EP1250365A2 - Composition de metal de transition, systeme de ligand, systeme de catalyseur et son utilisation pour la polymerisation et la copolymerisation d'olefines - Google Patents

Composition de metal de transition, systeme de ligand, systeme de catalyseur et son utilisation pour la polymerisation et la copolymerisation d'olefines

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Publication number
EP1250365A2
EP1250365A2 EP00988791A EP00988791A EP1250365A2 EP 1250365 A2 EP1250365 A2 EP 1250365A2 EP 00988791 A EP00988791 A EP 00988791A EP 00988791 A EP00988791 A EP 00988791A EP 1250365 A2 EP1250365 A2 EP 1250365A2
Authority
EP
European Patent Office
Prior art keywords
indenyl
group
dimethylsilanediyl
zirconium dichloride
butyl
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00988791A
Other languages
German (de)
English (en)
Inventor
Jörg SCHOTTEK
Markus Oberhoff
Carsten Bingel
David Fischer
Horst Weiss
Andreas Winter
Volker Fraaije
Roland Kratzer
Ralph-Dieter Maier
Wolfgang Bidell
Nicola Paczkowski
Jürgen Suhm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
Original Assignee
Basell Polyolefine GmbH
Basell Polypropylen GmbH
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
Priority claimed from DE1999162905 external-priority patent/DE19962905A1/de
Application filed by Basell Polyolefine GmbH, Basell Polypropylen GmbH filed Critical Basell Polyolefine GmbH
Priority to EP05001434.9A priority Critical patent/EP1548023B1/fr
Priority to EP05001432A priority patent/EP1548037A3/fr
Priority to EP05001433A priority patent/EP1548022A3/fr
Publication of EP1250365A2 publication Critical patent/EP1250365A2/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—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
    • 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
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to a process for the polymerization of olefins, in particular a process for the copolymerization of propylene with other olefins, specially substituted metallocenes, ligand systems and highly active catalyst systems.
  • supported catalyst systems have been proposed in which the metallocene and / or the aluminum compound serving as cocatalyst are fixed on an inorganic support material.
  • Metallocenes can be used as a catalyst component for the polymerization and copolymerization of olefins.
  • halogen-containing metallocenes are used as catalyst precursors, which can be converted, for example, by an aluminoxane into a polymerization-active cationic metallocene complex (EP-A-129368).
  • the production of metallocenes is known per se (US 4,752,597; US 5,017,714; EP-A-320762; EP-A-416815; EP-A-537686; EP-A-669340; HH Brintzinger et al .; Angew.
  • cyclopentadienyl metal compounds can be reacted with halides of transition metals such as titanium, zirconium and hafnium.
  • the supported catalyst systems deliver polymers, in particular polypropylenes, with melting points of a maximum of 156 ° C, typical 15 values for such systems are only in the range around 150 ° C.
  • copolymers with low molecular weights or low ethene incorporation are usually obtained.
  • the task was therefore to look for supported metallocene catalysts which avoid the disadvantages of the prior art and, in particular because of their high regio- and stereospecificity, provide copolymers with high molecular weight and high ethene incorporation rate under technically relevant polymerization conditions.
  • these metallocenes are said to show a significantly increased polymerization activity when carrying out heterogeneous polymerization and to provide an environmentally friendly and economical process for the preparation of the polymers.
  • the object on which the present invention is based is achieved by a process for the polymerization of olefins, in particular for the copolymerization of propylene with at least one further olefin, in which the polymerization in the presence of a catalyst system comprises the at least one specially substituted metal locene, at least one cocatalyst, optionally one contains inertized carrier and optionally contains at least one further additive component.
  • the metallocene used in the process according to the invention is a compound of the formula (I)
  • R 31 R 32 are the same or different and are a hydrogen atom, a C ⁇ -C ⁇ o-alkyl group, a C ⁇ -C ⁇ o-alkoxy group, a C 6 -C o-aryl group, a Cg-Cio-aryloxy group, a C -C ⁇ o-alkenyl group , an OH group, an N (R 32 ) group, where R32 is a C 1 -C 1 -alkyl group or C ⁇ to C 4 aryl group, or a halogen atom, R 31 and R 32 also being cyclically linked can,
  • R 34 , R 36 , R 37 and R 38 and R 34 ', R 36 ', R 37 'and R 38 ' are identical or different and represent a hydrogen atom, a hydrocarbon group which can be halogenated, linear, cyclic or branched, for example, a C 1 -C 8 alkyl group, C -C o ⁇ alkenyl group, C 6 -C o aryl group, a C 7 ⁇ C 4 o arylalkyl group, a C 7 -C 4 o alkylaryl group or a C 8 ⁇ C 4 o-arylalkenyl group.
  • R 33 and R 33 ' are the same or different, wherein
  • R 33 ' has the meaning of R 33 or a straight in ⁇ -position hydrocarbon group which may be halogenated, for example, a C ⁇ -C 2 o alkyl group, C 2 -C o-alkenyl, C 7 -C 4 o-arylalkyl group, or C 8 -C 4 o-arylalkenyl group
  • R 35, R 35 ' are identical or different and denote a C ⁇ to C o aryl group which carry a substituent R 43 or R 43 ' in the para position to the binding site on the indenyl ring,
  • R 35 and R 35 ' must not be the combinations phenyl and 1-naphthyl or 1-naphthyl and phenyl if R 33 is methyl or ethyl and R 33 ' isopropyl.
  • R 39 means a bridge
  • R 40 , R 4 - 1 can, even with the same indexing, be the same or different and denote a hydrogen atom, a halogen atom or a -C-C 0 carbon-containing group, such as a -C-C 20 alkyl, a C ⁇ -C ⁇ o- fluoroalkyl, a C ⁇ -C ⁇ 0 alkoxy, a C6-C ⁇ 4-aryl, a C ö -Cio-fluoroaryl group, a C 6 -C ⁇ o-aryloxy group, a C 2 -C ⁇ 0 alkenyl, a C 7 -C 4 o-arylalkyl, a C 7 -C 40 alkylaryl, or a C 8 -C 4 o-arylalkenyl group.
  • R 40 and R 41 can each form one or more rings with the atoms connecting them, x denotes an integer from zero to 18, M 12 means silicon, germanium or tin.
  • R 39 can also link two units of the formula I to one another.
  • R 43 represents a hydrogen atom if R 35 is different from R 35 ', or a Ci to C ⁇ o-alkyl radical, a C 2 to C ⁇ 0 alkenyl radical, a C 6 to Cis-aryl radical, a C 7 to C 2 o-arylalkyl radical a C 7 to C o _ Al kylarylrest, a CQ to C 2 o-arylalkenyl group, wherein the hydrocarbon radicals can be halogenated with fluorine or chlorine or teilha- logeniert, -N (R 4) 2, -P (R) 2 , -SR 44 , -Si (R 4 ) 3 , -N (R) 3+ or -P (R) 3+ , where the radicals R 44 are the same or different and a hydrogen atom, a hydrocarbon group, the can be halogenated, linear, cyclic or branched, for example a C 1 -C 8 alkyl group, C 1
  • R 43 > means hydrogen or the meanings given for R 43 .
  • R 4 5, R45 ', R 46 and R 46' are hydrogen or C-Co-aryl-, alkenyl- or alkyl-
  • Ring systems which can also be linked to the radicals R 36 , R 36 'or R 34 , R 34 '.
  • M is zirconium or hafnium
  • R 31 and R 32 are the same or different and are a C 1 -C 8 -alkyl group, a C ⁇ -C ⁇ o alkoxy group, a C ⁇ -Cio aryloxy group or a halogen atom, where R 31 and R 32 can also be cyclically linked,
  • R 33 represents a linear C 1 -C 6 -alkyl group or a linear C 2 -C 1 -C aloyl group,
  • R 33 ' is a cyclized in the ⁇ -position or a branched in the ⁇ -position hydrocarbon group in which the atom in the ⁇ -position is bonded to a total of three carbon atoms, for example a C 3 -C ⁇ o-alkyl group, C 3 -C ⁇ o-alkenyl group , C6-C ⁇ 4 -aryl group, a C 7 -C ⁇ s-arylene lalkyl distr, a C7-Ci5-alkylaryl group, or a Cs-Ci6-Arylal- kenyl distr means
  • R 34 , R 36 , R 37 and R 38 as well as R 34 ', R 36 ', R 37 'and R 38 ' are the same or different and represent a hydrogen atom or a C ⁇ -C ⁇ o-alkyl group which is halogenated, linear, cyclic or can be branched
  • R 45, R 45 ' are identical or different and denote a C 6 to C 20 aryl group which bear a substituent R 43 or R 43 ' in the para position to the binding site on the indenyl ring,
  • R 43 is a Ci to Cio-alkyl radical, a C 2 to C ⁇ 0 alkenyl group, a C 6 to 8 C ⁇ -aryl radical, a C 7 to C 20 arylalkyl radical, a C7 to C 20 rylrest -Alkyla-, a Cs to C 2 o ⁇ arylalkenyl radical, where the hydrocarbon radicals can also be halogenated or partially halogenated with fluorine or chlorine, -N (R) 2 , -P (R 4 ) 2 , -SR 44 ,
  • R 44 are the same or different and a hydrogen atom, one Hydrocarbon group, the halogenated, linear, cyclic or may be branched, for example, a group C ⁇ -C ⁇ 0 alkyl, C-C ⁇ o-alkenyl, C 6 -C 2 o ⁇ aryl group, a C 7 -C 40 arylalkyl group, a C7 Is -C 40 alkylaryl group or a C 8 _ C 4 o-arylalkenyl group,
  • R 43 'means the meanings given for R 43 or hydrogen
  • R 45 , R 45 ', R 46 and R 46 ' are hydrogen or a C 4 -C 6 -aryl ring system
  • M ii zirconium
  • R 31 , R 32 are the same and represent chlorine, methyl or phenolate,
  • R 33 ' is a cyclized in ⁇ -position or a branched in ⁇ -position hydrocarbon group in which the atom in ⁇ -position is bonded to three carbon atoms, for example a C 3 -C ⁇ group 0-alkyl or a C 3 -C ⁇ o ⁇ Alkenyl group means
  • R 34 , R 36 , R 37 and R 38 and R 3 ⁇ R 36 ', R 37 ' and R 38 ' are hydrogen
  • R 35 , R 35 ' are the same or different and are a C 6 to C 20 aryl group, in particular a phenyl or 1-naphthyl group which, in para position to the binding site on the indenyl ring, has a substituent R 43 or R 43 'bears, where R 43 or R 43 ' is a branched C 3 to C 1 -C 6 alkyl radical, a branched C 3 to C 1 -C alkenyl radical, a branched C 7 to C 20 alkylaryl radical or an Si (R 44 ) 3 radical with R 44 in the particularly preferred meaning of R 33 , the carbon hydrogen residues can also be halogenated or partially halogenated with fluorine or chlorine.
