CA2240452A1 - Transition metal compound - Google Patents
Transition metal compound Download PDFInfo
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- CA2240452A1 CA2240452A1 CA002240452A CA2240452A CA2240452A1 CA 2240452 A1 CA2240452 A1 CA 2240452A1 CA 002240452 A CA002240452 A CA 002240452A CA 2240452 A CA2240452 A CA 2240452A CA 2240452 A1 CA2240452 A1 CA 2240452A1
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- Prior art keywords
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- zirconium dichloride
- boratabenzene
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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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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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
- 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
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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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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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
- 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
Abstract
The present invention relates to a compound with the general formula (I): LnAmMXk, in which L is a borata benzene ligand of the general formula (II), in which the radicals R are identical or different and are a hydrogen atom or a C1-C10-carbon-containing group, A corresponds to a .pi.-ligand such as cyclopentadienyl, M is a metal of group IVb of the periodic system of elements, and X are identical or different and are a hydrogen atom, a C1-C40-carbon-containing group, an OH group, a halogen atom or NR22, n is a whole number 1 or 2, m is a whole number 0 or 1 and k is a whole number from 1 to 3, the sum of n+m+k being 3 or 4. The present invention also relates to a process for the preparation of the transition metal compound and the use thereof as catalyst constituent when preparing polyolefins.
Description
Description Transition metal compound The pre8ent invention relates to a tra~ition metal compound and a process for it~ preparation and also to its u-~e as a catalyst component in the preparation of polyolef in~ .
The literature di6clo~es the preparation of polyolefins u8ing soluble metallocene compounds in combination with aluminox~ne~ or other cocatalyst~ w~i~h, owing to their Lewi~ acidity, can convert ~he neutral tran~ition metal compound into a cation and stabilize it (EP-A-129 368, EP-A-351 392).
Me~allocenes and semisand~ich compound~ are of great interest not only for th~ polymerization or oligomerization of olefins. They can also be used as hydro~enation, epo~idation, i~omerization and C-C
coupling catalyst~ ~Chem. Rev. 1992, 92, 965-994).
WO 96/23004 di~clo6es certain boron-containing transition metal compounds.
of great interest are tran~ition metal compounds which have xufficient activity in re~pect of the abovedescribed ~ield~ of application.
It is an object of the present invention to provide a transition metal compound and an economical and environ-mentally friendly process for i~s preparation.
This object is achieved by a compound having the formulaI
LnAmMxk ( I ) where ~ is a boratabenzen~ ligand of the formula II
- -95/F ~13 K WO - 2 -R R
R ~ ~_y R R (Il) whe~e ~he radic~l~ R are identical or dif$erent and are each a hydrogen atom, a Cl-C20-group, preferably a C~-C10-group ~uch as a Cl-C~0-alkyl group or a C6-Cl0-aryl group, and two adja~ent radicals R together with the atoms connecting them can form a ring ~y~tem, and Y is a hydrogen atom, a Cl-C20-group, preferably a C~-C~0-group ~uch a~ a C~-C10-alkyl group or a C6-C10- aryl group, a ~alogen atom, an oR2, SR2, NR22 or PR22 radical, where R2 i~
a halogen atom, a C1-C1O-group such a~ a C~-C,~-alkyl 1~ group, preferably a C2-C~-alkyl grOup, or a C6-C1O-aryl group and two radical-~ R2 can form a ring ~ystem, A is a ~ ligand such a~ cyclopentadienyl which can be either substituted or un~ub~tituted and adjacent sub~
tuent~ on the cyclopentadienyl ligand can form a ring, M is a metal of group IVb of the Periodic Table of the Elements and X are identical or different and are eac~ a hydrogen atom, a C1-C40-~roup ~uch as a cl-C20-alkyl group, a ~-C~0-alkoxy group, a C~-C20-aryl group, a C2-Cl2-alkenyl group, a C,-C~0-arylalkyl group, a C7-C40-alkylaryl group, an OH
group, a halogen atom or ~R22, n is 1 or 2, m is 0 or 1 and k is an integer from 1 to ~, 2s where the sum of n+m~k is 3 ox 4.
L and A can be joined to one another by mean~ of a bridge. When n is 2, ~ can be identical or dlfferent The ~ridge is pre~erably ~ ~ RX ' , Rx RX
The literature di6clo~es the preparation of polyolefins u8ing soluble metallocene compounds in combination with aluminox~ne~ or other cocatalyst~ w~i~h, owing to their Lewi~ acidity, can convert ~he neutral tran~ition metal compound into a cation and stabilize it (EP-A-129 368, EP-A-351 392).
