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WO2010012587A1 - Polymères de l'éthylène - Google Patents

Polymères de l'éthylène Download PDF

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Publication number
WO2010012587A1
WO2010012587A1 PCT/EP2009/058993 EP2009058993W WO2010012587A1 WO 2010012587 A1 WO2010012587 A1 WO 2010012587A1 EP 2009058993 W EP2009058993 W EP 2009058993W WO 2010012587 A1 WO2010012587 A1 WO 2010012587A1
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WO
WIPO (PCT)
Prior art keywords
formula
process according
groups
radical
periodic table
Prior art date
Application number
PCT/EP2009/058993
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English (en)
Inventor
Davide Balboni
Simona Esposito
Giampiero Morini
Fabrizio Piemontesi
Original Assignee
Basell Polyolefine 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 Polyolefine Italia S.R.L. filed Critical Basell Polyolefine Italia S.R.L.
Publication of WO2010012587A1 publication Critical patent/WO2010012587A1/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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • 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

Definitions

  • Polymers based on non-conjugated cyclic dienes such as ethylene/propylene/ethylidene norbornene copolymers are those which are vulcanizable, are superior in weatherability, heat resistance and ozone resistance and are used for automobile industrial parts, industrial rubber products, insulating materials, civil and construction materials and rubber products such as gummed clothes and also widely used for materials to be blended with plastics such as a polypropylene and polystyrene.
  • the applicant find a class of bridged metallocene compound having a particular substitution pattern able to give in high yields ethylene and non conjugated cyclic diene copolymers having an high molecular weight and a relatively high non conjugated cyclic diene derived units content, without using an high concentration of non conjugated cyclic diene in the polymerization bath.
  • M is titanium zirconium or hafnium; preferably M is zirconium
  • X 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-C2o-alkyl, C3-C2o-cycloalkyl, C6-C 2 o-aryl, C7-C 2 o-alkylaryl or C 7 -C 2 o-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; preferably X is a hydrogen atom, a halogen atom, a OR'O or R group; more
  • R 2 , R 3 , R 4 , and R 5 are hydrogen atoms, or C 1 -C 2 0 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; two or more R , R , R , and R 5 can also be joined to forma a C3-C 1 0 ring that can be saturated or unsaturated optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; said ring can be substituted with one or more C 1 -C 10 hydrocarbon radicals; preferably R , R , R , and R , equal to or different from each other are hydrogen atoms or linear or branched, cyclic or acyclic, Ci-C4o-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C 6 -C 4 o-aryl, C 7 -C 4 o-alkylaryl or C 7 -C 4 ,
  • L is a divalent C 1 -C 4 0 hydrocarbon radical optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements or a divalent silylidene radical containing up to 5 silicon atom; preferably L is a divalent bridging group selected from C1-C40 alkylidene, C3-C40 cycloalkylidene, C6-C40 arylidene, C7-C40 alkylarylidene, or C 7 - C 4 0 arylalkylidene radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, or silylidene radical containing up to 5 silicon atoms such as SiMe 2 , SiPli 2 ; preferably L is a group (Z(R") 2 ) n wherein Z is a carbon or a silicon atom, n is 1 or 2 and R" is a C 1 -C 2 0 hydrocarbon radical optionally containing heteroatoms
  • metallocene of formula (I) is in the racemic form
  • the non-conjugated cyclic diene of the present invention is a cyclic compound having-two unsaturated bonds.
  • This non-conjugated cyclic diene is preferably a hydrocarbon cyclic compound having preferably 6 to 20 carbon atoms and more preferably 6 to 12 carbon atoms.
  • non-conjugated cyclic diene of the present invention may include, though not particularly limited to, bicycle [2.2.1]hept-2-ene derivatives having an alkylidene group such as 5- ethylidenebicyclo[2.2.1]hept-2-ene (5-ethylidene-2-norbornene), 5-ethylidene-6- methylbicyclo[2.2.1]hept-2-ene, 5-ethylidene-6-ethylbicyclo[2.2.1]hept-2-ene, 5-ethylidene-6- isopropylbicyclo[2.2.1]hept-2-ene, 5-ethylidene-6-butylbicyclo[2.2.1]hept-2-ene, 5-n- propylidenebicyclo[2.2.1]hept-2-ene, 5-n-propylidene-6-methylbicyclo[2.2.1]hept-2-ene, 5-n- propylidene-6-ethyl
  • bicyclo[2.2.1]hept-2-ene derivatives having a Ci-Cio alkylidene group as substituent and bicyclo[2.2.1]hept-2-ene derivatives having a Ci-Cio alkenyl group as substituent are preferable.
  • Particularly preferred are 5-ethylidene-2-norbornene (E/Z-5- ethylidenebicyclo[2.2.1]hept-2-ene) and 5-vinyl-2-norbornene are most preferable.
  • Preferred alpha olefin is propylene or 1-butene.