  • Examples of preferred metallocene components of the catalyst system according to the invention are combinations of the following molecule fragments of the compound I:
  • R 33 ' isopropyl, sec-butyl, cyclobutyl, 1-methylbutyl, 1-ethylbutyl, 1-methylpentyl, cyclopentyl, cyclohexyl, cyclopent-2-enyl, cyclopent-3-enyl, cyclohex-2-enyl, cyclohexyl 3-enyl, para-methyl-cyclohexyl,
  • R 34 , R6, R 37 and R 38 and R 34 ', R 36 ', R 37 'and R 38 ' hydrogen
  • R 35 , R 3 ⁇ ' p-isopropyl-phenyl, p-tert-butyl-phenyl, ps-butyl-phenyl, p-cyclohexyl, p-trimethylsilyl-phenyl, p-adamantyl-phenyl, p- ( Tris-fluoro) trimethyl-phenyl,
  • 2-cyclopentyl, 2-methyl, symmetrical substituents in 4-position dimethylsilanediyl (2-cyclopentyl-4- (p-isopropylphenyl) indeyl) (2-methyl-4- (p-isopropylphenyl) indenyl) zirconium dichloride, Dimethylsilanediyl (2-cyclopentyl-4- (p-tert.butylphenyl) indenyl) (2-methyl-4- (p-tert.butylphenyl) indenyl) zirconium dichloride, Dimethylsilanediyl (2-cyclopentyl-4- (p-sec.butylphenyl) indenyl) (2-methyl-4- (p-sec.butylphenyl) indenyl) zirconium dichloride, dimethylsilanediyl (2-cyclopentyl-4- (p-cyclohexylphenyl) indenyl) (2-
  • 2-p-methylcyclohexyl 2-methyl, symmetrical substituents in the 4-position, dimethylsilanediyl (2-p-methylcyclohexyl-4- (p-isopropylphenyl) indenyl) (2-methyl-4- (p-isopropylphenyl) indenyl) zirconium dichloride, Dimethylsilanediyl (2-p-methylcyclohexyl-4- (p-tert-butylphenyl) indenyl) (2-methyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride, dimethylsilanediyl (2-p-methylcyclohexyl-4- ( p-sec.butylphenyl) indenyl) (2-methyl-4- (p-sec.butylphenyl) indenyl) zirconium dichloride, dimethylsilanediyl (2-p-methylcyclohexyl
  • 2-cyclopentyl, 2-ethyl, symmetrical substituents in the 4-position dimethylsilanediyl (2-cyclopentyl-4- (p-isopropylphenyl) indenyl) (2-ethyl-4- (p-isopropylphenyl) indenyl) zirconium dichloride, di- methylsilanediyl (2-cyclopentyl-4- (p-tert-butylphenyl) indenyl) (2-ethyl-4- (p-tert-butylphenyl) indenyl) zirconium dichloride, dimethylsilanediyl (2-cyclopentyl-4- (p-sec.butylphenyl) indenyl) (2-ethyl-4- (p-sec.butylphenyl) indenyl) zirconium dichloride, dimethylsilanediyl (2-cyclopentyl-4- (p-sec.
  • Selected metallocenes in particular those which have different substitutions in position 2 and position 4 on the indyl ligand, solve the underlying problem particularly well.
  • the present invention therefore also relates to compounds of the formula
  • M is Ti, Zr or Hf, particularly preferably zirconium,
  • R 3 is a hydrogen atom, a C ⁇ ⁇ Co - containing carbon
  • Ci-Cis-alkyl such as methyl, ethyl, n-butyl, n-hexyl, or octyl, C 2 -C ⁇ o-alkenyl, C 3 -C ⁇ 5 alkylalkenyl, C 7 -C 20 aryl- lalkyl, fluorine-containing -C 2 alkyl, fluorine-containing C 6 -C 8 -aryl, fluorine-containing C 7 -C 20 arylalkyl or fluorine-containing C 7 -Co-alkylaryl, R5 is not equal to R 3 and is sec.butyl, isopropyl, 1-methylbutyl, 1-methylpentyl, cyclopentyl or cyclohexyl,
  • R 4 , R 6 , R 50 are the same or different and a hydrogen atom, a -C-C 20 - carbon-containing group, preferably Ci-Cis-alkyl, such as methyl, ethyl, n-butyl, cyclohexyl or octyl, C 2 -C ⁇ 0 -Alkenyl, C 3 -C 5 -alkylene-alkenyl, C 6 -C 8 -aryl, C 5 -Ci 8 heteroaryl, C 7 -C 20 arylalkyl, C 7 -C 2 o-alkylaryl, fluorine-containing C ⁇ -C ⁇ 2 alkyl, fluorine-containing C 6 "Ci 8 aryl, fluorine-containing C 7 -C 20 arylalkyl or fluorine-containing C 7 _C 0 alkylaryl,
  • R 2 °, R 2 - * - are identical or different and are a C 6 -C 8 aryl group, which can optionally be substituted, in particular phenyl, tolyl, xylyl, tert. -Butylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 4-ethylphenyl, 4-trimethylsilylphenyl, methoxypheny1, naphthyl, acenaphthyl, phenanthrenyl or anthracenyl, Cs-Cis-Heteroaryl , C 7 ⁇ C o-arylalkyl, C 7 -C 2 o-alkylaryl, fluorine-containing C 6 ⁇ Ci 8 aryl, fluorine-containing C 7 -C 20 arylalkyl or fluorine-containing C 7 _C o-alkylaryl and two radicals R 20 or R 21 can form a mono-
  • X is a halogen atom, in particular chlorine, alkyl group, in particular methyl, or substituted or unsubstituted phenolates,
  • Q is a C 4 -C 4 aryl ring system which in turn can be substituted by R 20 , a heteroaryl which forms azapentalenes, thiopentals or phosphoropentalenes with the cyclopentadienyl ring, which in turn can be substituted by R 20
  • z is an integer 0, 1, 2 or 3
  • B examples are groups M 3 R 13 R 14 , in which M 3 is silicon and R 13 and R 14, the same or different, are a C 1 -C 2 -hydrocarbon-containing group such as C 1 -C 8 -alkyl, C 6 -Ci 4 - Aryl, trialkylsilyl, especially trimethylsilyl, triarylsilyl or an alkyl aryl silyl group.
  • Particularly preferred groups for B are Si (Me), Si (Ph) 2 , Si (MeEt), Si (PhMe), Si (PHEt), Si (Et) 2 , where Ph is for substituted or unsubstituted phenyl and Et for Ethyl stands.
  • B can also form a mono- or polycyclic ring system with one or more R 7 or R 8 radicals.
  • Bridged metallocene compounds of the formula (II) are very particularly preferred,
  • M zirconium
  • R 3 are the same or different and are a hydrogen atom or a C 1 -C 2 alkyl group, preferably an alkyl group such as methyl, ethyl, n-butyl, n-hexyl or octyl, particularly preferably methyl or ethyl,
  • R5 is sec.butyl, isopropyl, 1-methylbutyl, 1-methylpentyl, cyclopentyl, cyclohexyl.
  • R 4 , R 6 ⁇ R 50 are hydrogen atoms,
  • X is chlorine, methyl
  • Q is a butadienediyl group which forms an indenyl system with the cyclopentadienyl ring, which in turn can be substituted by R 20 , heteroaryl which forms azapentalenes, thiopentals or phosphoropentalenes with the cyclopentadienyl ring, which in turn can be substituted by R 20 ,
  • 1, identical or different, is an integer between zero and 4, preferably 1 or 2, particularly preferably equal to 1,
  • B denotes a bridging structural element between the two indenyl radicals, B preferably being Si (Me) 2 , Si (Ph), Si (Et) 2 , Si (MePh).
  • the invention furthermore relates to ligand systems of the formula (Ha) in which the radicals have the same meaning as under formula (II).
  • the metallocenes of the formulas I and II according to the invention are highly active catalyst components for olefin copolymerization. Depending on the substitution pattern of the ligands, the metallocenes can be obtained as a mixture of isomers. The metallocenes are preferably used isomerically pure for the polymerization.
  • pseudo-rac isomeric metallocenes of the formulas (I) and (II) are preferably used, but it is also useful to use pseudo-rac-enriched rac / meso mixtures.
  • pseudo-rac, and, pseudo-meso are to be understood as they are disclosed in the document WO 00/31090 on page 8 as formulas II and Ha.
  • metallocenes according to the invention are:
  • Dimethylsilanediyl (2-ethyl-4-phenyl) -indenyl) -L-zirconium dichloride Dimethylsilanediyl (2-ethyl-4- (4'-methyl-phenyl) -indenyl) -L-zirconium dichloride
  • Dimethylsilanediyl (2-hexyl-4- (4 '-adamantyl-phenyl) -indenyl) -L-zirconium dichloride Dimethylsilanediyl (2-methyl-azapentalen) -L-zirconium dichloride Dimethylsilanediyl (2-methyl-hiapentalen) -L-zirconium dichloridyl -methyl-phosphapentalen) -L-zirconium dichloride Dimethylsilandiyl (2-ethyl-azapentalen) -L-zirconium dichloride Dimethylsilandiyl (2-ethyl-thiapentalen) -L-zirconium dichloride Dimethylsilandiyl (2-ethyl-phosphapentalenium) -L-zirconium dichloride
  • L (2-isopropyl-4, 5 benz-indenyl); (2-isopropyl-4- (4'-tert-butyl-phenyl) -indenyl); (2-sec.butyl-4- (4'-tert-butyl-phenyl) -indenyl), - (2-isopropyl-4-phenyl-indenyl); (2-isopropyl-4- (2-naphthyl) -indenyl), - 2-isopropyl-4- (1-naphthyl) -indenyl; (2-sec. Butyl-4-phenyl-indenyl); (2-sec. Butyl-4-phenyl-indeny1); (2-sec.butyl-4, 5 benz-indenyl), - (2-sec. Butyl-4- (2-naphthyl) -indenyl);
  • corresponding zirconium dimethyl compounds the corresponding zirconium- ⁇ 4 -butadiene compounds
  • the metallocenes of the formulas I and II according to the invention are particularly suitable as a constituent of catalyst systems for the production of polyolefins by polymerizing at least one olefin in the presence of a catalyst which contains at least one cocatalyst and at least one metallocene.
  • the cocatalyst which, together with a metallocenes of the formulas I and II according to the invention, forms the catalyst system, contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound, which converts this into a cationic compound by reaction with a metallocene ,
  • the cocatalyst component which can be contained in the catalyst system according to the invention contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic see compound which converts this into a cationic compound by reaction with a metallocene.
  • a compound of the general formula (III) is preferred as the aluminoxane
  • aluminoxanes can e.g. cyclic as in formula (IV)
  • aluminoxanes are described, for example, in JACS 117 (1995), 6465-74, Organometallics 13 (1994), 2957-2969.
  • the radicals R in the formulas (III), (IV), (V) and (VI) can be the same or different and a -C-C 2 o-hydrocarbon group such as a Ci-C ⁇ -alkyl group, a C 6 -C ⁇ 8 -Aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably 10 to 35.
  • the radicals R are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
  • radicals R are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen or isobutyl or n-butyl preferably containing 0.01-40% (number of the radicals R).
  • the aluminoxane can be prepared in various ways by known methods.
  • One of the methods is, for example, that an aluminum-hydrocarbon compound and / or a hydrodaluminium-hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent (such as, for example, toluene).
  • the Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C 1 -C 2 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated Groups such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3, 5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5 di (trifluoromethyl) phenyl.
  • organoboron or organoaluminum compound which contains C 1 -C 2 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluor
  • Lewis acids are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tributyl aluminum, trifluoroborane, triphenyl borane, tris (4-fluorophenyl) borane, tris (3, 5-difluorophenyl dyborane, tris (4-fluoromethylphenyl) borane, tris (4-fluoromethylphenyl) borane nyDborane, tris (tolyl) borane, tris (3, 5-dimethylphenyl) borane, tris (3, 5-difluorophenyl) borane and / or tris (3, 4, 5-trifluorophe- nyDboran. Tris (pentafluorophenyl) borane is particularly preferred.
  • Compounds which contain a non-coordinating anion such as, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbFe ", CF 3 S0 3 _ or CIO 4 " are preferably used as ionic cocatalysts.
  • Lewis bases such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N are used as the cationic counterion -dimethylaniline, p-nitro-N, N-dimethylaniline, triethyl phosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene and triphenylcarbenium are used.
  • Mixtures of at least one Lewis acid and at least one ionic compound can also be used.
  • Borane or carborane compounds such as e.g.
  • Tri (butyl) ammonium bis (undecahydrid-7, 8-dicarbaundecaborate) ferrate (III) is important.
  • Combinations of at least one amine and a support with organo-element compounds, as described in patent WO 99/40129, are also important as cocatalyst systems.
  • Preferred cocatalyst systems are the compounds of the formulas (A) and (B),
  • R 17 can also be a -OSiR 3 group, in which R are the same or different and have the same meaning as R 17 except for a further -OSiR 3 group.
  • a further preferred cocatalyst is general compounds which are formed by the reaction of at least one compound of the formula (C) and / or (D) and / or (E) with at least one compound of the formula (F).
  • R 7 is a hydrogen atom or a boron-free Ci-C-io-carbon-containing group such as -C-C 2 o-alkyl, C 6 -C 2 o-aryl, C 7 -C 4 o-arylalky, C 7 -C 4 can be o-alkyl - aryl and where
  • R I has the same meaning as above,
  • X is an element of VI.