Me~allocenes and semisand~ich compound~ are of great interest not only for th~ polymerization or oligomerization of olefins. They can also be used as hydro~enation, epo~idation, i~omerization and C-C
coupling catalyst~ ~Chem. Rev. 1992, 92, 965-994).
WO 96/23004 di~clo6es certain boron-containing transition metal compounds.
of great interest are tran~ition metal compounds which have xufficient activity in re~pect of the abovedescribed ~ield~ of application.
It is an object of the present invention to provide a transition metal compound and an economical and environ-mentally friendly process for i~s preparation.
This object is achieved by a compound having the formulaI
LnAmMxk ( I ) where ~ is a boratabenzen~ ligand of the formula II
- -95/F ~13 K WO - 2 -R R
R ~ ~_y R R (Il) whe~e ~he radic~l~ R are identical or dif$erent and are each a hydrogen atom, a Cl-C20-group, preferably a C~-C10-group ~uch as a Cl-C~0-alkyl group or a C6-Cl0-aryl group, and two adja~ent radicals R together with the atoms connecting them can form a ring ~y~tem, and Y is a hydrogen atom, a Cl-C20-group, preferably a C~-C~0-group ~uch a~ a C~-C10-alkyl group or a C6-C10- aryl group, a ~alogen atom, an oR2, SR2, NR22 or PR22 radical, where R2 i~
a halogen atom, a C1-C1O-group such a~ a C~-C,~-alkyl 1~ group, preferably a C2-C~-alkyl grOup, or a C6-C1O-aryl group and two radical-~ R2 can form a ring ~ystem, A is a ~ ligand such a~ cyclopentadienyl which can be either substituted or un~ub~tituted and adjacent sub~
tuent~ on the cyclopentadienyl ligand can form a ring, M is a metal of group IVb of the Periodic Table of the Elements and X are identical or different and are eac~ a hydrogen atom, a C1-C40-~roup ~uch as a cl-C20-alkyl group, a ~-C~0-alkoxy group, a C~-C20-aryl group, a C2-Cl2-alkenyl group, a C,-C~0-arylalkyl group, a C7-C40-alkylaryl group, an OH
group, a halogen atom or ~R22, n is 1 or 2, m is 0 or 1 and k is an integer from 1 to ~, 2s where the sum of n+m~k is 3 ox 4.
L and A can be joined to one another by mean~ of a bridge. When n is 2, ~ can be identical or dlfferent The ~ridge is pre~erably ~ ~ RX ' , Rx RX
2 - ~2 ~2 --C C--RY , F~l~ RY ' Rr RY
~ Rs --O--I Z o-- C
I
RY R~ RY Rr R~
RX RX ~X f~ TX RX
O ~-- - C--~ C C--C--RY ' RY RY ' RY R~ RY
~BRX, ~AIR~, -Ge-, -O-, -S-, ~SO, >SOz, ~NRX, ~CO, ~pRx or ~P(O)RX, where Rx and RY are identical or di~ferent and are each a hydrogen atom, a halogen atom or a Cl-C,O-group ~uch as a C1-C20-alkyl group, a Cl-C1O-fluoroalkyl group, a Cl-C1O-alkoxy group, a C~-Cl,-aryl group, a C6-C1O-fluoroaryl group, a C6-C~O-aryloxy group, a C2-C1O-alkenyl group, a C7-C~O-arylalkyl group, a C~-C40-alkylaryl group or a C~-C~O-arylalkenyl group and M~ i~ silicon, germani~m or ~in.
Examples of bridges are groups (M2RXRY)y~ where Ma i~
carbon, silicon, germanium or tin and Rx and RY are identical or different and are each a Cl-C20-hydrocarbon group such as Cl-C~O-alkyl or c6-C~4-aryl and y is 1 Qr 2, e.g. CH2, CH2CH2, CH ( CH3 ) CH2, C ( CH3 ) ( C6H5 ), C ( C6H5 ) CH(C~H~)C(CH3)z~ C(CH3)2, C(CH3) (C6H5), C(C6H5)2~ (CH3)2$i~
~CH3) 2Ge, tCH3) 2Sn, (C6H5) 2Si, (C6Hs) (CH3) Si, (C6H5) 2Ge, ~C6H5)2Sn, (CH2)~Si, CH2$i(CH3)z~ o-C6H4 or 2,2'-(C6H4)2 95/F 313 K WO - 4 ~
The pre8ent invention accordingly provides a tran~ition metal compound which contains as a ligand at lea~t one substituted or unQubxtituted boratabenzene group and is described by the formula I.