  • the process according to the present invention can be carried out in a gas phase, or in a 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 process is carried out in a liquid phase it can be in slurry, or in solution.
  • 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 -100 0 C and +200 0 C preferably comprised between 0° and 160 0 C, more preferably between 20 0 C and 8O 0 C.
  • the polymerization pressure is generally comprised between 0,5 and 100 bar.
  • R 2 , R 3 , R , R 5 , R and R 7 are hydrogen atoms.
  • R and R 7 are hydrogen atoms and the other substituents have the meaning specified above.
  • R 2 , R , R , R and R are hydrogen atoms and the other substituents have the meaning specified above.
  • R 3 , R 4 , R 5 , R 6 and R 7 are hydrogen atoms and the other substituents have the meaning specified above.
  • R 2 , R 3 , R 5 , R 6 and R 7 are hydrogen atoms and the other substituents have the meaning specified above.
  • R , R 3 , R 4 , R 6 and R 7 are hydrogen atoms and the other substituents have the meaning specified above.
  • R 2 , R are hydrogen atoms and the other substituents have the meaning specified above.
  • R , R 5 are hydrogen atoms and the other substituents have the meaning specified above.
  • R , R are hydrogen atoms and the other substituents have the meaning specified above.
  • R , R 5 are hydrogen atoms and the other substituents have the meaning specified above.
  • R , R are hydrogen atoms and the other substituents have the meaning specified above.
  • R , R are hydrogen atoms and the other substituents have the meaning specified above.
  • Alumoxanes used as component B) can be obtained by reacting water with an organo-aluminium compound of formula H j AlU3_ j or H j Al 2 Ue- J , where U substituents, same or different, are hydrogen atoms, halogen atoms, Ci-C 2 o-alkyl, C 3 -C 2 o-cyclalkyl, C 6 -C 2 o-aryl, C 7 -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.
  • organo-aluminium compound of formula H j AlU3_ j or H j Al 2 Ue- J where U substituents, same or different, are hydrogen atoms, halogen atoms, Ci-C 2 o-alkyl
  • 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 0 or an integer from 1 to 40 and the substituents U are defined as above, or alumoxanes of the formula: U
  • 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 tetra-(2,3-dimethylbutyl)alumoxane
  • TTMBAO tetra-(2,3,3-trimethylbutyl)alumox
  • 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 4 , 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(trifiuoromethyl)phenyl)borate, Tributylammoniumtetrakis(4-fluorophenyl)borate, N,N-Dimethylbenzylammonium-tetrakispentafiuorophenylborate, N,N-Dimethylhexylammonium-tetrakispentafluorophenylborate, N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)aluminate, Di(propyl)ammoniumtetrakis(pentafluorophenyl)borate, Di(
  • 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 polymer obtained with the present invention have preferably an ethylene derived units content ranging from 24.9 to 99.9 % by weight; a content of non-conjugated cyclic diene derived units ranging from 0.1 to 10.0 % by weight, preferably from 1.0 to 10.0 % by weight.
  • the ethylene derived units content ranges from 45.0 to 75.0 % by weight
  • the non-conjugated cyclic diene derived units ranging from 2.0 to 10.0 % by weight
  • a content of alpha olefins of formula CH 2 CHT derived units ranging from 15 to 53 % by weight.
  • the ethylene derived units content ranges from 65.0 to 70.0 % by weight
  • the non-conjugated cyclic diene derived units ranges from 4.0 to 9.0 % by weight the and a content of alpha olefins of formula
  • CH 2 CHT derived units ranging from 36.0 to 51.0 % by weight.
  • ENB content was determined with Infrared spectroscopy by using a method based on a calibration straight line obtained by using the absorption bands in the region between 4482 cm-1 and 3950 cm-1 and the absorption band at 1688 cm-1.
  • Ethylene and propylene content were obtained with a method based on Near Infrared absorption bands at 5669cm-l and 5891 cm-1 , the resulting value is then corrected for the ENB content.
  • the measures are carried out on a film sample obtained by molding the raw polymer with a hydraulic press (0.2 - 3 Kg/cm2) for about 30 seconds at either 160 0 C (ethylene/propylene determination) or 180 0 C (ENB determination) using an aluminium spacer of fixed thickness (0.1 - 0.2 mm).
  • a weighted amount of metallocene (Al) is transferred in a Schlenk flask under nitrogen.
  • This activated metallocene solution is maintained at room temperature under stirring for 12 h. After this, it can be used in polymerization and it maintains the initial polymerization over at least a week.
  • the autoclave is closed and the temperature is raised to 58 0 C and ethylene and propylene
  • the internal pressure is kept constant for the entire polymerization test by feeding an ethylene/propylene mixture having nearly the same weight ratio of the terpolymer under production.
  • table 1 the polymerization conditions are reported.