  • D is an element of VI. Main group of the Periodic Table of the Elements or an NR group, in which R is a hydrogen atom or a C 1 -C 8 hydrocarbon radical such as C 1 -C 8 alkyl or C 1 -C 20 aryl,
  • f is an integer from 0 to 3
  • g is an integer from 0 to 3, where z + y are not equal to 0,
  • h is an integer from 1 to 10.
  • the bimetallic compounds are combined with an organometallic compound of the formula VIII [M 4 R 19 q ]], in which M 4 is an element of I., II. And III.
  • Main group of the periodic table of the elements is, R 19 is the same or different and a hydrogen atom, a halogen atom, a -C-C 4 o-carbon-containing group, in particular C -C- 20 - alkyl, C 6 _ C 4 o-aryl, C 7 -C 4 o-aryl-alkyl or C 7 -C 4 o-alkyl-aryl group, q is an integer from 1 to 3 and k is an integer from 1 to 4.
  • the organometallic compounds of the formula VIII are preferably neutral Lewis acids in which M 4 is lithium, magnesium and / or aluminum, in particular aluminum.
  • Examples of the preferred organometallic compounds of formula VIII are trimethylaluminum, triethylaluminum, tri-isopropylalumi - nium, trihexylaluminum, trioctylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, Triisoprenaluminium, Dimethylaluminiummo- istlorid, diethyl aluminum monochloride, Diisobutylaluminiummo- striglorid , Methyl aluminum sesquichloride, ethyl aluminum sesquichloride, dimethyl aluminum hydride, diethyl aluminum hydride, diisopropyl aluminum hydride, dimethyl aluminum (trimethylsiloxide), dimethyl aluminum (triethylsiloxide), phenylalane, pen
  • the carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g. polyolefins).
  • Suitable inorganic oxides can be found in groups 2,3,4,5,13,14,15 and 16 of the periodic table of the elements.
  • preferred oxides as carriers include silicon dioxide, aluminum oxide and mixed oxides of the elements calcium, aluminum, silicon, magnesium, titanium and corresponding oxide mixtures.
  • Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for example, MgO, Zr0, Ti0 or B0 3 , to name just a few.
  • the carrier materials used have a specific surface area in the range from 10 to 1000 m 2 / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size from 1 to 500 ⁇ m.
  • Carriers with a specific surface area in the range from 50 to 500 ⁇ m, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 ⁇ m are preferred.
  • Carriers with a specific surface area in the range from 200 to 400 m 2 / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 ⁇ m are particularly preferred.
  • the carrier material used naturally has a low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as is the case when using silica gel as the carrier material, dehydration or drying is recommended.
  • the thermal dehydration or drying of the carrier material can take place under vacuum and at the same time inert gas blanket (e.g. nitrogen).
  • the drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. In this case, the pressure parameter is not critical.
  • the drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
  • Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane or organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane, dibutyl magnesium.
  • the chemical dehydration or inertization of the carrier material takes place, for example, by reacting a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent with exclusion of air and moisture.
  • suitable solvents are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane, Heptane, toluene or xylene.
  • the inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible.
  • the duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours.
  • the support material is isolated by filtration under inert conditions, washed one or more times with suitable inert solvents as described above and then dried in an inert gas stream or in vacuo.
  • Organic carrier materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and should also be freed of adhering moisture, solvent residues or other contaminants by appropriate cleaning and drying operations before use.
  • polyolefin powders e.g. polyethylene, polypropylene or polystyrene
  • the supported catalyst system At least one of the above-described metallocene components is brought into contact with at least one cocatalyst component in a suitable solvent, a soluble reaction product, an adduct or a mixture preferably being obtained.
  • a suitable solvent a suitable solvent, a soluble reaction product, an adduct or a mixture preferably being obtained.
  • the preparation thus obtained is then mixed with the dehydrated or rendered inert carrier material, the solvent is removed and the resulting supported metallocene catalyst system is dried to ensure that the solvent is completely or largely removed from the pores of the carrier material.
  • the supported catalyst is obtained as a free-flowing powder.
  • a method for producing a free-flowing and optionally prepolymerized supported catalyst system comprises the following steps:
  • Preferred solvents for the production of the metallocene / cocatalyst mixture are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which the individual components preferably dissolve.
  • the solubility of the individual components is not a prerequisite if it is ensured that the reaction product of metallocene and cocatalyst components is soluble in the chosen solvent.
  • suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane, and nonane; Cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene. Ethyl benzene and diethyl benzene. Toluene is very particularly preferred.
  • a molar ratio of aluminum to transition metal in the metallocene of 10: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 50: 1 to 500: 1.
  • the metallocene is dissolved in the form of a solid in a solution of the aluminoxane in a suitable solvent. It is also possible to dissolve the metallocene separately in a suitable solvent and then to combine this solution with the aluminoxane solution. Toluene is preferably used.
  • the preactivation time is 1 minute to 200 hours.
  • the preactivation can take place at room temperature (25 ° C). In individual cases, the use of higher temperatures can shorten the required preactivation time and cause an additional increase in activity. In this case, a higher temperature means a range between 50 and 100 ° C.
  • the preactivated solution or the metallocene / cocatalyst mixture is then combined with an inert carrier material, usually silica gel, which is in the form of a dry powder or as a suspension in one of the abovementioned solvents.
  • the carrier material is preferably used as a powder.
  • the order of addition is arbitrary.
  • the preactivated metallocene-cocatalyst solution or the metallocene-cocatalyst mixture can be metered into the support material or the support material can be introduced into the solution.
  • the volume of the preactivated solution or of the metallocene cocatalyst mixture can exceed 100% of the total pore volume of the support material used, or can be up to 100% of the total pore volume.
  • the temperature at which the preactivated solution or the metal-locene-cocatalyst mixture is brought into contact with the support material can vary in the range between 0 and 100 ° C. However, lower or higher temperatures are also possible.
  • the solvent is then completely or largely removed from the supported catalyst system, and the mixture can be stirred and optionally also heated. Both the visible portion of the solvent and the portion in the pores of the carrier material are preferably removed.
  • the solvent can be removed in a conventional manner using vacuum and / or purging with inert gas. During the drying process, the mixture can be heated until the free solvent has been removed, which usually requires 1 to 3 hours at a preferably selected temperature between 30 and 60 ° C.
  • the free solvent is the visible proportion of solvent in the mixture. Residual solvent is the proportion that is enclosed in the pores.
  • the supported catalyst system can also be dried only to a certain residual solvent content, the free solvent having been removed completely.
  • the supported catalyst system can then be washed with a low-boiling hydrocarbon such as pentane or hexane and dried again.
  • the supported catalyst system shown according to the invention can either be used directly for the polymerization of olefins or prepolymerized with one or more olefinic monomers before being used in a polymerization process.
  • the prepolymerization of supported catalyst systems is described, for example, in WO 94/28034.
  • an olefin preferably an ⁇ -olefin (for example vinylcyclohexane, styrene or phenyldimethylvinylsilane) can be used as a modifying component or an antistatic (as in US Serial No. 08 / during or after the preparation of the supported catalyst system). 365280) are added.
  • the molar ratio of additive to metallocene component compound I is preferably between 1: 1000 to 1000: 1, very particularly preferably 1:20 to 20: 1.
  • the present invention also relates to a process for the preparation of a polyolefin by polymerization of one or more olefins in the presence of the catalyst system according to the invention, comprising at least one transition metal component of the formula I.
  • polymerization is understood to mean homopolymerization and also copolymerization.
  • olefins examples include 1-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norbornadiene, ethyl norbornadiene and cyclic olefins such as norbornene, tetracyclododecenes or methylnorbornene.
  • 1-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norborna
  • propene or ethene is preferably homopolymerized, or propene with ethene and / or with one or more 1-olefins having 4 to 20 C atoms, such as butene hexene or vinylcyclohexane, and / or one or more dienes having 4 to 20 C atoms, such as 1,4-butadiene, norbornadiene, ethylidene norbones or ethyl norbornadiene, are copolymerized. Examples of such copolymers are ethene / propene copolymers or ethene / propene / 1,4-hexadiene terpolymers.
  • the polymerization is carried out at a temperature of 0 to 300 ° C., preferably 50 to 200 ° C., very particularly preferably 50 to 80 ° C.
  • the pressure is 0.5 to 2000 bar, preferably 5 to 64 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
  • the catalyst system shown according to the invention can be used as the only catalyst component for the polymerization of olefins having 2 to 20 carbon atoms, or preferably in combination with at least one alkyl compound of the elements from I. to III.
  • Main group of the periodic table such as an aluminum, magnesium or lithium alkyl or an aluminoxane can be used.
  • the alkyl compound is added to the monomer or suspending agent and is used to purify the monomer from substances which can impair the catalyst activity. The amount of alkyl compound added depends on the quality of the monomers used.
  • hydrogen is added as a molecular weight regulator and / or to increase the activity.
  • the catalyst system can be fed neat to the polymerization system or inert components such as paraffins, oils or waxes can be added for better meterability.
  • an antistatic can also be metered into the polymerization system together with or separately from the catalyst system used.
  • the polymers represented by the catalyst system according to the invention (hereinafter also referred to as (co) polymers according to the invention) have a uniform grain morphology and have no fine grain proportions. No deposits or caking occur during the polymerization with the catalyst system according to the invention.
  • the (co) polymers according to the invention are both homo- and random copolymers of propylene.
  • Their molar mass M w (measured with gel permeation chromatography) is in the range from 100,000 to 1,000,000 g / mol and their M w / M n (measured with gel permeation chromatography) is in the range from 1.8 to 4.0, preferably 1.8 to 3.5.
  • Random copolymers of propylene contain monomers copolymerizable with propylene in minor amounts, for example C -C 8 -alk-1-enes such as, inter alia, ethylene, but-1-ene, pent-1-ene, hex-1-ene or 4 methyl-1-pentene. Two or more different comonomers can also be used; one then obtains, for example, random terpolymers.
  • Particularly suitable include homopolymers of propylene or copolymers of propylene with up to 50% by weight of other alk-1-enes polymerized in with up to 8 carbon atoms.
  • the copolymers of propylene are statistical copolymers or block or impact copolymers. If the copolymers of propylene have a statistical structure, they generally contain up to 50% by weight, preferably up to 15% by weight, particularly preferably up to 1% by weight, other alk-1-enes with up to 8 carbon atoms, in particular ethylene, but-1-en-4-methyl-1-pentene or a mixture of ethylene and but-1-ene, ethylene and 1-hexene or ethylene and 4-methyl-1-pentene. 5
  • copolymers according to the invention are furthermore block or impact copolymers of propylene, in which in the first stage one, e.g. inventive propylene homopolymer or an inventive random copolymer of propylene with 0.001 to
  • further C 4 -Cs alk-1-enes for example ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene
  • ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene may be polymerized.
  • propylene-ethylene copolymer optionally containing as further monomers ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene
  • 20 second stage copolymer produced in the end product has a proportion of 3 to 60% by weight.
  • Propylene homopolymers and copolymers according to the invention are characterized by a content of meso-configured dyads (measured by 25 13 C-NMR spectroscopy, see examples) of at least 90%, preferably of at least 95% and particularly preferably of at least 98%.
  • the random copolymers according to the invention have at least four, preferably at least six and particularly preferably at least 7.5 (intra-chain) region errors per polymer chain.
  • Random copolymers not according to the invention are produced using single-site catalysts (e.g. metallocene catalysts),
  • Random copolymers that are produced with single-site catalysts are distinguished, for example, by a number of properties compared to Ziegler-Natta-catalyzed copolymers with comparable comonomer incorporation.
  • single-site-catalyzed copolymers have a uniform comonomer distribution over their molecular weight spectrum. Such a distribution can e.g. be determined via a coupled GPC-IR measurement.
  • the comonomers are randomly distributed, while Ziegler-Natta-catalyzed copolymers tend to incorporate the comonomer in blocks even at low incorporation rates. It fluctuates only slightly if the fractions have a sufficiently large proportion (at least 10%) of the total polymer. With copolymers according to the invention, the incorporation fluctuates by a maximum of 10%, preferably a maximum of 5%, particularly preferably a maximum of 1.5% between the fractions with a sufficiently large proportion.
  • Ziegler-Natta-catalyzed have wider molar mass distributions ex reactor.