A preferred ~mho~ nt of the invention is a compound in whic~ M i~ an element of group IVb of the Periodic Table of the Elements, in parti~ular zirconium.
A preferred embo~;me~t of the invention i8 a compound in which the radical~ R are identical and are ea~h a hydro-gen atom, a Cl- C4 - alkyl group or ~ C6 - C10 - aryl group and Y
i~ a Cl-C~-alkyl group or NR2Z, where R2 is a C -C4-alkyl group, preferably a Cz-C4-alkyl group.
A preferred embodiment of the in~ention is a compound in which A is a substituted cyclopentadienyl ligand.
A preferred embodi~ent of the invention is a compound in which X is Cl-C1O-alkyl or NRa2, where R2 i-~ a Cl-C4-alkyl group, a C6-C~O-aryl group or a halogen acom, in particular chlorine.
A preferred embodiment of the invention ie a compound in which m - O or 1 when n = 1 and m - O when n ~ 2.
A i~ preferably a ~-ligand ~uch as cyclopentadienyl, indenyl or fluore~yl, which can each be either substituted or unsu~tituted.
~-~igands are preferably an u~ub~tituted cyclopenta-dienyl group or sub~tituted cyclopentadienyl group whichpreferably bear one or more Cl-C~O-hydrocarbon radicals a3 sub~tituents, e.g. 2-methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, i~opropylcyclopentadienyl, di~ethylcyclopentadie~yl, trimethylethylcyclopent~;enyl, 5-phenylcyclopentadienyl, diphenylcyclopentadienyl, ~n~Anyl, 2-me~hyli n~enyl, ~-ethylin~nyl, 3-methylindenyl, 3-tert-butylin~yl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylinde~yl, 2-methyl-4-i~opropylindenyl, benzlnfl~nyl, 2-methyl-4,5-benzindenyl, 2-methyl-a-ace-naphthindenyl, ~-methyl-4,6-dii~opropylindenyl, ~luorenyl, 4-methylfluorenyl or 2,7-di-tert-butyl-fluorenyl.
Particular preference i~ given to compound~ of the formula I in which M i~ zirconium and X are identical and are each a halogen atom, in particular chlorine.
Particular preference is given to compound~ of ~he formula I i~ which L iQ a boratabenzene ligand of the formula II and the radical~ R are preferably identical and are each a hydrogen atom ~nd Y is preferably a C1-C~-alkyl group ~uch aq methyl, ethyl, propyl, isopropyl or butyl, or NRa2 in which R2 i~ a Cl-C,-alkyl group such a~
methyl, ethyl, propyl, isopropyl or butyl. When m i~ 1, A is preferably a cyclopentadienyl ligand s~ch as cyclo-pentadienyl, methylcyclopentadienyl, pentamethylcyclo-pentadienyl or indenyl. Pre~erence i-~ al~o given to compounds of the formula I in which X are identical and are each a Cl-C4-alkyl group, in particular methyl, or a C7-C~O-alkylaryl group, in particular benzyl, or a halogen atom, in particular ch~orine, and n i~ 1 or 2 and m is O
or 1 when n i~ 1 and m is O when n is 2 and the ~um of n+m+k can be 3 or 4.