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  • 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

L'invention porte sur un procédé de copolymérisation de l'éthylène, d'un ou plusieurs diènes cycliques non conjugués et facultativement d'une ou plusieurs alpha-oléfines de formule CH2=CHT, dans laquelle T représente un radical alkyle en C1-C20. Ce procédé comprend l'étape de mise en contact des monomères dans des conditions de polymérisation, en présence d'un système catalytique contenant un composé métallocène de formule (I), dans laquelle : M représente titane, zirconium ou hafnium; X représente un atome d'hydrogène, un atome d'halogène, un groupe R, OR, OR'O, OSO2CF3, OCOR, SR, NR2 ou PR2, où R est un radical hydrocarboné et R' est un radical alkylidène en C1-C20, arylidène en C6-C20, alkylarylidène en C7-C20 ou arylalkylidène en C7-C20; R1 représente un radical alkyle en C1-C20; R2, R3, R4, R5, R6 et R7 représentent des atomes d'hydrogène ou des radicaux hydrocarbonés en C1-C20 ou au moins deux R parmi R2, R3, R4, et R5 peuvent également être réunis pour former un cycle en C3-C10; L est un radical hydrocarboné en C1-C40 divalent.
PCT/EP2009/058993 2008-08-01 2009-07-14 Polymères de l'éthylène WO2010012587A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP08104952 2008-08-01
EP08104952.0 2008-08-01
US18855908P 2008-08-11 2008-08-11
US61/188,559 2008-08-11

Publications (1)

Publication Number Publication Date
WO2010012587A1 true WO2010012587A1 (fr) 2010-02-04

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9382361B2 (en) 2014-03-21 2016-07-05 Exxonmobil Chemical Patents Inc. Process to produce ethylene propylene copolymers
WO2017048448A1 (fr) 2015-09-14 2017-03-23 Exxonmobil Chemical Patents Inc. Procédé de fabrication d'epdm ramifié et epdm ainsi obtenu
US11041034B2 (en) 2018-02-09 2021-06-22 Exxonmobil Chemical Patents Inc. Ethylene-a-olefin-diene elastomers and methods of making them

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0718325A2 (fr) * 1994-12-20 1996-06-26 Mitsui Petrochemical Industries, Ltd. Procédé de préparation de copolymère statistique éthyléne/alpha-oléfine/polyène non conjugué, copolymère ainsi obtenu et ses utilisations
EP0751156A2 (fr) * 1995-06-28 1997-01-02 Mitsui Petrochemical Industries, Ltd. Composition d'un copolymère d'éthylène caoutchouteux, composition de caoutchouc vulcanisable contenant le copolymère caoutchouteux et procédé de préparation du copolymère caoutchouteux
US5776851A (en) * 1993-11-24 1998-07-07 Targor Gmbh Metallocenes, process for their preparation and their use as catalysts
US5883275A (en) * 1996-10-31 1999-03-16 Targor Gmbh Process for the hydrogenation of metallocenes
EP1195386A1 (fr) * 2000-03-14 2002-04-10 Denki Kagaku Kogyo Kabushiki Kaisha Composant catalyseur a metal de transition pour la polymerisation, et procede de production de polymere a l'aide de ce composant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5776851A (en) * 1993-11-24 1998-07-07 Targor Gmbh Metallocenes, process for their preparation and their use as catalysts
EP0718325A2 (fr) * 1994-12-20 1996-06-26 Mitsui Petrochemical Industries, Ltd. Procédé de préparation de copolymère statistique éthyléne/alpha-oléfine/polyène non conjugué, copolymère ainsi obtenu et ses utilisations
EP0751156A2 (fr) * 1995-06-28 1997-01-02 Mitsui Petrochemical Industries, Ltd. Composition d'un copolymère d'éthylène caoutchouteux, composition de caoutchouc vulcanisable contenant le copolymère caoutchouteux et procédé de préparation du copolymère caoutchouteux
US5883275A (en) * 1996-10-31 1999-03-16 Targor Gmbh Process for the hydrogenation of metallocenes
EP1195386A1 (fr) * 2000-03-14 2002-04-10 Denki Kagaku Kogyo Kabushiki Kaisha Composant catalyseur a metal de transition pour la polymerisation, et procede de production de polymere a l'aide de ce composant

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9382361B2 (en) 2014-03-21 2016-07-05 Exxonmobil Chemical Patents Inc. Process to produce ethylene propylene copolymers
WO2017048448A1 (fr) 2015-09-14 2017-03-23 Exxonmobil Chemical Patents Inc. Procédé de fabrication d'epdm ramifié et epdm ainsi obtenu
US10800865B2 (en) 2015-09-14 2020-10-13 Exxonmobil Chemical Patents Inc. Process for making branched EPDM and the EPDM therefrom
US11041034B2 (en) 2018-02-09 2021-06-22 Exxonmobil Chemical Patents Inc. Ethylene-a-olefin-diene elastomers and methods of making them
US11859032B2 (en) 2018-02-09 2024-01-02 Exxonmobil Chemical Patents Inc. Ethylene-a-olefin-diene elastomers and methods of making them

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