO 02055566A2
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WO
WIPO (PCT)
Prior art keywords
present
polymeric material
polymer
alkyl
article
Prior art date
Application number
PCT/US2001/044467
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English (en)
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WO2002055566A3 (fr
Inventor
Judith Preuschen
Bernhard Rieger
Carsten Troll
Original Assignee
The Procter & Gamble Company
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
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU2002243244A priority Critical patent/AU2002243244A1/en
Publication of WO2002055566A2 publication Critical patent/WO2002055566A2/fr
Publication of WO2002055566A3 publication Critical patent/WO2002055566A3/fr

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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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • 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
    • C08F110/14—Monomers containing five or more carbon atoms
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

  • a great proportion of the specific material properties of polyolefins stems from the fact that such material are not entirely crystalline but rather comprise crystallites of varying size.
  • Many macroscopic properties can be linked to size of the crystallites more or less directly.
  • One such property is the stress strain behaviour, the tensile forces required to strain the material need to be higher if the size of the crystallites becomes larger.
  • Another macroscopic property linked to the size of the crystallites is the colour or transparency of the material. If the crystallite sizes are of the same size as the wavelength of visible light, the light is dispersed.
  • the present invention provides a polymeric material comprising substantially linear polyolefin molecules comprising a C 3 -C 20 monomers.
  • the molecular weight of said linear polyolefin molecules is at least 500kg/mol.
  • the present invention further provides a polymeric material wherein said monomer is propene.
  • the present invention further provides a polymeric material wherein the relative content of [mmmm] of said polyolefin is between 10% and 60%.
  • the present invention further provides a polymeric material wherein said polymeric material has a ratio k of at least 0.2 where k is defined as
  • the present invention further provides a synthetic material comprising substantially linear polyolefin molecules comprising a C 3 -C 20 monomers wherein said synthetic material recovers after having been stretched to 220% of its original length to less than 120% of its original length.
  • the present invention further provides a catalyst combination for polymerising linear polyolefin molecules comprising a C 3 -C 20 monomers wherein said catalyst combination comprises a metallocene of the general formula
  • R 3 /R 4 , R 6 /R 7 can be partially or simultaneously integrated into 5- to 7-linked cycloalkyl or aryl rings fused thereto
  • R 9 and R 10 refer to H, C, to C 8 alkyl, 4- to 7-linked cycloalkyl, aryl in which case R 9 , R 10 can jointly with E form a 4- to 7-linked cycloalkyl - X refers to a C, to C 8 alkyl, aryl, or benzyl, preferably methyl
  • - E refers to carbon, silicon, germanium, or 1.2-ethyl, 1.3-propyl, or 1.4-butyl,
  • - E 2 refers to methyl, oxygen or sulphur, and n is 1 or 2. and an activator selected from B(C 6 F 5 ) 3 , R 9 3 C[B(C 6 F 5 ) 4 ], [R 9 3 NH] [B(C 6 F 5 ) 4 ] where R 9 is a C, - C 4 alkyl group or an aryl group.
  • the present invention further provides a process for making polymeric material comprising substantially linear polyolefin molecules comprising a C 3 -C 20 monomers wherein said process comprises a step of polymerising said monomers using the catalyst combination according to Claim 6.
  • the present invention further provides a process for making a polymeric material comprising linear polyolefin molecules wherein the molecular weight of said linear polyolefin molecules is at least 500kg/mol.
  • the first monomer of the polymer of the present invention is a C 3 -C 20 alk-1-ene, such as for example propene, 1-butene, 2-butene, -pentene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecne, 1-eicosene, and the like.
  • the first monomer may be a cycloolefin such as for example cyclopentene, cyclohexene, norbornadiene and its derivatives.
  • the polymer of the present invention may be a homopolymer or may be a copolymer of two or more different monomers.
  • the first monomer In order for the polymer of the present invention to have the above stereo characteristics at least the first monomer must be at least C 3 .
  • the second monomer and other additional monomers are preferably C 3 -C 30 as defined above or may further be cycloolefins such as those specified above.
  • the polymer is a homopolymer comprising propene monomers.
  • the molecular weight of the polymer of the present invention is preferably at least 500kg/mol, more preferably at least 800kg/mol, yet more preferably 1000 kg/mol, yet more preferably at least 1250 kg/mol, yet more preferably 1500 kg/mol, yet more preferably 1750kg/mol, most preferably at least 2000kg/mol.
  • the molecular weight is determined for example by Gel Permeation Chromatography (GPC) with microstyragel as the column material, with 1 , 2, 4- trichlorobenzole as solvent, and with the appropriate closely distributed calibration standards such as polyethylene, polystyrene, or the like.
  • the molecular weight distribution M w /M n of the polymer of the present invention is preferably less than 6, more preferably less than 5, yet more preferably less than 4, yet more preferably less than 2.
  • the material may be preferred for the material to have a broad molecular weight distribution.
  • Mw/Mn is at least 5, more preferably at least 10, yet more preferably at least 15, yet more preferably at least 20, most preferably at least 30.
  • the tacticity i.e. the relative content of [mmmm] pentads, of the polymer of the present invention is preferably at least 10.0%, more preferably at least 15.0%, yet more preferably at least 20.0%, most preferably at least 22.5%.
  • the tacticity of the polymer of the present invention is less than 60%, more preferably less 50%, yet more preferably less than 40%, most preferably less than 35%. It is to be noted, however, that for certain applications other tacticities may be required.