Example~ of transition metal compound~ of the invention are: -(l-methylboratabenzene)~pentamethylcyclopentadienyl)-zirconium dichloride (1-butylboratabenzene)(pentamethylcyclopentadienyl)-zirconium dichloride (l-methylbora~benzene)(pentamethylcyclopentadien~l)-dimethylzirconium (l-butylboratabenzene)(pentamethylcyclopentadienyl)-dibenzylzirconium [1-(dimethylamino)boratabenzene](pentamethylcyclo-pentadienyl)-zirconium dichloride [1-(diethylamino)boratabenzene](cyclopentadienyl)-zirconium dichloride [l-(dimethylamino)boratabenze~e](pentamethylcyclo-pentadienyl)dimethylzirconium ~1-(diethylamino)boratabenzene](cyclopentadienyl)di-benzylzirconium (1-methylbora~abenzene)(cyclopentadienyl)zirconium dichloride (l-methylborat~h~n~ene)(methylcyclopentadienyl) 2 irconium dichloride (1-methylboratabenzene)(cyclopentadienyl)dimethylzir-conium (1-methylboratabenzene)(methylcyclopentadienyl)di-benzylzirconium bi~ methylboratabenzene)zirconium dichloride bis(1-methylboratabenzene)dimethylzirconium bis(l-methylborata~enzene)hafnium dichloride bis(l-methylboratabenzene)dibenzylzirconium (l-methylboratabenzene)zirconiumtrichloride (1-ethylboratabenzene)zirconium trichloride (l-methylboratabenzene)(indenyl)zirconium dichloride (l-~ethylboratabenzene)(indenyl)dimethyl zirconium (l-me~hylboratabenzene)(indenyl)dibenzyl zirconium [1-(dimethylamino)boratabenzene~(indenyl)zirconium dichloride (1-methylboratabenzene)(pentamethylcyclopentadienyl)-titanium dichloride (1-methylbor~tabenzene)(cyclopentadienyl)titanium dichloride [1-(dimethylamino)boratabenzene](cyclopentadienyl)-titanium chloride bi~(l-methylboratabenzsne)titanium dichloride bi~ methylboratabenzene)titanium chloride (1-methylboratabenzene)titanium ~richloride (1-methylboratabenzene)titanium dichloride (l-methylboratabenzene)(indenyl)titanium dichloride ~ dimethylamino)boratabenzene](indenyl)titanium chloride [l-(diethylamino)boratabenzene](pentamethylcyclopenta-dienyl~titanium dichloride tl-(diethylamino)boratabenzene~lpentamethylcyclopenta-dienyl)hafnium dichloride [1-(diethylamino)boratabenzene]~pentamethylcyclopenta-dienyl)zirconium dichloride ~1-(diethylamino)boratabenzene](pentamethylcyclopenta-dienyl)dimethylzirconium [1-(pyrrolidino)boratabenzene](pentamethylcyclopenta-dienyl)zirconium dichloride [l-(piperidino)borataben~ene](pentamethylcyclopenta-dienyl)zirconium dichloride tl-(pyrrolo)boratabenzene](pentamethylcyclopentadienyl)-zirconium dichloride~1-(bi8trimethylsilylamino)boratabenzene~(pentamethyl-cyclopentadienyl)zirconium dichloxide tl-(diisopropylamino)boratabenzene](pentamethylcy pe~tadienyl)zirconium dichloride [1-(N-methylanilino)bora~Ahen7,~e](pentamethylcyclopenta-dienyl)zirconium dichloride [1-(diphenylamino)boratabenzene~(pentamethylcyclopenta-dienyl)zirconium dichloride tl-(pyrrolidino)borat~h-n7ene]~cyclopentadienyl)zirconium dichloride [l-(piperidino)boratabenzene](cyclopentadienyl)zirconium dic~loride [l-(pyrrolo)boratabenzene](cyclopentadienyl)zirconium dichloride [l-~bi~trimethyl~ilylamino)boratabenzene](cyclopenta-dienyl)zirconium dichloride [1-(diisopropylamino)boratabenzene](cyclopentadienyl)-zirconium dichloride [1-(N-methylanilino)boratabenzene~tcyclopen~adien~l)-zirconium dichloridetl-(diphenylamino)~ora t aben z ene](cycl opent adienyl)-zirconium dichloride [l-(diphenylpho~phino) borat abenzene](pentamethylcyclo-pentadienyl) titanium dichloride [l-(~iphenylphosphino)boratabenzene~(pentamethylcyclo-pentadienyl)zirconium dichloride ~l-(diphenylphosphino)boratabenzene3(pentamethylcyclo-pentadienyl)dimethylzirconium S [l-(di~ethylphosphino)boratabenzene](pen~amethylcyclo-pentadienyl)zirconium dichloride [1-(dibutylphosphino)boratabenzene](pen~amethylcyclo-pentadienyl)zirconium dichloride [1-(dii~opropylphosphino)bora~abenzene](pentamethylcyclo-pentadienyl)zirconiu~ dichloride[1-(dicyclohexylphosphino)boratabenzene](pentamethyl-cyclopentadienyl)zirconium dichloride [1-(diphenylpho8phino)borat~benzene](cyclopentadienyl)-zirconium dichloride [1-(dimethylpho~phino)boratabenzene](cyclopentadienyl)-zirconium dichloride [1-(dibutylphosphino)boratabenzene](cyclopentadienyl)-zirconium dichloride