WO2010009955A1 - Copolymères de 1-butène - Google Patents

Copolymères de 1-butène Download PDF

Info

Publication number
WO2010009955A1
WO2010009955A1 PCT/EP2009/058108 EP2009058108W WO2010009955A1 WO 2010009955 A1 WO2010009955 A1 WO 2010009955A1 EP 2009058108 W EP2009058108 W EP 2009058108W WO 2010009955 A1 WO2010009955 A1 WO 2010009955A1
Authority
WO
WIPO (PCT)
Prior art keywords
octene
aluminium
decene
tmi
tris
Prior art date
Application number
PCT/EP2009/058108
Other languages
English (en)
Inventor
Luigi Resconi
Davide Balboni
Gilberto Moscardi
Simona Esposito
Original Assignee
Basell Poliolefine Italia S.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basell Poliolefine Italia S.R.L. filed Critical Basell Poliolefine Italia S.R.L.
Publication of WO2010009955A1 publication Critical patent/WO2010009955A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/05—Cp or analog where at least one of the carbon atoms of the coordinating ring is replaced by a heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—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
    • C08F4/65927—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 two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to crosslinked copolymers of 1-butene and higher linear alpha- olefins, such as 1-octene or 1-decene.
  • This class of copolymers is obtained by using a specific metallocene -based catalyst system.
  • butene-1 based polymers are well known in the art and have found application in several highly demanding end uses, thanks to their high pressure resistance, creep resistance, impact strength, and flexibility. These properties can be modified by the use of comonomers.
  • butene- 1 copolymers with a higher content of comonomer can be used for example as components of blends with other polyolefin or polymeric products, in order to modulate particular properties such as sealing strength, flexibility and softness of the plastic materials.
  • crosslinks can be introduced between different molecular chains of a thermoplastic polymer by a number of mechanisms, one of which consists in generating polymer radicals by peroxide, which eventually lead to crosslink formation via a coupling reaction.
  • other characteristics e.g.
  • crosslinked polymers suitable for several applications e.g., wire and cable insulation, weatherstripping, fibers, seals, gaskets, foams, footware, flexible tubing, pipes, bellows, tapes, etc.
  • the crosslink process can lead to thermoplastic vulcanizates (TPV) which can be processed as thermoplastic materails, or to fully vulcanized materials showing thermoset properties. In this case, shaping of the final item must take place before the crosslinking step.
  • TPV thermoplastic vulcanizates
  • EP 186 287 relates to random 1-butene copolymers comprising from 50% to 99% mol of 1- butene.
  • the copolymers are described with very broad ranges of properties. In particular the melting point ranges from 30 to 120 0 C depending on the type and the amount of the comonomer used. This document is silent about the possibility to crosslink the copolymers
  • US 6,288,192 relates to 1-butene homo or copolymers having a high molecular weight and being amorphous.
  • the copolymers of the present invention even not presenting a melting point are substantially isotactic. Thus the intrinsic stickiness of atactic or poorly isotactic polymers is avoided.
  • EP 1 260 525 relates to 1-butene copolymers having among other features a stereoregularity index (mmmm)/mmrr + rmmr at most 20.
  • the polymers of the present invention are not endowed with this feature. Also in this case the document is silent about the possibility to crosslink
  • copolymers of 1-butene and 1-octene or 1-decene can be affectively crosslinked also with low amount of comonomer.
  • the resulting crosslinked copolymer is endowed with an improved elasticity.
  • An object of the present invention is a crosslinked copolymer of 1-butene and 1-octene or 1- decene; containing from 3.0% to 20.0% by mole of 1-octene or 1-decene derived units; preferably the content of 1-octene or 1-decene derived units is comprised between 3.5% to 15.0% by mole, more preferably the content of 1 -octene or 1 -decene derived units is comprised between
  • the copolymer of 1-butene and 1-octene or 1-decene before the crosslinking process is endowed with the following features i) isotactic pentad mmmm higher than or equal to 90%; pentads (mmrr+mrrm) lower than 4 and pentad rmmr not detectable by 13 C NMR.
  • C is the molar content of 1-octene or 1-decene derived units
  • D is equal to 110
  • TmI is the highest melting peak in the first melting transition measured by DSC on a compression moulded plaque aged for 10 minutes in an autoclave at 2000
  • a crosslinked copolymer of 1-butene and 1-octene is a copolymer having a tension set value at 100% of deformation lower than the corresponding 1- butene or 1-octene copolymer not subjected to a crosslinking process.