  • the polymeric material of the present invention preferably comprises a relatively high amount of mrrm pentads.
  • This pentad is characteristic for a polymer side chain which exhibits a stereo chemistry opposite its two neighbouring polymer side chains.
  • the opposing central side chain is referred to as a single stereo error.
  • the polymer of the present invention only has a low content of atactic sequences or rather regular sequences as can be seen from its low content of rmrm pentads.
  • [rmrni] preferably is less than 5%, more preferably less tan 4%, yet more preferably less than 3%, most preferably less than 2%.
  • the melting point of the polymer of the present invention is preferably at least 80°C, more preferably at least 100°C, more preferably at least 120°C, yet more preferably at least 130°C.
  • the glass transition temperature of the polymer of the present invention is preferably below 30°C, more preferably below 10°C, yet more preferably below 0°C, most preferably below -5°C. High melting points and low glass transition temperatures ensure stability and usability of the polymeric material of the present invention over a wide range of temperatures. Melting point and glass transition temperature may be determined for example by Differential Scanning Calorimetry (DSC) methods such as well known art.
  • DSC Differential Scanning Calorimetry
  • the polymer material of the present invention preferably has a low density of below 0.96g/cm 3 , more preferably below 0.92g/cm 3 , yet more preferably below 0.88g/cm 3 .
  • the polymer of the present material shows elastomeric behaviour as can be seen from its relaxation characteristics after stretching and as is quantified by the following measure of inelasticity.
  • the 'Measure of Inelasticity' refers to a protocol (ASTM D174-90) of stretching the sample to 220%, 150%, and 115%, respectively of its original length, at a cross-head speed of 25 mm/min., holding the sample for 3 minutes at 23°C, then releasing tension and allowing the sample to recover to an equilibrium length.
  • a suitable machine for this set of experiments is a standard universal tensile tester manufactured by Instron Corp., Canton, MA., model 5564. The results reported for strain are true strain values versus engineering strain values.
  • the material of the present invention preferably recovers after having been stretched to 220% of its original length to less than 120% of its original length, more preferably to less than 115% of its original length, yet more preferably to less than 110% of its original length, yet more preferably to less than 108% of its original length, most preferably to less than 106% of its original length.
  • the material preferably recovers after having been stretched to 150% of its original length to less than 110% of its original length, more preferably to less than 108% of its original length, yet more preferably to less than 106% of its original length, yet more preferably to less than 105% of its original length, most preferably to less than 104% of its original length.
  • the material of the present invention preferably recovers after having been stretched to 120% of its original length to less than 108% of its original length, more preferably to less than 106% of its original length, yet more preferably to less than 105% of its original length, yet more preferably to less than 104% of its original length, most preferably to less than 103% of its original length.
  • the polymeric material of the present invention preferably has a shore A hardness of at least 15, more preferably of at least 25, yet more preferably at least 35. Further, the polymeric material of the present invention has a shore A harness of less than 90, more preferably less than 80, yet more preferably less than 70. it is to be noted, however, that for certain application a different hardness may be required.
  • the catalyst of the present invention has the following chemical structure
  • R 1 through R 8 refer to linear or branched C 1 to C 10 alkyl, 5- to 7-linked cycloalkyl which in its turn, can carry one ore several C, to C 6 alkyl residues as substituents, C 6 to C 18 arylalkyl or alkylaryl, in which case R R 2 , R 3 /R 4 , R 6 /R 7 can be partially or simultaneously integrated into 5- to 7-linked cycloalkyl or aryl rings fused thereto
  • R 9 and R 10 refer to H, C 1 to C 8 alkyl, 4- to 7-linked cycloalkyl, aryl in which case R g , R 10 can jointly with E form a 4- to 7-linked cycloalkyl X refers to C 1 to C 8 alkyl, aryl, benzyl, preferably alkyl, more preferably methyl
  • E refers to carbon, silicon, germanium, or 1.2-ethyl, 1.3-propyl, or 1.4-
  • the catalyst of the present invention also has surprisingly been found to yield the high molecular weight of the polymer of the present invention as well as the other beneficial properties of the polymer.
  • Preparation of the catalyst can be carried out in analogy to the catalyst preparation described in WO99/52955, pages 12 through 16, except for the substitution of Zr with Hf.
  • the catalyst of the present invention may be precipitated on a suitable carrier system such as those well known in the art.
  • the polymerisation process of the present invention involves the catalyst of the present invention and an activator according to one of the general formulas
  • the catalyst of the present invention and the above activators are employed in such quantities that the atomic ratio between the boron from the activator and hafnium from the catalyst is at least 1 :1 and more preferably is less than 100:1 , yet more preferably less than 10:1 , most preferably less than 2:1.
  • the polymerisation process of the present invention is carried at a pressure of at least 1 bar more preferably at least 3 bars, yet more preferably at least 5 bars.
  • the polymerisation process of the present invention is carried out at a pressure of less than 100 bars, more preferably less than 20 bars, yet more preferably less than 15 bars. It is to be noted, however, that the pressure during the reaction of course depends on the reaction temperature.
  • the present invention provides an article comprising a first element and a second element separated from and joined to said first element, said first element being a body of polymeric material.