E1-(diisopropylpho~phino)boratabenzene](cyclopenta-dienyl)zirconium dichloride[1-(dicyclohexylphoQphino)boratabenzene]( cyc lopenta-dienyl)zirconium dichlo~ide bis[1-(diethylamino)boratabenzene]zirconium dichloride bistl-(diethylamino)boratabenzene]dimethylzirconium bis[1-(pyrrolidino)boratabenzene]zirconium dichloride bis[1-(diphenylphosphino)boratabenzene~zirconium dichloride bi~[l-(dimethylphosphino)boratabenzene]zirconium dichloride [1-(diethylamino)boratabenzene](indenyl)zirconium dichloride ~1-(diethylamino)boratabenzene](fluorenyl)zirconium dichloride ~l-(~e~hylboratabenzene](fluorenyl)zirconium dichloride [l-(diethylamino)boratabenzene]titanium trichloride ~1-(diethylamino)boratabenzene] titanium dichloride bi~[l-(diethyla~ino)boratabenzene]ti~anium chloride ethylenebis[4~ methylboratabenzene)~zirconium dichloride - 95/F 313 K W0 - ~ -ethylenebi~[3~ methylboratabenzene)~zirconium dichloride ethylenebis[2-~1-methylboratabenzene)]zirconium dichloride ethylenebis(1-boratabenzene)]zirconium dichloride ethylenebi~s-(1-dimethylaminoboratabenzene)~zirconium dichloride ethylenebi~3-(l-dimethylaminoboratabenzene)~zirconium dichloride ethylenebis~2-tl-dimethylaminoboratabenzene)]zirconium dichloride ethylenebis[4-~l-diethylami~oboratabenzene)]zirconium dichloride ethylenebi~[4-(l-diphenylphosphinoboratabenzene)]-zirconium dichlorideethylenebis~4-(1-pyrrolidinoboratabenzene)]zirconium dichloride ethylenebi~[4~ methylboratabenzene)]titanium dichloride ethylenebix[3~ methylboratabenzene)]titanium dichloride ethylenebis~2-(1-methylbora~be~ene)]titanium dichloride ethylenebis(1-boratabenzene)titanium dichloride ethylene~(4-(1-methylboratabenzene))cyclopentadienyl~-zirconium dich-loride ethylene~(4-(1-~ethylboratabenzene))penta~ethylcyclo-pentadienyl~zirconium dichlorideethylene[(4-(1-methylboratabenzene))indenyl]zirconium dichloride ethylene[(4-(1-~ethylboratabenzene))fluorenyl]zirconium dichloride 3~ ethylene[(1-boratabenzene)cyclopentadienyl]zirconium dichloride ethyleneL(l-boratabenzene)indenyl~zirconium dichloride ethylene[(l-boratabenzene)fluorenyl]zirconium dichloride ethylenebis(1-methylaminoboratabenzene)]zirconium dichloride ethylenebis~l-phenylphosphino~oratabenzene)]zirconium dichloride ethylenebis(1-oxyboratabenzene)]zirconium dichloride ethylenebi~l-thioboratabenzene)]zir~onium dichloride dimethylsilanediylbi~4-(1-methylboratabenzene)]zirconium dichloride dimethyl~ilanediylbis~4-(l-dimethylaminoboratabenzene)]-zirconium dichloride dimethylsilanediylbiQ~4-(1-diphenylpho~phinoborata-benzene)]zirconium dichloride dimethylsilanediylbi~[(l methyleneboratabenzene)~-zirconium dichloride dimethyl~ilanediylbi~[(l-methylaminoboratabenzene)~-zirconium dichlo~idedimethylsilanediylbis[(l-oxyboratabenzene)~zirconium dichloride dimethylsilanediyl[(4-(1-methylboratabenzene)) cyclopenta-dienyl]zirconium dichloride lS dimethylsilanediyl[(4-(1-methylboratabenzene))penta-~ethylcyclopentadienyl]zirconium dichloride dimethyl3ilanediyl[(4-(l-methylboratabenzene))indenyl]
zirconium dichloride dimethylsilanediyl[(4-(l-methylborar~hen7.ene))fluorenyl]-zirconium dichloridedimethyl~ilanediyl[(4-(l-dimethylAmjno~oratabenzene)) cyclopentadienyl]zirconium dichloride dimethylsilanediyl[(4-(1-diphenylpho6phinolborata-benzene))cyclopentadienyl]zirconium dichloride dimethylsilanediyl[(3-(1-dime~hylaminoboratabenzene))-cyclopentadienyl~zirconium dichloride dimethylsilanediyl~(2-~l-dimethyl~minohoratabenzene))-cyclopentadienyl]zirconium dichloride dimethylsilanediyl[(l-methylaminoboratabenzene))cyclo-pentadienyl]zirconium dichlorideisopropylidenyl[(4-(1-dimethylaminoboratabenzene))cyclo-pentadienyl]zirconium dichloride isopropylid~nylbi~[s-(l methylboratabenzene)]zirconium dichloride ~
35 The invention provideQ a proce~ for preparing the navel transition metal compound-~ h~ving the formula (I). The process is illustrated by the synthesis schemes below ~or co...~ounds of the formulae IV, v and VI. I~ these ~ormulae, R, Y, M and X are defined as in formulae I and II. A i~ a li~and ~uch as cyclopentadienyl, indenyl or fluorenyl, each of which may be either ~ubstituted or un~u~tituted. Ml i~ a metal of main group Ia of the Periodic Table of the ~lement~.