  • single-site-catalyzed copolymers are characterized by a low proportion of soluble components. If 10 mol% of ethylene is incorporated, the ether-soluble fraction is less than 2% by weight.
  • a combination of the above-mentioned features also means that the polymers according to the invention (homo- and copolymers) are eluted within a narrow temperature range in a TREF (measurement method see examples).
  • 80 to 100% by weight are eluted within a temperature interval which extends from 15 ° C. below to 15 ° C. above the temperature with the maximum elution (“peak temperature”).
  • the range preferably extends from 15 ° C. below to 10 ° C. above the peak temperature and particularly preferably from 10 ° C below to 10 ° C above the peak temperature.
  • the polymers 5 produced by the process according to the invention are suitable for producing tear-resistant, hard and rigid moldings such as fibers, filaments, injection molded parts, foils, plates or large hollow bodies (e.g. pipes).
  • the molded parts are particularly characterized by high toughness, even at temperatures below 20 ° C, in conjunction with high rigidity.
  • Shaped articles from the block polymers according to the invention are generally produced using the customary injection molding processes known to the person skilled in the art and have a novel combination of properties of rigidity, toughness and
  • the modulus of elasticity is generally in the range from 500 to 6000, preferably in the range from 20 800 to 2000, very particularly preferably in the range from 900 to 1400
  • the Charpy impact strength is at 25 23 ° C. at> 200 kj / m 2 and at -20 ° C. at> 20 kJ / m 2 , Preferably no break of the test specimen is registered at 23 ° C.
  • the injection molded articles according to the invention can also contain the usual 35 thermoplastic additives in the usual amounts.
  • Suitable additives are antistatic agents, lubricants such as fatty acid amides, for example erucic acid amide, stabilizers, fire retardants, neutralizing agents such as calcium stearate, pigments, dyes such as pigment dyes or liquid colors, carbon black, and also inorganic fillers such as talc, chalk, aluminum oxide, aluminum sulfate, Barium sulfate, calcium magnesium carbonate, silicon dioxide, titanium dioxide, glass fibers and organic fillers such as polyester, polystyrene, polyamide and halogenated organic polymers.
  • Preferred additives are also nucleating agents, such as talc, alkali metal, alkaline earth metal or aluminum salts of alkyl, aryl, arylalkyl or alkylaryl carboxylic acids, certain polymers, such as polyvinylcyclohexane or polycyclopentene, and also polyhydroxy compounds, such as sorbitol derivatives.
  • talc, alkali metal, alkaline earth metal or aluminum salts of alkyl, aryl, arylalkyl or alkylaryl carboxylic acids certain polymers, such as polyvinylcyclohexane or polycyclopentene, and also polyhydroxy compounds, such as sorbitol derivatives.
  • Talc, aluminum, alkali and alkaline earth salts of cyclic arylalkylcarboxylic acids and sorbitol derivatives are preferred. Sorbitol derivatives are particularly preferred.
  • the homopolymers and copolymers according to the invention are suitable for producing tear-resistant, hard and rigid moldings, fibers, filaments, injection molded parts, foils, plates or large hollow bodies (e.g. pipes).
  • block copolymers according to the invention are well suited for the production of moldings by means of injection molding and extrusion processes. In particular for the production of injection molded articles for various uses, as described below by way of example.
  • the block copolymers according to the invention are suitable for uses
  • dairy and food packaging in particular also for refrigerated and deep-freeze applications, such as yogurt cups, dessert cups, milk and milk product packaging such as cheese packaging, delicatessen cups, portion containers, menu trays, tubes, bottles, such as ketchup bottles, bottle caps, refrigeration and Freezer containers, such as ice cream containers;
  • cooling and deep-freezing applications such as drinking cups, dishes, bowls, containers for foodstuffs, in particular for the cooling and deep-freezing sector, such as cheese cans or sausage cans, microwave applications, catering, injection-blown containers, bottles, tubes, Waste container, filter housing, Hangers, vacuum jugs, baby bottles, lids for baby bottles, pacifier parts, cartridges, clips;
  • in the office supplies area such as storage boxes, sorting boxes, magazine boxes, waste paper baskets,
  • cream and toothpaste containers for example tubes or
  • Dosing dispenser ointment container, caps, bottles, tubes, tubes,
  • detergent sales packaging such as container boxes, bottles or tubes, dosing containers, dosing balls;
  • toothbrush holders such as toothbrush holders, cups, brush bodies, wet razor bodies, bathroom shelves, bathroom furniture, mirror cabinets, toilet seats and toilet lids, soap dispensers;
  • electrical appliance housings such as coffee machine housings, viewing windows for coffee machines or kettles, egg cooker covers, refrigerator and freezer interior parts such as cladding, vegetable compartments or storage baskets, bathroom scales, irons, lamp covers, electrical appliance housings e.g. B. Computer and monitor housing, tool housing;
  • toys such as toys or toy parts and their packaging, for example playing card packaging, toy storage containers;
  • the laboratory area such as measuring cups, measuring cylinders, laboratory bottles, for example for aggressive substances, buckets, quivers
  • motor vehicle sector such as covers for interior lighting, glass substitutes, polycarbonate or polystyrene substitutes, impact-resistant inner linings and outer linings;
  • garden supplies such as flower boxes, flower pots, watering cans, water containers, composters, buckets, irrigation systems, parts of garden tools.
  • Heteropental systems are displayed according to a rule by Ewen et al. , Metalorganic Catalysts for Synthesis and Polymerization, 1999, Springer-Verlag, 150-169.
  • the Grignard suspension cooled to room temperature, is added portionwise via a cannula to a suspension of 305 mg (mmol) copper [I] iodide and 137.6 g (mmol) 2-chlorobenzonitrile dissolved in 240 ml THF. Towards the end of the Grignard addition, the suspension is refluxed for 2 hours. A solution of 327 ml of water is added dropwise to the strongly stirred suspension. Then 218 ml of 37% hydrochloric acid are added in 20 minutes. The emulsion is stirred vigorously at 50 ° C. for 1 hour, after which the aqueous phase is separated from the organic phase.
  • the solvent is completely removed and the residue is then mixed with 50 ml of toluene.
  • the toluene is removed on a rotary evaporator, the remaining water being distilled off azeotropically.
  • the raw product is used for the next level. 205.5 g of crude product are isolated, which is used for the next stage without further purification.
  • the 2-isopropyl-4-phenyl-indene (2), 2-isopropyl-4 - (2-naphthyl) -indene (3), 2-isopropyl-4- (1-naphthyl) -indene (4) is used analogously, by coupling with the corresponding boronic acids as described in Example 3.
  • the NMR data of these compounds are noted in the table below.
  • the resulting reaction mixture is stirred at room temperature overnight.
  • the reaction solution is then poured into 100 ml of water and the organic phase is separated off.
  • the aqueous phase is extracted once with 50 ml of toluene and the combined organic phases are dried over magnesium sulfate.
  • the solvent is removed in an oil pump vacuum and 10.2 g (75%) of the desired ligand system are isolated.
  • Example 14 Preparation of dimethylsilanediyl (2-isopropyl-4- (1-naphthyl) -indene) (2-methyl-4- (4 'tert.butylphenyl) -indene)
  • the organic phase is washed with 100 ml of water and the combined aqueous phases are extracted twice with a total of 100 ml of toluene.
  • the combined organic phases are then dried over magnesium sulfate. After removal of the magnesium sulfate, the solvent is removed and the residue in an oil pump.
  • the organic phase is washed with 90 ml of water and the combined aqueous phases are extracted twice with a total of 100 ml of toluene.
  • the combined organic phases are then dried over magnesium sulfate. After the magnesium sulfate has been separated off, the solvent is removed and the residue is dried under an oil pump vacuum.
  • the desired dimethylsilanediyl (2-isopropyl-4-phenyl) -1-indene) (2-methyl-4- (4'-tert.-butylphenyl) -1-indene) is obtained in a yield of 25.9 g ( 85%) isolated.
  • Example 17 Preparation of dimethylsilanediyl (2-methyl-4- (1-naphthyl) -inden) (2-isopropyll-4- (4 'tert.butyl-phenyl) -inden)
  • Example 18 Preparation of dimethylsilanediyl (2-methyl-4- (4 'tert-butyl-phenyl) -indenyl) (2-isopropyl-4- (4' -tert. -Butyl-phenyl) -indenyl) zirconium dichloride
  • the orange precipitate is then separated off on a G3 frit and washed twice with 50 ml of THF and once with 70 ml of pentane. The residue is then dried in an oil pump vacuum. The complex is obtained in a yield of 23.5 g (50%).
  • Example 20 Preparation of dimethylsilanediyl (2-methyl-4- (4 'tert -butyl-phenyl) -indenyl) (2-isopropyl-4-phenyl-indenyl) zirconium dichloride
  • Example 21 Preparation of dimethylsilanediyl (2-methyl-4-phenyl) -1-indenyl) (2-isopropyl-4- (4'-tert-butylphenyl) -1-indenyl) zirconium dichloride
  • the resulting orange precipitate is then separated off on a G4 frit and washed twice with 60 ml of THF and once with 100 ml of pentane. The residue is then dried in an oil pump vacuum. The complex is obtained in a yield of 10.4 g (50%).
  • Pseudo-meso 7.8-7.0 (m, 15 H, arom-H), 3.22 (m, IH, CH-isopropyl), 2.41 (s, 3H, CH 3 ), 1.33 (s, 18H, tert-butyl), 1.49, 1.27 (each s, each 3H, Si-CH 3 ), 1.18 (m, 6H, isopropyl-CH 3 ).
  • Example 22 Preparation of dimethylsilanediyl (2-ethyl-4- (4 'tert.butyl-phenyl) -indenyl) (2-isopropyl 4-phenyl) -indenyl) zirconium dichloride
  • Pseudo-meso 7.7-6.7 (m, 14 H, arom- H), 3.27 (m, IH, CH-isopropyl), 2.6, 2.3 (per m, each IH, CH 2 ), 1.35 (each s, each 3H, Si-CH 3 ), 1.34 (s, 18H, tert-butyl), 1.25 (m, 6H, CH 3 -isopropyl), 0.93 (t, 3H, CH 3 ).
  • the precipitate is then separated off on a G3 frit and washed twice with 60 ml of THF and once with 80 ml of pentane. The residue is then dried in an oil pump vacuum. The complex is obtained in a yield of 8.8 g (40%).
  • Pseudo-meso 7.7-6.8 (m, 10 H, arom-H), 6.4-6.2 (m, IH, H-thiopentalen), 3.35 (m, IH, CH-isopropyl), 2.3 (m, 3H, CH 3 ), 1.35 (s, 9H, tert-butyl), 1.2 (s, 6H, Si-CH 3 ), 1.15 (m, 6H, isopropyl-CH 3 ).
  • Example 24 Preparation of dimethylsilanediyl (2-isopropyl-4- (4 'tert-butyl-phenyl) -indenyl) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
  • the precipitate is then separated off on a G4 frit and washed twice with 60 ml of THF.
  • the complex is recrystallized from a toluene-pentane mixture.
  • the residue is then dried in an oil pump vacuum.
  • the complex is obtained in a yield of 3.1 g (30%).
  • Pseudo-meso 8.0-6.9 (m, 12 H, arom- H),), 3.39 (m, IH, CH-isopropyl), 2.25 (s, 3H, CH 3 coincides with the rac form), 1.35 ( s, 9H, tert-butyl, coincides with the rac form), 1.37 (s, 6H, Si-CH 3 ), 1.24 (m, 6H, isopropyl-CH 3 ).
  • Example 25 Preparation of dimethylsilanediyl (2-methyl-4- (4 'tert-butyl-phenyl) -indenyl) (2-isopropyl 4- (1-naphthyl) -indenyl) zirconium dichloride
  • Pseudo-meso 7.9-7.07 (m, 17 H, arom-H), 3.37 (m, IH, CH-isopropyl), 2.50 (s, 3H, CH 3 ), 1.35 (each s, each 3H, Si-CH 3 ), 1.32 (s, 18H, tert-butyl, coincides with the rac form), 1.25 (m, 6H, CH 3 -isopropyl).
  • Example 26 Preparation of dimethylsilanediyl (2-isopropyl-4- (4 'tert-butyl-phenyl) -indenyl) (2-methyl 4- (1-naphthyl) -indenyl) zirconium dichloride
  • the mixture is allowed to warm to room temperature and stirred for 2 hours at this temperature.