  • crosslinking process known in the art can be used.
  • any crosslinking agent known in the art can be used for the preparation of the cross- linked polyolefin compositions of the present invention.
  • cross-linking agents comprising organic peroxides.
  • peroxides are: 1 ,l'-bis(tert- butylperoxy)diisopropylbenzene; dicumyl peroxide; n-butyl-4,4'-bis(tert-butylperoxy)valerate; 2,5-di(tert-butylperoxy)2,5-dimethylhexane, dibenzoyl peroxide.
  • the peroxides are generally used in quantities ranging from 0.5% to 10%, preferably from 1% to 5% by weight with respect to the total weight of the composition which is subjected to cross-linking.
  • One or more coadjuvants are used together with the peroxides.
  • Preferred examples of coadjuvants are 1,2- polybutadiene, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethylmethacrylate, divinylbenzene.
  • Storage modulus (G') is proportional to the extent of the elastic component (contributed by crosslinking, entanglement, and/or aggregation) of the system, and loss modulus (G") is proportional to the extent of the viscous component (contributed by the liquidlike portion) of the system.
  • the magnitude of the ratio G"/ G' tan ⁇ which is called the damping factor ( ⁇ phase angle) is a useful quantifier of the presence and extent of elasticity in a fluid. The smaller the tan ⁇ (or the greater G') the higher is extent of elasticity.
  • the elasticity of the crosslinked copolymers object of the present invention is shown from the tension set value, in fact the crosslinked copolymers of the present invention shows an improved elasticity with respect to the non-crossliked copolymers.
  • copolymers of the present invention to be subjected to the crosslinking process are prepared by using metallocene -based catalyst system wherein the metallocene compound has a particular substitution pattern.
  • 1-butene 1-octene or 1-decene copolymers can be obtained by contacting under polymerization conditions 1-butene and 1-octene or 1-decene, in the presence of a catalyst system obtainable by contacting:
  • the stereorigid metallocene compound belonging to the formula (I) is:
  • M is an atom of a transition metal selected from those belonging to group 4; preferably M is zirconium;
  • X equal to or different from each other, is a hydrogen atom, a halogen atom, a R, OR, OR'O, OSO 2 CF 3 , OCOR, SR, NR 2 or PR 2 group wherein R is a linear or branched, saturated or unsaturated Ci-C 2 o-alkyl, C3-C 2 o-cycloalkyl, C6-C 2 o-aryl, C7-C 2 o-alkylaryl or C 7 -C 20 -arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; and R' is a Ci-C 2 o-alkylidene, C6-C 2 o-arylidene, C7-C 2 o-alkylarylidene, or C7-C 2 o-arylalkylidene radical
  • R and R are preferably C 1 -C 10 alkyl or C 6 -C 2 O aryl radicals; more preferably they are methyl radicals;
  • R 5 is preferably a hydrogen atom or a methyl radical; or can be joined with R 6 to form a saturated or unsaturated, 5 or 6 membered ring, said ring can bear Ci-C 2 O alkyl radicals as substituents;
  • R 6 is preferably a hydrogen atom or a methyl, ethyl or isopropyl radical; or it can be joined with R 5 to form a saturated or unsaturated, 5 or 6 membered rings as described above;
  • R 7 is preferably a linear or branched, saturated or unsaturated Ci-C 2 o-alkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the
  • Ci-Cio-alkyl radical preferably a Ci-Cio-alkyl radical; more preferably R 7 is a methyl or ethyl radical; otherwise when R is different from a hydrogen atom, R 7 is preferably a hydrogen atom R and R , equal to or different from each other, are linear or branched, saturated or unsaturated Ci-C 2 o-alkyl radicals, optionally containing heteroatoms belonging to groups
  • R and R equal to or different from each other are Ci-Cio-alkyl radicals; more preferably R is a methyl, or ethyl radical; and
  • R 4 is a methyl, ethyl or isopropyl radical
  • the compounds of formula (I) have formula (Ia) or (Ib):
  • R is a linear or branched, saturated or unsaturated Ci-C 2 o-alkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R is a
  • Ci-Cio-alkyl radical more preferably R is a methyl, or ethyl radical.
  • Alumoxanes used as component B) can be obtained by reacting water with an organo-aluminium compound of formula H J AIU 3 - J or H j Al 2 Ue- J , where U substituents, same or different, are hydrogen atoms, halogen atoms, Ci-C 2 o-alkyl, C3-C 2 o-cyclalkyl, C6-C 2 o-aryl, C7-C 2 o-alkylaryl or or C7-C20- arylalkyl radical, optionally containing silicon or germanium atoms with the proviso that at least one
  • U is different from halogen, and j ranges from 0 to 1 , being also a non-integer number.
  • the molar ratio of Al/water is preferably comprised between 1 : 1 and 100:1.
  • the molar ratio between aluminium and the metal of the metallocene generally is comprised between about 10: 1 and about 20000: 1, and more preferably between about 100: 1 and about 5000: 1.