For example, in a proces~ for preparing a compound havi~g the formula (I), a compound having the formula (III) reacts wi~h MXl where 1 i~ an integer from 3 to 5.
In an alternative proce~s for preparing a compound having the formula (I), a compound having the formul~ ~V) reacts with A-Ml'.
In a further alternative proces~ for preparing a compound having the formula (I), a compou~d having the formula ~III) reacts with AMX~
R~ R
~Q ~ R
~ r ~' R~--r R
In an alternative proce~R for preparing a compound having - 95~F 313 K WO - 12 -the formula ~I), a compound having the formula (VII) reacts with MX, where 1 is an integer from 3 to 5 and Z
is an element of group IVa of the Periodic Table of the Element~ and R3 are identical or different and are each a hydrogen atom, a Cl-C2D-group,- for example a Cl-C20-hydrocarbon radical such as a C1-C20-alkyl group or a C6-C20-aryl group, or ~wo adjacent radical~ R3 together with the atoms connecting them can form a ring y~tem.
Preferably Z i~ ~ilicon, germanium, tin or lead and R3 are identical and are particularly preferably each a Cl-Clc-alkyl group 8uch a~ methyl, ethyl, i~opropyl or butyl or a C~-C1c-aryl group such a~ phenyl.
In an alternative process for preparing a compound having the formula (I), a compound having the formula react~ with AMX1-l R R
R~Y
R R ZR,~ R
R R~~
R~ y t~l ~
R R
~Y
Y
q R
~he compound~ of the formulae III and VII can be prepared ~ 95/F 313 K WO - 13 -by literat~re methods (Organometallics 1995, 14, 471).
The conver~ion of the compound~ of the formula III into the de~ired tran~ition metal complexes i~ k~own in principle. For this purpose, the monoanion of the formula III i~ reacted in an inert solvent with the corresponding metal halide ~uch as zirconium tetrachloride. A is a li~and Yuch aQ cyclopentadienyl, indenyl or fluorenyl which can eac~ be either ~ubstituted or un~ubstituted.
S~itable solvents for the reaction are aliphatic or aromatic ~olvents such as h~nP or toluene, ether solvent~ such as ~etrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons ~uch as o-dichloro-benzene.
The invention provide~ for the use of the compound ha~ing the formula I as a catalyst component in ~he polymerization of olefins. The present invention accordin~ly provides a process for preparing a polyolefin by polymerization of one or more olefin~ in the pre~ence 2 0 of a transition metal compound of the ~ormula I . For the purposes of the invention, the term polymeriza~ion refer~
to both homopolymerization and copolymerization.