  • the precipitate is then separated off using a G4 frit and washed twice with 50 ml THF and 70 ml pentane.
  • the residue is then dried in an oil pump vacuum.
  • the complex is obtained in a yield of 6.8 g (41%).
  • Pseudo-meso 7.9-7.05 (m, 17 H, arom-H), 3.35 (m, IH, CH-isopropyl), 2.48 (s, 3H, CH 3 ), 1.35 (each s, each 3H, Si-CH 3 ), 1.32 (s, 18H, tert-butyl, coincides with the rac form), 1.22 (m, 6H, CH 3 -isopropyl).
  • VZ viscosity number in cm 3 / g
  • M w molar mass weight average in g / mol
  • Mp. Melting point in ° C, determined according to ISO 3146 by differential
  • RI regio error in%
  • the 13 C-NMR measurement was carried out with broadband decoupling of the protons.
  • the values of the 2.1 insertions must be divided by two.
  • the given ratios of the signals of the 2, 1 insertions to the 1, 3 insertions are identical to the molar ratios.
  • both 2.1 and 1.3 insertions each generate a further signal which is in the integration range of the mr triad. Since the signals in the integration area of the mr triads can sometimes not be detected separately from the baseline, it is not possible to state the molar ratios directly. To calculate the molar ratios of the mm triads to the mr triads, the signal intensities of the regio-irregular insertions must first be subtracted from the given intensities of the mr triads.
  • the GPC was measured on a Waters 150C HT-GPC system. The results were calibrated with polystyrene. An interface model 300 from Lab Connections, Marlborough, MA (USA) was used for the coupling. The eluent is atomized in an vacuum chamber by an ultrasound signal and removed by heating and vacuum. The remaining polymer is continuously collected on a rotating germanium disc. This disc is then scanned by means of an optical module in an FTIR Spectometer Impact 40OD from Nicolet.
  • GPC eluent: trichlorobenzene
  • flow rate 1.1 ml / min
  • inject volume 150 ⁇ l
  • temperature 150 ° C.
  • Interface nozzle temperature: 110 ° C
  • flow rate 1.1 ml / min
  • disk heating 165 ° C
  • transfer line 145 ° C
  • FTIR Continuous spectra recording at 10 ° / min with Omnic series software: 270 spectra in 30 minutes (one spectrum every 8 seconds) with 16 scans each, detector: DTGS.
  • mol% PE 39.7 * ln [A (2922 cm- 1 ) + A (2850 cm- 1 ) / A (2953 cm-)] - 9.2
  • A denotes the peak heights of the signals at those in brackets specified wavenumbers.
  • a dry 16 dm 3 reactor which had been flushed first with nitrogen and then with propene, was liquid with 10 dm 3 .
  • the catalyst activity was 123 kg PP / (g MC xh) or 1.4 kg PP / (g Kat xh)
  • Example 27 The procedure of Example 27 was repeated with other metallocenes.
  • Example 27 The procedure of Example 27 was repeated with other catalysts.
  • the polymerization was carried out analogously to Example 27, but an additional 5 Ndm 3 of hydrogen were used in the polymerization.
  • the result was 3.2 kg of polypropylene powder.
  • the catalyst activity was 146 kg PP / (g MC xh) or 1.6 kg PP / (g Kat xh).
  • a dry 24 dm 3 reactor was flushed with propylene and with 12 dm 3 of liquid propylene, 150 g of ethylene (Examples 41 to 48) or 450 g of ethylene (Examples 49 to 56) and 22 cm 3 of a hexane triisobutylaluminum solution (8 mmol Al , 2 cm 3 of triisobutyl aluminum diluted with 20 cm 3 of hexane) and the reactor stirring set to 250 rpm.
  • 0.7 g of the supported catalyst prepared in Examples 27 to 34 were suspended in 25 cm 3 of a de-aromatized gasoline cut with a boiling range of 100 to 120 ° C. and the suspension was added to the reactor.
  • the reactor was heated to the polymerization temperature of 70 ° C. (7.5 ° C./min) and kept at this polymerization temperature for 1 h by cooling the reactor jacket. The polymerization was stopped by rapidly venting the excess monomers. The polymer was dried in vacuo.
  • the following table shows the polymer yield, catalyst activity and product data.
  • N, N-dimethylaniline 0.5 ml of N, N-dimethylaniline is added to a suspension of 2 g of SiO 2 (see Example 27) in 30 ml of toluene at room temperature. It is cooled to 0 C and 40 ml of a clear, light yellow solution (0.1 M based on Al) of bis (pentafluorophenylboroxy) methylalane in 95 ml of toluene are added dropwise via a dropping funnel. The mixture is allowed to warm to room temperature and stirred for 3 hours. The suspension is then filtered and washed with pentane. The residue is then dried to constant weight in an oil pump vacuum. The result is 3.96 g of a light purple-colored carrier material.
  • the polymerization was carried out analogously to Example 69, but only 0.4 g of cat were used and an additional 5 Ndm 3 of hydrogen were used in the polymerization. The result was 3.2 kg of polypropylene powder.
  • the catalyst activity was 8 kg PP / (g cat x h).
  • a dry 24 dm 3 reactor was flushed with propylene and pressurized with 0.5 bar of hydrogen.
  • the reactor was then filled with 12 dm 3 of liquid propylene and 22 cm 3 of a hexane triisobutyl aluminum solution (8 mmol Al, 2 cm 3 triisobutyl aluminum diluted with 20 cm 3 hexane) and the reactor stirring was set to 250 rpm.
  • 0.7 g of the supported catalyst prepared in Example 27 were suspended in 25 cm 3 of a dearomatized gasoline cut with a boiling range of 100 to 120 ° C. and the suspension was added to the reactor.
  • the reactor was heated to the polymerization temperature of 70 ° C. (7.5 ° C./min) and kept at this polymerization temperature for 1 h by cooling the reactor jacket.
  • Example 78 was repeated using a supported catalyst shown in Example 36.
  • Example 78 was repeated using a supported catalyst with dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride as the metallocene.
  • a block copolymer with the following properties was obtained:
  • Example 78 was repeated, but the reactor was only filled with 10 dm 3 of liquid propylene and the catalyst was metered in as a paste.
  • 20 g of the catalyst prepared in Example 27 were stirred into 100 ml of an oil (white oil Ondina G 33, from Guatemala Shell AG) / petroleum jelly (from Deutsche Shell AG) (4/1).
  • Example 78 was repeated, but the first polymerization step was carried out at 65 ° C. in the presence of 60 g of ethylene.
  • a block copolymer with the following properties was obtained:
  • Example 27 was repeated, but the reactor was let down to 18 bar before the second polymerization stage and then only 5 bar of ethylene was applied.
  • a low-whitening block copolymer was obtained with the following properties:
  • Examples 84 to 86 were repeated with a catalyst prepared from dimethylsilanediyl - 40 bis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride as metallocene. Polymer yield, metallocene activities and product data can be found in the table below.
  • a dry 24 dm 3 reactor was filled with 10 l of a dearomatized gasoline cut with a boiling range of 100 to 120 ° C. Then the gas space was flushed by pressing 2 bar propylene five times and releasing the pressure. After adding 2000 g of propylene, 300 g of ethylene and optionally 100 g of another monomer (see Table 3), 10 cm 3 of toluene methylaluminoxane solution (corresponding to 15 mmol of AI, molecular weight according to cryoscopic determination 1200 g / mol) were added. The reactor contents were heated to 60 ° C.
  • Examples 90 to 93 were repeated with 2.0 mg of dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride. Polymer yields, metallocene activities and product data can be found in the table below.
  • butyl-phenyl) indenyl) zirconium dichloride was added to a reaction vessel, the solution was stirred for 1 h and left to sit for a further 30 min. The solution is then fed to the pretreated carrier material with the drain closed. When the addition is complete, the drain is opened and the filtrate is drained. If nothing else runs out, the drain is closed, the filter cake is stirred for 15 minutes and left to rest for 1 hour. It is then pressed with 3 bar nitrogen pressure with the drain open. 15 l of isododecane are added to the remaining solid, the mixture is stirred for 15 min and filtered off. The washing step is repeated, and finally it is pressed dry with a nitrogen pressure of 3 bar. For use in the polymerization, the total amount of the catalyst is resuspended in 15 l of isododecane.
  • the propylene was introduced in gaseous form into the first polymerization reactor and polymerized at a mean residence time in accordance with Table 1 using the metallocene catalyst A (see above) at a pressure and temperatures in accordance with Table 1.
  • the dosage of the metallocene catalyst described was such that the transfer from the 1st to the 2nd polymerization reactor corresponds on average to the amounts of polymer shown in Table 1.
  • the metallocene catalyst was metered in with the fresh propylene added for pressure control. Triethylaluminum was also metered into the reactor (in the form of a 1 molar heptane solution, in an amount corresponding to Table 1).
  • the polymer was gradually removed from the reactor by briefly relaxing the reactor via a dip tube.
  • the propylene polymer formed in the first reactor was thereby introduced into the second reactor together with the catalyst and together with unreacted monomers.
  • a mixture of propylene and ethylene was polymerized in there at a total pressure, a temperature and an average residence time in accordance with Table 1.
  • the proportion of ethylene was the volume% indicated in Table 1, the ethylene concentration in the reaction gas being determined by gas chromatography.
  • the weight ratio between the propylene polymer (PP (I)) formed in the first reactor and the copolymer (EPR (II)) formed in the second reactor is shown in Table 1.
  • Iso-propanol in the form of a 0.5 molar heptane solution
  • the amount of isopropanol metered in was measured so that the weight ratio PP (I): EPR (II) according to Table 1 was maintained.
  • the dried polymer powders were mixed intimately with a standard additive mixture (additive with 0.05% by weight of Irganox 1010, 0.05% by weight of Irgafos 168, 0.1% by weight of calcium stearate and 0.2% by weight of Millad 3988). Extrusion was carried out on a twin-screw extruder ZSK 30 from Werner & Pfleiderer at a melt temperature of 250 ° C. and then pelletized in a granulator. The test specimens required for the application tests and their testing were produced in accordance with the standard regulations specified in Table 3.
  • Examples 103 to 109 Homopolymers and random copolymers of propylene and their properties Manufacture of catalysts
  • the volatile constituents are removed in an oil bath heated to 40 ° C on a vacuum line equipped with an oil pump until approximately 4 hours of constant weight is reached.
  • the residual content of volatile constituents is determined on a moisture analyzer from Mettler-Toledo and is 2.05%.
  • the solid is resuspended in 11 l of toluene and 291 g of diethylcyclohexylammonium tetrakis (pentafluorophenyl) borate are added to the suspension. Then heated to 80 ° C internal temperature and 30 min. stirred at this temperature. Then the complex rac-dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride is added give and stirred for a further 1.5 hours at 80 ° C. The catalyst is then dried at about 80 ° C. internal temperature in a vacuum (about 40 mbar).
  • a dry 16 dm 3 reactor which had first been flushed with nitrogen and then with propene, was filled with 10 dm 3 of liquid propene.
  • 8 cm 3 of 20% by weight triethylaluminum solution in Varsol (Witco) were added as scavengers and the mixture was stirred at 30 ° C. for 15 min.
  • a suspension of 1.5 g of the catalyst Al in 20 cm 3 of Exxsol was then added to the reactor, heated to the polymerization temperature of 65 ° C. and the polymerization system was kept at this temperature for 1 hour. The polymerization was stopped by degassing and the polymer obtained was dried in vacuo. The result was 2.05 kg of polypropylene powder.
  • GPC-IR spectroscopy The spectra are combined in such a way that one chromatographic minute corresponds to one spectrum (120 scans / spectrum).
  • a dry 16 dm 3 reactor which had been flushed first with nitrogen and then with ethylene, was filled with ethylene until a pressure increase of 500 Pa had occurred at 30 ° C. 10 l of liquid propene were then added and 8 cm 3 of 20% by weight triethylaluminum solution in Varsol (from Witco) were added as a scavenger, the mixture was stirred for 15 minutes and then heated to 65.degree. A suspension of 1.1 g of catalyst Al in heptane was then added to the reactor. Immediately afterwards, 110 mg of breathing 163 were added. The polymerization was stopped after 10 minutes by degassing and the polymer obtained was dried in vacuo. 22 g of polypropylene copolymer resulted.