  • the present invention further provides a method for manufacturing a body from polymeric material comprising a step of processing said polymeric material selected from the group of to injection moulding, extrusion blow moulding, extrusion, casting, solution sedimentation, and combinations thereof.
  • the present invention further provides a method for processing a body of polymeric material comprising a step selected from the group of thermoforming, laser forming, carving, and combinations thereof.
  • the body of the present invention has been found to exhibit a relative low tackiness at room temperature due to the high molecular weight of the polymer.
  • the second element of the article of the present invention can preferably be made from the same homopolymer as the first element, either having the same low isotacticity or a different isotacticity depending on the intended use of the second element.
  • the configuration of the polymeric material of the second element can also be a body or it could be a foam, a fibre, a film, or the like. Making articles from different grades of the same material is beneficial when recycling material from a disposed article. If the same homopolymer is used for the different elements of the article, no separation step into the various materials is necessary before recycling of the material.
  • additives may be useful to blend additives into the homopolymer of the present invention.
  • a broad variety of such additives is known in the art and can be used accordingly.
  • small amounts of a thermal stabilizer such as 0.1 %-0.25% of a phenol/phosphite blend, can be mixed into the homopolymer of the present invention to increase the thermal stability of the polymer during processing.
  • the article according to the present invention may be a hygienic article.
  • the term "hygienic article” as used herein refers to articles which are intended to be used in contact with or in proximity to the body of a living being. Such hygienic articles may be disposable or intended for multiple or prolonged use. Such hygienic articles include but are not limited to catheters, tubing, drainage systems, syringes, grafts, prosthetics, body implants, instrumentation, support means, toothbrushes, bed covers, stents, gaskets, pump diaphragms, baby bottle nipples, pacifiers, and the like. Having regard to the specific advantages of the polymers used for the articles of the present invention, it will be readily apparent to the skilled practitioner to apply the bodies of polymeric material according to the present invention in the above and similar hygienic articles.
  • the article according to the present invention may be a household article.
  • the term "household article” as used herein refers to articles intended to be used when running a household.
  • the household articles of the present invention include but are not limited to garbage bins, storage containers, hoses, toys, kitchenware, clothing and in particular heavy duty clothing up to bullet proof clothing, shoes and in particular show soles, scuba fins and the like, furniture in particular garden furniture, sporting goods, bellows, and the like.
  • the present invention provides an article comprising a first element and a second element joined to the first element, the first element comprising a film web material.
  • the present invention further provides a method for manufacturing a film web material comprising a step of processing the aforementioned polymeric material, the step of processing selected from the group of casting, extruding, blowing, and combinations thereof.
  • the present invention further provides a method for processing a film web material comprising the aforementioned polymer, the process comprising a step selected from the group of orienting, bi- axially stretching, crazing, stretching, shrinking, and combinations thereof.
  • the polymer may be mixed with a particulate filler material such as calcium carbonate prior to manufacturing the film and be stretched subsequent to manufacturing the film in order to create micro pores at the location of the included filler material by stretching the film material.
  • the breathable film material of the present invention has a moisture vapour transmission rate (MVTR) of at least 1000 g per 24 hours per square meter, more preferably at least 2000 g/24hours/m 2 , yet more preferably at least 3000 g/24h/m 2 , most preferably at least 4000 g/24h/m 2 .
  • MVTR moisture vapour transmission rate
  • the article of the present invention may also be a packaging article such as produce bags, trash bags, ice bags, shipping sacks, containers, pouches, and the like.
  • packaging article refers to articles which are intended to at least partially envelope other articles.
  • the first element of such an article is a specifically contoured piece of the film web material and the second element may be a sealing such as a thermobond seal of the film web material onto itself.
  • the article of the present invention may also be a package article where the first element of the article is the wrap material used for packaging the second element.
  • the present invention provides a fibrous web material comprising a plurality of fibres of the polymer of the present invention.
  • the present invention further provides a method for manufacturing fibres from the aforementioned polymeric material comprising a step of processing the polymeric material selected from the group of wet spinning, dry spinning, melt spinning, semi dry spinning (solvent evaporation or sedimentation), and combinations thereof.
  • the present invention further provides a method for manufacturing a fibrous web material comprising the steps of providing fibres of the aforementioned polymeric material and of combining the fibres into a web material.
  • the present invention further provides a method for stabilizing a fibrous web material according to the present invention comprising the steps of providing a fibrous web material and of stabilizing step the fibrous web material.
  • additives may be added to the homopolymer of the present invention to change the properties of the polymer such as is well known in the art.
  • Fibres suitable for the web materials of the present invention may be mono fibres or the may comprise filaments.