In the process of the in~ention, preference is given to polymerizing one or more olefin~ of the formula R'-CH=CH-R~ where R~ and Rb are iden~ical o~ different and are eacha hydrogen atom or a ~ydrocarbon radical having from 1 to 2~ carbon atom~, in particular from 1 to 10 carbon atoms, or Ra and Rb together with the atoms connecting them form one or more rings. Examples of such olefi~ are l-olefins ha~ing 1-20 carbon atom~, for example ethylene, propene, 1-butene, l-pentene, l-hexene, 4-methyl-1-pentene or l-octene, styrene, cyclic or acyclic diene~ ~uch as 1,3-butadiene, isoprene, 1,4-hexadiene, norbornadiene, vinylnorbornene, s-ethylidenenorbornene or cyclic mono-olefins such a~ nor~ornene or tetracyclododecene. In theproceyy o~ the in~ention, pre~erence is given to homopo-lymerizing ethylene or propylene or copolymerizing ethylene with one or more acyclic 1-olefins having ~rom 3 to 20 carbon atoms, for example propylenç, and/or one or more diene~ havi~g from 4 to 20 carbon atoms, for 5 examlple 1, 3-butadiene .
The polymerization i-~ preferably carried out at a temperature of from -60 ~o 250~C, more preferably 20 to 70~C, particularly preferably from 50 to 20~C. The pressure is preferably from 0.5 to 2000 bar, particularly preferably ~rom 4 to 64 bar, very particularly prefera~ly from 5 to 64 bar.
The polymerization can ~e carried out in solution, in bulk, in su~pen~ion or in the gas pha-~e, continuously or batchwise, in one or more ~tage~.
The catalyst used in the proces~ of the invention prefera~ly comprise~ a ~ran~ition metal compound. It i~
also po~sible ~o use mix~ure~ of two or more transition metal compound~ ~r mixture~ with metallocenes, for example for preparing polyolefins having a broad or multimodal molecular weight distribution.
In principle, a suitable cocatalyst in the proce~s of the invention is any compound which, owing to i~ Lewis acidity, can eonvert the neutral transition metal compound in~o a cation and Qtabilize the latter ("labile coordination"). Furthermore, the cocatalyst or the anion formed therefrom 6hould undergo no further reactions with the cation formed (EP-A-427 6g7). A6 cocatalyst, pre~erence i~ given to using an aluminum compound and/or a boron compound.
The boron compound preferably has the formula R5XNH4.xBR~, RsxpH~-xBR6~ R53CBR6~ or BR63, where x i~ from l ~o, 4, preferably 3, and the radical~ R5 are identical or different, preferably identical, and are C~-Cl0-alkyl or C6-ClR-aryl or two radicals R5 together with the atoms connecting them ~orm a ring, and the radicals R6 are identical or different, preferably identical, and are C6-Cl~-aryl which may be sub~tituted by alkyl, haloalkyl or fluorine. In particular R5is ethyl, propyl, butyl or phenyl and R6 is phenyl, pentafluorophènyl, 3,5-bi~-(trifluoromethyl)phenyl, mesityl, xylyl or tolyl (EP-A-2~ 003, EP-A-2~7 004 and EP-A-426 63~).
The cocatalyst used is preferably an all~m~ m compound ~uch as aluminoxane and/or an aluminum alkyl.
The cocataly~t used i~ particularly preferably an aluminoxane, in particular one of the formula VIIa for the linear type and/or the formula VIIb for ~he cyclic type, ~ R~ -¦ ~ R~
~ O- Al O Al ~ ~n~J) R~ _ _ D R4 Al O ~llO) _ _ p~2 where, in the ~ormulae VIIa and VIIb, the radicals R~ are identical or different and are each hydr~gen or a Cl-C20-hydrocarbon group such as a C1-Cle-alkyl group, a C6-C1,-aryl gr~up or benzyl and p is an integer from 2 to 50, preferably from 10 to 35.
The radical~ R4 are p~eferably identical and are hydro-gen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl I~ the radical~ R4 are different, then they are pre~erably me~hyl and hydro~en or alternati~ely methyl ~ 95/F 313 K W0 - 16 -and isobutyl, with hydrogen or i~obutyl preferably ~eing present in a proportion of from 0.01 to 40~ by number (of the radicals R4).
The methods of preparing the al~mi~o~nes are known. The exact -~patial structure of the al~m~nox~ne~ not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it i~
concei~able that chains and rings can joi~ to ~or~ larger two-dimen~ional or three-dimen~ional ~tructure~.
Regardless of the method of pr~paration, all al~;nox~e ~olution~ ha~e in common a varying content of unreacted alu~nl~ starting compound which i9 pre-~ent in free form or a~ adduct.