  • the alumoxanes used in the catalyst according to the invention are considered to be linear, branched or cyclic compounds containing at least one group of the type:
  • n 1 is 0 or an integer from 1 to 40 and the substituents U are defined as above, or alumoxanes of the formula:
  • U (Al — O)n 2 can be used in the case of cyclic compounds, wherein n is an integer from 2 to 40 and the U substituents are defined as above.
  • alumoxanes suitable for use according to the present invention are methylalumoxane (MAO), tetra-(isobutyl)alumoxane (TIBAO), tetra-(2,4,4- trimethyl-pentyl)alumoxane (TIOAO), tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) and tetra-(2,3,3-trimethylbutyl)alumoxane (TTMBAO).
  • MAO methylalumoxane
  • TIBAO tetra-(isobutyl)alumoxane
  • TIOAO tetra-(2,4,4- trimethyl-pentyl)alumoxane
  • TDMBAO t
  • Non-limiting examples of aluminium compounds according to WO 99/21899 and WOO 1/21674 are: tris(2,3,3-trimethyl-butyl)aluminium, tris(2,3-dimethyl-hexyl)aluminium, tris(2,3-dimethyl- butyl)aluminium, tris(2,3-dimethyl-pentyl)aluminium, tris(2,3-dimethyl-heptyl)aluminium, tris(2-methyl-3-ethyl-pentyl)aluminium, tris(2-methyl-3-ethyl-hexyl)aluminium, tris(2-methyl-3- ethyl-heptyl)aluminium, tris(2-methyl-3-propyl-hexyl)aluminium,
  • TMA trimethylaluminium
  • TIBAL triisobutylaluminium
  • TIOA tris(2,4,4-trimethyl-pentyl)aluminium
  • TDMBA tris(2,3-dimethylbutyl)aluminium
  • TTMBA tris(2,3,3-trimethylbutyl)aluminium
  • Non-limiting examples of compounds able to form an alkylmetallocene cation are compounds of formula D + E " , wherein D + is a Br ⁇ nsted acid, able to donate a proton and to react irreversibly with a substituent X of the metallocene of formula (I) and E " is a compatible anion, which is able to stabilize the active catalytic species originating from the reaction of the two compounds, and which is sufficiently labile to be able to be removed by an olefinic monomer.
  • the anion E " comprises of one or more boron atoms.
  • the anion E " is an anion of the formula BAr/ , wherein the substituents Ar which can be identical or different are aryl radicals such as phenyl, pentafiuorophenyl or bis(trifluoromethyl)phenyl. Tetrakis-pentafluorophenyl borate is particularly preferred examples of these compounds are described in WO 91/02012. Moreover, compounds of the formula BAr 3 can conveniently be used. Compounds of this type are described, for example, in the published International patent application WO 92/00333.
  • Non limiting examples of compounds of formula D + E " are: Tributylammoniumtetrakispentafiuorophenylaluminate, Tributylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
  • Organic aluminum compounds used as compound C) are those of formula H j AlUs-, or H j Al 2 Ue -J described above.
  • the catalysts of the present invention can also be supported on an inert carrier.
  • an inert support such as, for example, silica, alumina, Al-Si, Al-Mg mixed oxides, magnesium halides, styrene/divinylbenzene copolymers, polyethylene or polypropylene.
  • the supportation process is carried out in an inert solvent such as hydrocarbon for example toluene, hexane, pentane or propane and at a temperature ranging from 0 0 C to 100 0 C, preferably the process is carried out at a temperature ranging from 25°C to 90 0 C or the process is carried out at room temperature.
  • an inert solvent such as hydrocarbon for example toluene, hexane, pentane or propane
  • a suitable class of supports which can be used is that constituted by porous organic supports functionalized with groups having active hydrogen atoms. Particularly suitable are those in which the organic support is a partially crosslinked styrene polymer. Supports of this type are described in
  • inert supports particularly suitable for use according to the invention is that of polyolefin porous prepolymers, particularly polyethylene.
  • a further suitable class of inert supports for use according to the invention is that of porous magnesium halides such as those described in International application WO 95/32995.
  • the process for the polymerization of 1-butene and Cs-Ci 2 alpha olefins according to the invention can be carried out in the liquid phase in the presence or absence of an inert hydrocarbon solvent.
  • the hydrocarbon solvent can either be aromatic such as toluene, or aliphatic such as propane, hexane, heptane, isobutane or cyclohexane.
  • the copolymers of the present invention are obtained by a solution process, i.e. a process carried out in liquid phase wherein the polymer is completely or partially soluble in the reaction medium.
  • the polymerization temperature is generally comprised between 0 0 C and +200 0 C preferably comprised between 40° and 90 0 C, more preferably between 50 0 C and 80 0 C.
  • the polymerization pressure is generally comprised between 0,5 and 100 bar.
  • copolymers of the present inventions can be used alone or in blend with other polymers in films, sheets and manufactured articles.