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Abstract

L'invention concerne : un procédé de polymérisation d'oléfines, en particulier un procédé de copolymérisation de propylènes avec d'autres oléfines ; des métallocènes spécialement sélectionnés, en particulier ceux qui possèdent des substitutions différentes en position 2 et en position 4 sur le ligand indényle ; des systèmes de ligands ; des systèmes de catalyseurs hautement actifs ; de nouveaux copolymères de polypropylène. La polymérisation selon l'invention se fait en présence des métallocènes spécialement sélectionnés.
EP00988791A 1999-12-23 2000-12-13 Composition de metal de transition, systeme de ligand, systeme de catalyseur et son utilisation pour la polymerisation et la copolymerisation d'olefines Withdrawn EP1250365A2 (fr)

Priority Applications (3)

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EP05001434.9A EP1548023B1 (fr) 1999-12-23 2000-12-13 Composition de métal de transition, système de catalyseur et son utilisation pour la polymérisation et la copolymérisation d'oléfines
EP05001432A EP1548037A3 (fr) 1999-12-23 2000-12-13 Copolymères propylène-éthylène statistiques
EP05001433A EP1548022A3 (fr) 1999-12-23 2000-12-13 Composition de métal de transition, système de ligand, système de catalyseur et son utilisation pour la polymérisation et la copolymérisation d'oléfines

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DE1999162905 DE19962905A1 (de) 1999-12-23 1999-12-23 Übergangsmetallverbindung, Ligandensystem, Katalysatorsystem und seine Verwendung zur Polymerisation und Copolymerisation von Olefinen
DE19962905 1999-12-23
DE10044983 2000-09-11
DE10044983 2000-09-11
PCT/EP2000/012642 WO2001048034A2 (fr) 1999-12-23 2000-12-13 Composition de metal de transition, systeme de ligand, systeme de catalyseur et son utilisation pour la polymerisation et la copolymerisation d'olefines

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EP05001432A Division EP1548037A3 (fr) 1999-12-23 2000-12-13 Copolymères propylène-éthylène statistiques
EP05001433A Division EP1548022A3 (fr) 1999-12-23 2000-12-13 Composition de métal de transition, système de ligand, système de catalyseur et son utilisation pour la polymérisation et la copolymérisation d'oléfines

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EP00988791A Withdrawn EP1250365A2 (fr) 1999-12-23 2000-12-13 Composition de metal de transition, systeme de ligand, systeme de catalyseur et son utilisation pour la polymerisation et la copolymerisation d'olefines
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009054833A2 (fr) 2007-10-25 2009-04-30 Novolen Technology Holdings, C.V. Composés métallocènes, catalyseurs les comportant, procédé de fabrication d'un polymère d'oléfine à l'aide des catalyseurs et homopolymères et copolymères d'oléfines
US8299287B2 (en) 2007-10-25 2012-10-30 Lammus Novolen Technology GmbH Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
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US6376413B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376410B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6380122B1 (en) 2000-06-30 2002-04-30 Exxonmobil Chemical Patents Inc. Metallocene compositions
US6376412B1 (en) 2000-06-30 2002-04-23 Exxonmobil Chemical Patents Inc. Metallocene compositions
WO2002100908A1 (fr) * 2001-06-12 2002-12-19 Basell Polyolefine Gmbh Procede de polymerisation de 1-butene
JP4332029B2 (ja) * 2001-06-12 2009-09-16 バーゼル・ポリオレフィン・ゲーエムベーハー １−ブテンの重合方法
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DE60213452T2 (de) 2001-11-30 2007-08-23 Basell Polyolefine Gmbh Metallocene und verfahren zur herstellung von propylenpolymeren
BR0311862B1 (pt) * 2002-06-12 2013-08-06 composição copolimérica de propileno, processo para preparar composições copoliméricas de propileno, uso da composição copolimérica de propileno,fibras, filmes, ou artigos moldados.
EP1511803B1 (fr) * 2002-06-12 2007-09-19 Basell Polyolefine GmbH Compositions copolymeres de propylene presentant une bonne resistance aux chocs a basse temperature et une transparence elevee
US20030236365A1 (en) * 2002-06-24 2003-12-25 Fina Technology, Inc. Polyolefin production with a high performance support for a metallocene catalyst system
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US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
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US20060252637A1 (en) * 2003-05-28 2006-11-09 Basell Polyolefine Gmbh Bisindenyl zirconium complexes for use in the polymerization of olefins
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EP1871832B1 (fr) * 2005-04-21 2012-06-13 Basell Poliolefine Italia S.r.l. Films de polymeres du propylene orientes biaxialement
EP1877453A1 (fr) * 2005-05-03 2008-01-16 Basell Polyolefine GmbH Procede de polymerisation d'alpha-olefines
JP2008540752A (ja) 2005-05-11 2008-11-20 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ ポリオレフィンブレンドを製造するための重合方法
US7232869B2 (en) * 2005-05-17 2007-06-19 Novolen Technology Holdings, C.V. Catalyst composition for olefin polymerization
BRPI0613343A2 (pt) * 2005-06-13 2011-01-04 Basell Polyolefine Gmbh processo para a copolimerização de propileno
DE602006014709D1 (de) * 2005-10-21 2010-07-15 Basell Polyolefine Gmbh Propylenpolymere
US20090118451A1 (en) * 2005-10-21 2009-05-07 Basell Polyolefine Gmbh Polypropylene Random Copolymers Having High Melt Flow Rates for Injection Molding and Melt Blown Applications
JP5379479B2 (ja) * 2005-10-21 2013-12-25 バーゼル・ポリオレフィン・ゲーエムベーハー 射出成形用のポリプロピレン
DE102005061326A1 (de) * 2005-12-20 2007-06-21 Basell Polyolefine Gmbh Verfahren zur Herstellung von Metallocenen aus recycelten, substituierten Cyclopentadienylderivaten
US7947348B2 (en) 2005-12-20 2011-05-24 Basell Poliolefine Italia, s.r.l. Polypropylene compositions for stretched articles
US20090017710A1 (en) * 2006-02-02 2009-01-15 Basell Polyolefine Gmbh Propylene Melt Blown Resins, Propylene Melt Blown Resin Fibers and Non-Woven Fabric Made From the Same, and Methods of Making the Same
EP1847552A1 (fr) * 2006-04-18 2007-10-24 Borealis Technology Oy Système catalytique
EP1847555A1 (fr) * 2006-04-18 2007-10-24 Borealis Technology Oy Polypropylène à ramifications multiples
EP1847551A1 (fr) 2006-04-18 2007-10-24 Borealis Technology Oy Procédé pour la préparation de polypropylène
DE102006020486A1 (de) 2006-04-28 2007-10-31 Basell Polyolefine Gmbh Geträgerte Metallalkylverbindung und Verfahren zur Polymerisation von Olefinen in deren Gegenwart
JP2008000906A (ja) * 2006-06-20 2008-01-10 Moriyama Kasei Kk 綴じ穴付袋状ファイル
ATE421760T1 (de) 2006-07-10 2009-02-15 Borealis Tech Oy Elektrischer isolierfilm
ATE487755T1 (de) 2006-07-10 2010-11-15 Borealis Tech Oy Biaxial orientierte polypropylenfolie
EP1881507B1 (fr) * 2006-07-10 2009-09-02 Borealis Technology Oy Cables en nappé a base de polypropylene presentant une meilleure résistance au claquage diélectrique
DE102006033102A1 (de) * 2006-07-14 2008-01-24 Basell Polyolefine Gmbh Behältnisse aus Polypropylen mit Barriereschicht zur Verpackung, Aufbewahrung und Konservierung von Lebensmitteln
DE602006008470D1 (de) 2006-08-25 2009-09-24 Borealis Tech Oy Geblasene Polypropylenfolie
EP1892264A1 (fr) * 2006-08-25 2008-02-27 Borealis Technology Oy Substrat couche par extrusion
EP1900764B1 (fr) 2006-08-25 2009-04-01 Borealis Technology Oy Mousse de polypropylène
EP1903579B1 (fr) 2006-09-25 2010-03-24 Borealis Technology Oy Câble coaxial
ATE424424T1 (de) 2006-12-28 2009-03-15 Borealis Tech Oy Verfahren zur herstellung von verzweigtem polypropylen
EP1990353B1 (fr) 2007-05-08 2009-08-05 Borealis Technology Oy Film à isolement électrique
US8399536B2 (en) 2007-06-29 2013-03-19 Basell Poliolefine Italia, s.r.l. Irradiated polyolefin composition comprising a non-phenolic stabilizer
ATE547439T1 (de) * 2007-10-25 2012-03-15 Lummus Novolen Technology Gmbh Racemoselektive synthese von ansa-metallocen- verbindungen, ansa-metallocen-verbindungen, diese enthaltende katalysatoren, verfahren zur herstellung eines olefinpolymers durch verwendung der katalysatoren und olefinhomopolymere und - copolymere
EP2363433B1 (fr) 2007-12-17 2018-02-07 Borealis Technology OY Polypropylène hétérophasique doté de propriétés de grande aptitude à l'écoulement et une résistance aux chocs à basse température
WO2009077115A1 (fr) 2007-12-18 2009-06-25 Basell Polyolefine Gmbh Procédé de préparation de composés de métaux de transition pour la polymérisation d'oléfines
ATE457323T1 (de) 2007-12-18 2010-02-15 Borealis Tech Oy Heterophasisches polypropylen mit hoher schlagfestigkeit
JP5466826B2 (ja) * 2008-02-08 2014-04-09 日本ポリプロ株式会社 プロピレン／エチレン−αオレフィン系ブロック共重合体の製造方法
EP2113591A1 (fr) * 2008-04-29 2009-11-04 Total Petrochemicals Research Feluy Fibres et non tissés dotés de propriétés mécaniques et de liaison améliorées
EP2113541A1 (fr) 2008-04-28 2009-11-04 Borealis AG Composition de polymère en propylène adhésive adaptée à l'extrusion de revêtement de substrats papiers
EP2133389A1 (fr) 2008-06-12 2009-12-16 Borealis AG Composition de polypropylène
US8580902B2 (en) 2008-08-01 2013-11-12 Exxonmobil Chemical Patents Inc. Catalyst system, process for olefin polymerization, and polymer compositions produced therefrom
SG195587A1 (en) 2008-08-01 2013-12-30 Exxonmobil Chem Patents Inc Catalyst system and process for olefin polymerization
JP5409294B2 (ja) 2008-12-17 2014-02-05 日本ポリプロ株式会社 メタロセン錯体およびオレフィンの重合方法
US7935740B2 (en) 2008-12-30 2011-05-03 Basell Poliolefine Italia S.R.L. Process for producing high melt strength polypropylene
EP2384343A1 (fr) * 2008-12-31 2011-11-09 Lummus Novolen Technology Gmbh Nouveaux composés de métallocène, catalyseurs comprenant ceux-ci, procédé pour produire un polymère d'oléfine par utilisation des catalyseurs, et homo- et copolymères d'oléfine
US20120028866A1 (en) 2010-07-28 2012-02-02 Sudhin Datta Viscosity Modifiers Comprising Blends of Ethylene-Based Copolymers
US8378042B2 (en) 2009-04-28 2013-02-19 Exxonmobil Chemical Patents Inc. Finishing process for amorphous polymers
EP2480707B1 (fr) 2009-09-21 2014-03-05 Basell Poliolefine Italia S.r.l. Filament polymère
EP2316882A1 (fr) 2009-10-29 2011-05-04 Borealis AG Résine de propylène hétérophase.