  • the amount of the low isotacticity homopolymer of the present invention present in the fibre of the present invention needs to be reduced in order to accelerate crystallization of the fibres after spinning.
  • the fibre of the present invention comprises less than 80% of the low isotacticity homopolymer, more preferably less than 60%, yet more preferably less than 40%, most preferably less than 30%.
  • a high isotacticity polymer having a broader molecular weight distribution may be used in order to accelerate crystallization times.
  • the addition of the low isotacticity homopolymer of the present invention reduces the requires forces, pressures, or torques respectively to process the polymer.
  • suitable methods to manufacture fibrous web material according to the present invention from fibres including but not being limited to meltblowing, spunbonding, carding, air laying, wet laying, weaving, knitting, bailing, and the like.
  • suitable methods for optional stabilization of the fibrous web material of the present invention including but not being limited to hydroentangling, thermo bonding, pressure bonding, air through bonding, needling, resin bonding, combinations thereof, and the like. It is a further aspect of the present invention to provide an article comprising a fibrous web material according to the present invention.
  • the article according to the present invention may be a hygienic article.
  • the article of the present invention may also be a clothing article or a household article including but not being limited to bed covers, underwear, tights, socks, gloves, sport clothing, outdoor clothing, low temperature clothing, shoes and show covers, protective clothing such as for motor biking, blankets, covers, bags, items of furniture, and the like.
  • the fibrous web material according to the present invention may also be used as a construction element in an article.
  • the functionalities of the fibrous web material includes but is not limited to supporting, carrying, fixing, protecting other elements of the article and the like.
  • Such articles include but are not limited to adhesive tapes, protective wraps, complex constructions such as buildings (floor coverings, house wraps, and the like), cars, household appliances, horticultural and agricultural constructions (geotextiles), and the like.
  • the article of the present invention may further a membrane such as in filters, car batteries, and the like.
  • the present invention provides a coating composition for covering at least a portion of the surface of an element with a polymeric coating according to the present invention.
  • the present invention further provides an article comprising an element and the aforementioned polymeric coating material covering at least portion of the surface of said element.
  • the present invention further provides a method for coating an element with the aforementioned polymeric coating material comprising a step selected from the group of dip coating, spray coating, emulsion coating, and combinations thereof.
  • the coating of the present invention can be applied at relatively low basis weights.
  • the basis weight of the coating of the present invention is less than 50 grams per square meter, more preferably less than 40 g/m 2 , yet more preferably less than 30 g/m 2 , yet more preferably less than 20 g/m 2 , most preferably less than 10 g/m 2 .
  • a wide variety of suitable techniques to manufacture coating articles are known including but not being limited to dip coating, spray coating, emulsion coating, and combinations thereof.
  • the coating of the present invention is not limited to a specific substrate as long as the polymer of the coating is capable of sufficiently adhering to the substrate material.
  • Suitable substrates include but are not limited to bodies of various material such as metal, polymer, wood, and the like, woven and nonwoven web materials, films, and the like.
  • the aforementioned methods for manufacturing coating articles all have specific advantages which are known to the skilled person. Hence, the skilled person will be able to select a suitable method for manufacturing the coating material of the present invention depending on the specific requirement of the respective application of the coating material.
  • foam materials In the prior art, a wide variety of suitable techniques to manufacture foam materials are known including but not being limited to inert gas expansion, evaporated solvent expansion, reactive reagent gas expansion, high internal phase emulsion, bead expansion, and combinations thereof.
  • the aforementioned methods for manufacturing foam materials all have specific advantages which are known to the skilled person.
  • Suitable gases or evaporated solvents for expanding the foams of the present invention include but are not limited to CO 2 , N 2 , propene, pentane, and the like. It has been found that due to the low tacticity of the polymer, the processability of the polymer during manufacture of the foam has been greatly improved.
  • the foam material according to the present invention may also be used as a construction element in an article.
  • the functionalities of the foam material include but is not limited to heat insulation, electric insulation, shock absorption, cushioning, acoustic wave damping, protecting other elements of the article, sealing, packaging, storing, providing buoyancy, and the like.
  • Such articles include but are not limited to toys, furniture, mattresses, carpets, clothing, shoes, sport equipment, complex constructions such as buildings (floor coverings, house wraps, and the like), cars, household appliances, and the like.
  • the foam material of the present invention may be oil absorbent and may be rendered water absorbent by suitable surface energy modifiers. Suitable surface energy modifiers are well known in the art.
  • the foam material of the present invention may be used in instances including but not being limited to oil absorption, solvent absorption, spill absorption, liquid distribution, liquid transportation, and the like.
  • various additives such as those known in the art may be added to the external and internal surfaces of the foam of the present invention.
  • the foam material of the present invention may further be used to deliver absorbed liquids such as for example adhesive, shoe polish, ink, lubricants and the like upon compression of the foam material.