  • composition of the 1 -butene/higher olefin copolymers was calculated as follows using the S ⁇ carbons:
  • B is 1-butene and X is 1-octene or 1-decene.
  • the melting temperatures and relative enthalpy of fusion of the polymers were measured by Differential Scanning Calorimetry (DSC) on a Perkin Elmer DSC-I calorimeter equipped with Pyris 1 software, performing scans in a flowing N 2 atmosphere.
  • DSC apparatus was previously calibrated at indium and zinc melting points with particular attention in determining the baseline with required accuracy.
  • the preparation of the samples, for calorimetric investigations, was performed by cutting them into small pieces by using a cutter.
  • the weight of the samples in every DSC crucible was kept at 6.0 ⁇ 0.5 mg.
  • the weighted sample was sealed into aluminium pans and heated to 180 0 C at 10°C/minute.
  • the sample was kept at 180 0 C for 5 minutes to allow a complete melting of all the crystallites, and then cooled down to -20 0 C at
  • Melting temperature (TmI) and the relative enthalpy of fusion in the first heating DSC run were detected on compression-molded samples aged 10 minutes in the autoclave at high pressure (2000 bar) at room temperature and then aged at least 24 hours at 23°C.
  • the glass transition temperature (Tg) was also detected from DSC analysis in the second heating run from -90 0 C up to 180 0 C at 10°C/min.
  • the weight of the samples in every DSC crucible was kept at
  • Frequency sweep experiments were performed with dynamic oscillatory MCR 300 or RMS 800 rheometer with parallel plates (25 mm diameter) geometry and a gap of 2 mm, following the international standard ISO 6721-10.
  • the samples were set between the parallel plates preheated to 190 0 C (temperature of the dynamic experiment).
  • the specimens were kept in a nitrogen atmosphere during the rheological test.
  • Compression-molded samples were prepared by heating the samples at temperatures higher than the melting temperatures (200 0 C) under a press for 5 minutes and then cooling the melt to room temperature with a cooling rate of 30°C/min. Before performing the tensile measurements, these compression molded butene copolymers were aged for 10 minutes in an autoclave (water) at high pressure (2000 bar) at room temperature and then aged for additional 24 hours at 23°C. Rectangular specimens 30 mm long, 5 mm wide, and 2 mm thick were uniaxially drawn up to the break at room temperature at 500 mm/min and stress-strain curves were collected. For each samples 6 stress-strain curves were collected and averaged. In this way stress at yield, elongation at yield, stress at break and elongation at breack have been measured.
  • Compression-molded samples were prepared by heating the samples at temperatures higher than the melting temperatures (200 0 C) under a press for 5 minutes and then cooling the melt to room temperature with a cooling rate of 30°C/min. Before performing the tensile measurements, these compression molded butene copolymers were aged for 10 minutes in an autoclave (water) at high pressure (2000 bar) at room temperature and then aged for additional 24 hours at 23°C. The values of the tension set were measured according to the method ISO 2285.
  • Rectangular specimens 50 mm long, 2 mm wide, and 2 mm thick were uniaxially drawn from their initial length Lo up to a length (deformation rate not constant but high), and held at this elongation for 10 minutes, then the tension was removed and the final length of the relaxed specimens L r was measured after 10 minutes.
  • the value of the tension set is the average of two measures.
  • Dimethylsilanediyl ⁇ (l -(2,4,7 -trimethylindenyl)-7-(2,5-dimethyl-cyclopenta[ 1,2 -b:4 ,3-b']- dithiophene) ⁇ Zirconium dichloride (Al) was prepared according to WO 01/47939.
  • Methylalumoxane (MAO) was supplied by Albemarle as a 30% wt/wt toluene solution and used as such.
  • Triisobutylaluminium (TIBA) was supplied by Crompton as pure chemical and diluted to about 100 g/L with anhydrous cyclohexane. All chemicals were handled using standard Schlenk techniques.
  • the polymerization tests were carried out in a 4.4 L jacketed stainless-steel autoclave equipped with a mechanical stirrer and a 35 -mL stainless-steel vial, connected to a thermostat for temperature control, by using the following procedure.
  • the autoclave Prior to the polymerization experiment, the autoclave was purified by washing with a IM Al(z-Bu)3 solution in hexane and dried at 70 0 C in a stream of nitrogen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un copolymère réticulé de 1-butène et de  1-octène ou de 1-décène contenant de 3,0 % à 20,0 % en mole d’unités dérivées de 1-octène ou de 1-décène.
PCT/EP2009/058108 2008-07-25 2009-06-29 Copolymères de 1-butène WO2010009955A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08104881.1 2008-07-25
EP08104881 2008-07-25
US13734308P 2008-07-30 2008-07-30
US61/137,343 2008-07-30