PL2319885T3 (pl) 2009-10-29 2012-05-31 Borealis Ag Heterofazowa żywica polipropylenowa z rozgałęzieniem długołańcuchowym
EP2325248B1 (fr) 2009-11-16 2012-05-16 Borealis AG Fibres de fusion-soufflage de compositions de polypropylène
WO2011061087A1 (fr) 2009-11-17 2011-05-26 Basell Poliolefine Italia S.R.L. Compositions de polyoléfine souple présentant une aptitude à la transformation améliorée
CN106947166A (zh) 2009-11-24 2017-07-14 巴塞尔聚烯烃意大利有限责任公司 具有改善密封能力的聚烯烃组合物
EP2330136B1 (fr) 2009-12-07 2013-08-28 Borealis AG Procédé de préparation d'un système solide catalyseur de métallocène et son utilisation pour la polymérisation d'oléfines
EP2341088B1 (fr) 2009-12-30 2012-06-20 Borealis AG BOPP avec morphologie de film homogène
EP2341086A1 (fr) 2009-12-30 2011-07-06 Borealis AG Film BOPP
EP2341087B1 (fr) 2009-12-30 2014-04-09 Borealis AG Nouvelle manière de produire un grade de polypropylène dans un processus séquentiel
WO2011090859A1 (fr) 2010-01-22 2011-07-28 Exxonmobil Chemical Patents Inc. Copolymères d'éthylène, leurs procédés de production et leur utilisation
RU2541470C9 (ru) 2010-04-21 2015-04-20 Бореалис Аг Композиция сополимера пропилена/1-гексена с низкой температурой тепловой сварки
ES2385142T3 (es) 2010-04-21 2012-07-18 Borealis Ag Composición de copolímero o propileno/1-hexeno con ventana de sellado amplia
EP2386584A1 (fr) 2010-05-11 2011-11-16 Borealis AG Composition de polypropylène adaptée au revêtement par extrusion
EP2402376A1 (fr) 2010-06-29 2012-01-04 Borealis AG Procédé de production d'un catalyseur prépolymérisé, ledit catalyseur prépolymérisé et son utilisation pour produire un polymère
EP2601332B1 (fr) 2010-08-02 2015-12-16 Borealis AG Milieux ayant subi une fusion soufflage pour la filtration de l'air
EP2415791B1 (fr) 2010-08-06 2012-11-21 Borealis AG Film BOPP à résistance élevée contre la panne CA
EP2418237A1 (fr) 2010-08-12 2012-02-15 Borealis AG Film de polypropylène facile à déchirer sans entaille
EP2603548A1 (fr) 2010-08-12 2013-06-19 Borealis AG Film de polypropylène facile à déchirer sans entaille
EP2426171A1 (fr) 2010-08-30 2012-03-07 Borealis AG Polypropylène hétérophasique avec des propriétés mécaniques améliorées et à grande aptitude à l'écoulement
KR101164962B1 (ko) * 2010-09-20 2012-07-12 에스케이이노베이션 주식회사 위생성이 우수한 에틸렌 공중합체 및 이의 제조방법
EP2433982B1 (fr) 2010-09-28 2014-12-03 Borealis AG Composition avec une facteur de dissipation tan "delta" basse
EP2623522B1 (fr) * 2010-09-29 2018-08-29 LG Chem, Ltd. Procédé de préparation d'un catalyseur métallocène hybride supporté
WO2012049132A1 (fr) 2010-10-15 2012-04-19 Basell Poliolefine Italia S.R.L. Filament polymère
EP2632689B2 (fr) 2010-10-26 2022-03-23 Basell Poliolefine Italia S.r.l. Procédé de production de conteneurs en polyoléfine moulés par injection- étirage-soufflage
CN103339158B (zh) * 2010-12-01 2017-02-22 道达尔研究技术弗吕公司 包含丙烯无规共聚物的帽和封闭件及其制造方法
JP2014500371A (ja) 2010-12-21 2014-01-09 バーゼル・ポリオレフィン・ゲーエムベーハー 高弾性高透明性ポリプロピレン組成物
US9273201B2 (en) 2011-01-03 2016-03-01 Borealis Ag Sealing material of polypropylene with high melting temperature
CN103298874B (zh) 2011-01-03 2016-03-09 博里利斯股份公司 具有改进的光学性能的聚丙烯密封材料
US9029478B2 (en) 2011-02-07 2015-05-12 Equistar Chemicals, Lp High clarity polyethylene films
EP2487203B2 (fr) 2011-02-14 2020-11-25 Borealis AG Copolymère de propylène scellant
EP2492293B1 (fr) 2011-02-28 2017-09-20 Borealis AG Composition de polypropylène adaptée au revêtement par extrusion
EP2495264B1 (fr) 2011-03-04 2013-05-08 Borealis AG Article automobile extérieur avec défaillance de peignabilité réduite
US9643900B2 (en) 2011-03-25 2017-05-09 Dow Global Technologies Llc Hyperbranched ethylene-based oils and greases
EP2520425B1 (fr) 2011-05-02 2017-11-08 Borealis AG Polypropylène pour mousse et mousse de polypropylène
EP2535372B1 (fr) 2011-06-15 2016-09-14 Borealis AG Mélange en réacteur in situ d'un polypropylène nucléé catalysé par Ziegler-Natta et d'un polypropylène catalysé par métallocène
EP2540499B1 (fr) 2011-06-27 2014-02-26 Borealis AG Film polymère multicouche biaxialement orienté
ES2478020T3 (es) 2011-06-27 2014-07-18 Borealis Ag Película soplada multi-capa
EP2540497B1 (fr) 2011-06-27 2014-08-06 Borealis AG Film coulé multicouche
KR101966085B1 (ko) 2011-07-08 2019-04-05 보레알리스 아게 촉매
EP2562215B1 (fr) 2011-08-26 2016-03-30 Borealis AG Mélange de polypropylène pour conduits
EP2573091A1 (fr) 2011-09-23 2013-03-27 Lummus Novolen Technology Gmbh Procédé de recyclage de ligand libre provenant de leurs complexes de métallocènes correspondants
EP2586824B1 (fr) 2011-10-31 2016-09-14 Borealis AG Mélange de polypropylène doté d'un équilibre amélioré entre la température d'auto-inflammation et le point de fusion
US9012578B2 (en) 2012-04-19 2015-04-21 Exxonmobil Chemical Patents Inc. Blocky ethylene propylene copolymers and methods for making them
EP2914638A4 (fr) 2012-10-31 2016-07-27 Exxonmobil Chem Patents Inc Compositions à base de copolymère de propylène et leurs procédés de production
JP6176015B2 (ja) 2012-11-01 2017-08-09 日本ポリプロ株式会社 メタロセン錯体およびオレフィンの重合方法
EP2746336B1 (fr) 2012-12-20 2017-04-12 Borealis AG Mélange de polypropylène pour conduits sous pression
ES2645256T3 (es) 2012-12-21 2017-12-04 Borealis Ag Catalizadores
EP2746301B1 (fr) * 2012-12-21 2018-05-30 Borealis AG Catalyseur
US20150329653A1 (en) 2012-12-21 2015-11-19 Borealis Ag Catalyst
JP5710035B2 (ja) 2013-02-27 2015-04-30 日本ポリエチレン株式会社 メタロセン化合物およびオレフィン重合体の製造方法
JP5695687B2 (ja) 2013-03-05 2015-04-08 日本ポリエチレン株式会社 エチレン／α−オレフィン共重合体の製造方法
EP2978782B2 (fr) 2013-03-26 2020-11-18 Borealis AG Copolymère de propylène avec des propriétés de résistance aux chocs élevée
WO2014169017A1 (fr) * 2013-04-11 2014-10-16 Exxonmobil Chemical Patents Inc. Procédé de fabrication de polyoléfines à l'aide de catalyseurs de polymérisation métallocène et copolymères obtenus par ce procédé
KR101631702B1 (ko) * 2013-05-10 2016-06-17 주식회사 엘지화학 올레핀 중합용 촉매 및 이를 이용한 폴리올레핀의 제조방법
CA2915067C (fr) 2013-06-28 2021-08-03 Dow Global Technologies Llc Oligomeres a base d'ethylene hyper-ramifies
EP2986586B1 (fr) 2013-06-28 2018-08-08 Dow Global Technologies LLC Processus de préparation d'un composé hydrophobe, ses dérivés en tant que surfactants and leurs utilisations en tant que telles.
WO2014209712A1 (fr) 2013-06-28 2014-12-31 Dow Global Technologies Llc Procédé pour la préparation de polyoléfines ramifiées pour des applications comme lubrifiants
US9458260B2 (en) 2013-07-17 2016-10-04 Exxonmobil Chemical Patents Inc. Process using substituted metallocene catalysts and products therefrom
EP3022234B1 (fr) 2013-07-17 2018-12-26 ExxonMobil Chemical Patents Inc. Catalyseurs de métallocènes substitués
US9938364B2 (en) 2013-07-17 2018-04-10 Exxonmobil Chemical Patents Inc. Substituted metallocene catalysts
EP3033389B1 (fr) 2013-08-14 2017-10-11 Borealis AG Composition de propylène présentant une meilleure résistance aux chocs à basse température
BR112016002682A8 (pt) 2013-08-21 2020-01-28 Borealis Ag composição de poliolefina de alto fluxo com alta rigidez e tenacidade
JP6190961B2 (ja) 2013-08-21 2017-08-30 ボレアリス・アクチェンゲゼルシャフトＢｏｒｅａｌｉｓ Ａｇ 高い剛性および靭性を有する高流動ポリオレフィン組成物
ES2587781T3 (es) 2013-09-27 2016-10-26 Borealis Ag Películas adecuadas para procesamiento BOPP de polímeros con altos XS y alta Tm
EP2860031B1 (fr) 2013-10-11 2016-03-30 Borealis AG Film orienté dans le sens machine pour étiquettes
CN105612188B (zh) 2013-10-24 2018-09-28 北欧化工公司 具有高含量的区域错误和高分子量的低熔点pp均聚物
PL2865713T3 (pl) 2013-10-24 2016-10-31 Wyrób formowany z rozdmuchiwaniem na bazie dwumodalnego bezładnego kopolimeru
CN105722869B (zh) 2013-10-29 2017-09-12 北欧化工公司 具有高聚合活性的固体单点催化剂
KR101682342B1 (ko) 2013-11-22 2016-12-05 보레알리스 아게 고 용융 유동을 갖는 저 배출 프로필렌 단독중합체
BR112016011829B1 (pt) 2013-12-04 2022-01-18 Borealis Ag Composição de polipropileno, fibra e trama soprada em fusão, artigo e uso da composição de polipropileno
CN104448069B (zh) * 2013-12-06 2017-05-03 中国石油化工股份有限公司 固体催化剂悬浮液、丙烯聚合固体催化剂组分的分散方法及其应用和丙烯聚合的方法
PL2886563T3 (pl) 2013-12-18 2017-09-29 Borealis Ag Wyrób formowany z rozdmuchiwaniem o dobrych właściwościach mechanicznych i optycznych
JP6203405B2 (ja) 2013-12-18 2017-09-27 ボレアリス エージー 剛性／靭性バランスが改良されたｂｏｐｐフィルム
US10227427B2 (en) 2014-01-17 2019-03-12 Borealis Ag Process for preparing propylene/1-butene copolymers
US10100185B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft copolymers with high impact strength
JP6474417B2 (ja) 2014-02-06 2019-02-27 ボレアリス エージー 軟質及び透明衝撃コポリマー
EP2907841A1 (fr) 2014-02-14 2015-08-19 Borealis AG Composition de polypropylène
ES2659640T3 (es) 2014-04-04 2018-03-16 Borealis Ag Copolímero heterofásico de propileno con pocas sustancias extraíbles
EP2947118B1 (fr) 2014-05-20 2017-11-29 Borealis AG Composition de polypropylène pour des applications d'intérieur d'automobile
EP2995631A1 (fr) 2014-09-12 2016-03-16 Borealis AG Procédé de production de copolymères greffés à un squelette de polyoléfine
EP3015503A1 (fr) 2014-10-27 2016-05-04 Borealis AG Polypropylène hétérophasique avec un équilibre amélioré en termes de rigidité/impact
EP3015504A1 (fr) 2014-10-27 2016-05-04 Borealis AG Polypropylène hétérophasique présentant une répartition de rigidité et une résistance à l'impact améliorées en cas de perforation
EP3302918B1 (fr) 2015-05-26 2019-05-22 Basell Poliolefine Italia S.r.l. Joints de polyoléfine destinés à des fermetures
US10329360B2 (en) 2015-06-05 2019-06-25 Exxonmobil Chemical Patents Inc. Catalyst system comprising supported alumoxane and unsupported alumoxane particles
EP3303422B1 (fr) 2015-06-05 2021-03-17 ExxonMobil Chemical Patents Inc. Production de polymères hétérophasiques en phase gazeuse ou en suspension