Abstract

L'invention concerne des polyoléfines et plus particulièrement des polyoléfines comprenant un monomère en C3-C20, et possédant un poids moléculaire d'au moins 5000kg/mol. L'invention concerne également un catalyseur métallocène à base d'hafnium et un procédé de production desdites polyoléfines.
PCT/US2001/044467 2000-11-30 2001-11-27 Polyolefine de poids moleculaire eleve, catalyseur et procede de polymerisation de ladite polyolefine WO2002055566A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002243244A AU2002243244A1 (en) 2000-11-30 2001-11-27 High molecular weight polyolefin and catalyst and process for polymerising said polyolefin

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00126192.4 2000-11-30
EP00126192 2000-11-30
EP01114578.6 2001-06-18
EP01114578 2001-06-18

Publications (2)

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WO2002055566A2 true WO2002055566A2 (fr) 2002-07-18
WO2002055566A3 WO2002055566A3 (fr) 2002-10-03

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PCT/US2001/044949 WO2002046247A2 (fr) 2000-11-30 2001-11-30 Polyolefine a haute masse moleculaire, catalyseur et procede de polymerisation de ladite polyolefine

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EP (1) EP1339763A2 (fr)
JP (1) JP2004515581A (fr)
KR (1) KR20030061407A (fr)
CN (1) CN1478109A (fr)
AU (3) AU2002243244A1 (fr)
BR (1) BR0115686A (fr)
CA (1) CA2427377A1 (fr)
MX (1) MXPA03004845A (fr)
WO (2) WO2002055566A2 (fr)

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WO2007001694A1 (fr) 2005-06-24 2007-01-04 Exxonmobil Chemical Patents Inc. Composition adhésive de copolymère de propylène fonctionnalisé
US8614277B2 (en) 2007-12-20 2013-12-24 Exxonmobil Research And Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them

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US20100324242A1 (en) 2006-10-20 2010-12-23 Idemitsu Kosan Co., Ltd. Highly pure, terminal-unsaturated olefin polymer and process for production thereof
CN103980395B (zh) * 2014-04-30 2016-08-24 中国科学院化学研究所 一种可用于3d打印的超高分子量无规聚丙烯树脂及其制备方法和应用

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AU2002241542B2 (en) 2005-03-17
BR0115686A (pt) 2003-09-09
KR20030061407A (ko) 2003-07-18
WO2002046247A3 (fr) 2002-08-01
WO2002046247A2 (fr) 2002-06-13
EP1339763A2 (fr) 2003-09-03
JP2004515581A (ja) 2004-05-27
AU4154202A (en) 2002-06-18
AU2002243244A1 (en) 2002-07-24
WO2002055566A3 (fr) 2002-10-03
WO2002046247A8 (fr) 2003-11-20
CA2427377A1 (fr) 2002-06-13
CN1478109A (zh) 2004-02-25
MXPA03004845A (es) 2004-01-26

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