Publications (1)

Publication Number Publication Date
WO2010009955A1 true WO2010009955A1 (fr) 2010-01-28

Family

ID=41077658

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/058108 WO2010009955A1 (fr) 2008-07-25 2009-06-29 Copolymères de 1-butène

Country Status (1)

Country Link
WO (1) WO2010009955A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004099269A2 (fr) * 2003-05-12 2004-11-18 Basell Polyolefine Gmbh Processus de polymerisation de 1-butene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004099269A2 (fr) * 2003-05-12 2004-11-18 Basell Polyolefine Gmbh Processus de polymerisation de 1-butene

Similar Documents

Publication Publication Date Title
EP2158235B1 (fr) Copolymère 1-butène éthylène
EP1802669B1 (fr) Polymere 1-butene et processus de preparation de celui-ci
EP1735355B1 (fr) Procede de polymerisation de 1-hexene ou d'alpha-olefines superieures
JP2008506824A (ja) １−ブテンポリマー組成物
JP5027665B2 (ja) １−ブテンポリマー及びこの調製方法
EP2252654B1 (fr) Terpolymères de 1-butène
EP2254946B1 (fr) Compositions de polymères à base de 1-butène
KR101536796B1 (ko) 1-부텐 삼원중합체
EP1819743B1 (fr) Procede de preparation de copolymeres 1-butene/propylene
JP2006509064A (ja) １−ブテンコポリマー類およびそれらの製造方法
US7534848B2 (en) 1-butene copolymers and process for preparing them
US20100324238A1 (en) 1-butene terpolymers
US20110003951A1 (en) 1-butene copolymers
WO2010009955A1 (fr) Copolymères de 1-butène
US20100324244A1 (en) 1-butene copolymers

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09780003

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09780003

Country of ref document: EP

Kind code of ref document: A1