US10294316B2 (en) 2015-06-05 2019-05-21 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
CN107690441A (zh) 2015-06-05 2018-02-13 埃克森美孚化学专利公司 聚合物在气相或淤浆相中的单反应器制备
WO2016196331A1 (fr) 2015-06-05 2016-12-08 Exxonmobil Chemical Patents Inc. Systèmes de catalyseurs métallocènes supportés pour polymérisation
US9809664B2 (en) 2015-06-05 2017-11-07 Exxonmobil Chemical Patents Inc. Bimodal propylene polymers and sequential polymerization
US10280235B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers
US10280233B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst systems and methods of making and using the same
CN106632781B (zh) * 2015-10-29 2020-05-12 中国石油化工股份有限公司 具有支化结构的乙烯/丙烯共聚物的制备方法和该共聚物
PL3805674T3 (pl) * 2015-11-25 2022-08-16 Electrolux Appliances Aktiebolag Sposób wytwarzania wykładziny urządzenia chłodniczego
US10883197B2 (en) 2016-01-12 2021-01-05 Chevron Phillips Chemical Company Lp High melt flow polypropylene homopolymers for fiber applications
EP3241611B1 (fr) 2016-05-02 2020-03-04 Borealis AG Procédé d'alimentation d'un catalyseur de polymérisation
DK3255189T3 (en) 2016-06-06 2018-10-29 Borealis Ag Meltblown tissue with good water barrier properties
KR102301007B1 (ko) 2016-06-23 2021-09-10 보레알리스 아게 촉매 비활성화 방법
WO2018091653A1 (fr) 2016-11-18 2018-05-24 Borealis Ag Catalyseur
US11208510B2 (en) * 2017-01-13 2021-12-28 Total Research & Technology Feluy High purity polypropylenes and polypropylene compositions for molding
EP3673013B1 (fr) 2017-08-21 2023-05-03 Borealis AG Composition de polypropylène présentant un meilleur comportement de percussion et optique
KR102375854B1 (ko) 2017-11-28 2022-03-17 주식회사 엘지화학 폴리프로필렌 및 그 제조방법
CN111757896B (zh) 2017-12-21 2023-10-13 博里利斯股份公司 制备固体催化剂的方法
KR102412130B1 (ko) 2017-12-26 2022-06-23 주식회사 엘지화학 담지 메탈로센 촉매의 제조방법 및 이로부터 제조된 촉매를 이용하는 폴리프로필렌의 제조방법
EP4017887A4 (fr) 2019-08-22 2023-01-18 ExxonMobil Chemical Patents Inc. Homopolymères et copolymères de propylène isotactique produits avec des catalyseurs métallocènes symétriques en c1
US11472828B2 (en) 2019-10-11 2022-10-18 Exxonmobil Chemical Patents Inc. Indacene based metallocene catalysts useful in the production of propylene polymers
JP2023501982A (ja) 2019-10-30 2023-01-20 中国石油化工股▲ふん▼有限公司 メタロセン化合物及びその製造方法並びに適用
WO2021233875A1 (fr) 2020-05-22 2021-11-25 Basell Poliolefine Italia S.R.L. Composition de polyoléfines souples et à charge élevée
EP4155327A4 (fr) * 2020-09-08 2024-01-03 Lg Chem, Ltd. Résine de polypropylène de type poudre et son procédé de préparation
EP4247825A1 (fr) 2020-11-23 2023-09-27 ExxonMobil Chemical Patents Inc. Polypropylène métallocène préparé à l'aide de supports exempts de solvant aromatique
CN116670228A (zh) 2020-12-15 2023-08-29 巴塞尔聚烯烃意大利有限公司 具有高透明度的聚烯烃组合物
EP4444944A1 (fr) 2021-12-10 2024-10-16 Basell Poliolefine Italia S.r.l. Filament de polyoléfine
WO2023104697A1 (fr) 2021-12-10 2023-06-15 Basell Poliolefine Italia S.R.L. Filament de polyoléfine
CN114989519B (zh) * 2022-06-09 2023-08-25 重庆理工大学 一种环烯烃聚合物在长余辉材料上的应用
CN116162185B (zh) * 2023-01-04 2024-06-25 万华化学集团股份有限公司 一种茂金属催化剂和制备方法及其在烯烃聚合中的应用

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA844157B (en) 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control
US4752597A (en) * 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
DE3726067A1 (de) * 1987-08-06 1989-02-16 Hoechst Ag Verfahren zur herstellung von 1-olefinpolymeren
DE3742934A1 (de) 1987-12-18 1989-06-29 Hoechst Ag Verfahren zur herstellung einer chiralen, stereorigiden metallocen-verbindung
US5017714A (en) * 1988-03-21 1991-05-21 Exxon Chemical Patents Inc. Silicon-bridged transition metal compounds
NZ235032A (en) 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
EP0537686B1 (fr) 1991-10-15 2005-01-12 Basell Polyolefine GmbH Procédé de préparation d'un polymère oléfinique à l'aide de métallocènes ayant des ligands indényl substituées d'une manière spécifique
TW294669B (fr) * 1992-06-27 1997-01-01 Hoechst Ag
US5449650A (en) 1992-12-08 1995-09-12 Mitsubishi Petrochemical Company Limited Catalyst components for polymerization of olefins and use thereof
DE4325824A1 (de) 1993-07-31 1995-02-02 Basf Ag Verfahren zur Herstellung von Homopolymerisaten des Ethylens oder Copolymerisaten des Ethylens
FI945958A (fi) 1993-12-21 1995-06-22 Hoechst Ag Menetelmä polyolefiinien valmistamiseksi
DE4344689A1 (de) 1993-12-27 1995-06-29 Hoechst Ag Metallocenverbindung
DE4406109A1 (de) * 1994-02-25 1995-08-31 Witco Gmbh Verfahren zur Herstellung von verbrückten stereorigiden Metallocenen
US5730985A (en) * 1994-06-13 1998-03-24 Governing Council Of The University Of Toronto Immunogens for the production of cocaine-hydrolyzing catalytic antibodies
TW401445B (en) * 1995-07-13 2000-08-11 Mitsui Petrochemical Ind Polyamide resin composition
ATE245665T1 (de) * 1995-09-28 2003-08-15 Basell Polyolefine Gmbh Geträgertes katalysatorsystem, verfahren zu seiner herstellung und seine verwendung zur polymerisation von olefinen
DE19606167A1 (de) 1996-02-20 1997-08-21 Basf Ag Geträgerte Katalysatorsysteme
US6121182A (en) * 1996-04-22 2000-09-19 Japan Polyolafins Co., Ltd. Polyolefin production catalyst and method of preparing polyolefins
DE19622207A1 (de) 1996-06-03 1997-12-04 Hoechst Ag Chemische Verbindung
EP0824112B1 (fr) 1996-08-13 2006-05-10 Basell Polyolefine GmbH Composé chimique supporté
ES2160289T3 (es) * 1996-08-13 2001-11-01 Basell Polyolefine Gmbh Sistema catalizador soportado, un procedimiento para su obtencion y su empleo para la polimerizacion de olefinas.
DE19757563A1 (de) * 1997-03-07 1999-07-08 Targor Gmbh Geträgertes Katalysatorsystem, Verfahren zur Herstellung und seine Verwendung zur Polymerisation von Olefinen
KR100624632B1 (ko) 1997-03-07 2006-09-15 타고르 게엠베하 메탈로센 및 그의 제조 방법
DE19733017A1 (de) 1997-07-31 1999-02-04 Hoechst Ag Chemische Verbindung
TW482770B (en) * 1997-08-15 2002-04-11 Chisso Corp Propylene/ethylene random copolymer, molding material, and molded article
DE69823969T2 (de) 1997-12-22 2005-05-12 Mitsui Chemicals, Inc. Katalysatorbestandteil, Katalysator und Verfahren zur Polymerisation von äthylenisch ungesättigten Monomeren
US6272841B2 (en) * 1998-01-23 2001-08-14 Mitsubishi Heavy Industries, Ltd. Combined cycle power plant
DE19804970A1 (de) 1998-02-07 1999-08-12 Aventis Res & Tech Gmbh & Co Katalysatorsystem
DE19806918A1 (de) * 1998-02-19 1999-08-26 Aventis Res & Tech Gmbh & Co Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE19813657A1 (de) 1998-03-27 1999-09-30 Aventis Res & Tech Gmbh & Co Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE19903306A1 (de) * 1999-01-28 2000-08-03 Targor Gmbh Organometallverbindung, Katalysatorsystem enthaltend diese Organometallverbindung und seine Verwendung
IT1315263B1 (it) * 1999-12-21 2003-02-03 Bracco Spa Composti chelanti,loro chelati con ioni metallici paramagnetici, loropreparazione ed uso
RU2002120467A (ru) * 1999-12-21 2004-01-10 Базель Полиолефин Гмбх (De) Частично кристаллическая пропилен-полимерная композиция для получения биаксиально вытянутых полипропиленовых пленок
DE10028432A1 (de) * 2000-06-13 2001-12-20 Basell Polyolefine Gmbh Auf calciniertes Hydrotalcit geträgerter Katalysatorfeststoff zur Olefinpolymerisation
KR100557640B1 (ko) * 2004-01-09 2006-03-10 주식회사 엘지화학 신규한 헤테로폴리산 촉매 및 그의 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0148034A2 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009054833A2 (fr) 2007-10-25 2009-04-30 Novolen Technology Holdings, C.V. Composés métallocènes, catalyseurs les comportant, procédé de fabrication d'un polymère d'oléfine à l'aide des catalyseurs et homopolymères et copolymères d'oléfines
US8299287B2 (en) 2007-10-25 2012-10-30 Lammus Novolen Technology GmbH Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
US8507706B2 (en) 2007-10-25 2013-08-13 Lummus Novolen Technology Gmbh Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
WO2015009472A1 (fr) 2013-07-17 2015-01-22 Exxonmobil Chemcal Patents Inc. Métallocènes et compositions catalytiques dérivées de ceux-ci
WO2015009473A1 (fr) 2013-07-17 2015-01-22 Exxonmobil Chemical Patents Inc. Catalyseurs métallocènes à substitution cyclopropyle
WO2015009471A1 (fr) 2013-07-17 2015-01-22 Exxonmobil Chemical Patents Inc. Métallocènes et compositions catalytiques dérivées de ceux-ci
EP3539993A1 (fr) 2013-07-17 2019-09-18 ExxonMobil Chemical Patents Inc. Catalyseurs métallocènes à substitution cyclopropyle
WO2017204830A1 (fr) 2016-05-27 2017-11-30 Exxonmobil Chemical Patents, Inc. Compositions de catalyseur métallocène et procédé de polymérisation les utilisant

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BR0016723A (pt) 2003-02-18
EP1548022A2 (fr) 2005-06-29
BRPI0016723B1 (pt) 2018-02-27
RU2276671C2 (ru) 2006-05-20
RU2002120465A (ru) 2004-01-10
EP1548023B1 (fr) 2013-08-14
EP1548023A2 (fr) 2005-06-29
US20060020096A1 (en) 2006-01-26
CN1249096C (zh) 2006-04-05
EP1548022A3 (fr) 2007-06-13
EP1548037A2 (fr) 2005-06-29
CN1590355A (zh) 2005-03-09
US7342078B2 (en) 2008-03-11
US7569651B2 (en) 2009-08-04
PL199958B1 (pl) 2008-11-28
EP1548023A3 (fr) 2007-06-13
CA2395552A1 (fr) 2001-07-05
CN1433435A (zh) 2003-07-30
AU2511001A (en) 2001-07-09
US20030149199A1 (en) 2003-08-07
PL356214A1 (en) 2004-06-28
EP1548037A3 (fr) 2007-09-12
KR20020084423A (ko) 2002-11-07
CN1590422A (zh) 2005-03-09
KR100789201B1 (ko) 2007-12-31
JP2003533550A (ja) 2003-11-11
AU782996B2 (en) 2005-09-15
WO2001048034A2 (fr) 2001-07-05
CN100575324C (zh) 2009-12-30
CA2395552C (fr) 2010-02-16
JP4901043B2 (ja) 2012-03-21
WO2001048034A3 (fr) 2002-06-20

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