It is pos~ible to preacti~ate the tran~ition metal compound u~ing a cocatalyst, in particular an alumin-oxane, prior to use in the polymerization reaction. Thissignificantly increa~e~ the polymerization acti~ity. The preactivation of the transition metal compound i~
preferably carried out in ~olution. The transition metal compound i~ here preferably di~olved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbo~ are aliphatic or aromatic hydrocarbons.
Preference i~ given to u~ing toluene.
The concentration of the al~ oxane in the solution is in the range from about 1~ by weight to the saturation limit, preferably from 5 to 30~ by weight, in each case ba~ed on the total amount of solution. The transition metal compound can be u~ed in the same concentration, ~ut it is preferably u~ed in an amount of from 10-~ to 1 mol per mol of aluminoxane. The preactivation time i~ from 5 minutes to 60 hours, preferably from 5 to 60 min~te~.
The preactivation is carried out at a temperature of from -78 to 100~C, preferably from o to 70~C.
The tran~ition metal compound i8 preferably u~ed in a concentration, ba-~ed on the ~ran~ition ~etal, of from 10~1 to lO-a mol, pre~erably from lO-' to 10-7 mol, of tran~ition metal per d~ of sol~ent or per dm3 of reactor volume. The aluminoxane is preferably used in a concentration of from 1o-6 to 1o-l mol, preferably fro~ 10-5 to 10-2, mol per dml of solvent or per dm~ of rea~tor volume. The other cocatalysts mentioned are used in approximately equimolar amount~ to the transition metal compound. However, higher concentrations are alRo posYible in principle.
To re~ove catalyst poisons pre~e~t in the ole~in, purification using an aluminum compound, preferably an al~m; ~l~m alkyl such ag trimethyla~lm;nl~m or trie~hyl-al~minum, is advantageous. Thi~ purification can be carried out either in the polymerization system itself or the ole~in i~ brought into contac~ with the aluminum com-pound and sub~equently separated off again before addition to the polymerization system.
In the proceYs of the invention, hydrogen can be added as a molecular weight regulator and/or to increa~e ~he catalyst activity. This enables low molecular weight polyolefin~ ~uch a~ waxe~ to be obtained.
In the process of the pre~ent inve~tion, the tran~ition metal catalyst is preferably reacted with the cocataly~t outside the polymerization reac~or in a separate step using a suitable golvent. Application to a support can also be carried out during thi~ procedure.
In the process of the invention, a prepolymerlzation can be carried out with the aid o~ the transition metal compound. For the prepolymerization, pre~erence is given to using the (or one of the) olefin(s) used in the polymerization.
The catalyst u~ed in the proce~s of the invention can be ~upported. Application to a support enables, for example, the particle morphology of the polyolefin prepared to be controlled. Here, the transition metal compound can be f irst reacted with the ~upport and ~ub~equently wich the cocatalys~. The cocataly~t can al~o be supported ~irst and subsequently reacted with the tran~ition metal co~pound. It is also possible to support t~e reaction product of tran~ition metal compound and cocatalyst.
Suitable ~upport materials are, for example, ~ilica gel~, aluminum oxide~, ~olid aluminoxane or other inorganic ~upport ma~erial~ such as magnesium chloride. Ano~her lo ~uitable Qupport material i~ a polyolefin powder i~
finely di~ided form. The preparation of the ~upported cocatalyst can be carried out, for example, as de~cribed in EP-A-567 952.
If the polymerization is carried out as a ~uspen~ion or solution polymeri~ation, an inert 601vent cu~tomary for the Ziegler low-pres~ure process is used. For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon, for example propane, butane, h~Y~n~, heptane, isooctane, cyclohexane, methylcyclo-hexane. A petroleum or hydrogenated diesel oil fxactioncan al~o be u~ed. It i9 also po~sible to use toluene.
Preference i~ given to carrying out t~e polymerization in the liquid monomer.
Before addition of the cataly~t, in particular the -~upported catalyst system (compri~ing the tran~ition metal compound of the invention and a ~upported cocatalyst), another aluminum alkyl compound such as trimethylaluminum~trie~hylaluminum~triisobutylalllm;nllm~
trioctylaluminum or i~oprenrlaluminum can be introduced into the reactor to make the polymerization sy~te~ inert (for example to remove catalyst poi~ons pre~ent in t~
olefin). ~iQ compound is added to the polymer~zatlo~
sy~tem in a concentration of from 100 to 0.01 mmol o~ Al per kg of reactor conten~. Pre~erence is given, to trii~obutylaluminum and triethylaluminum in a concentration o~ from 10 to o.1 mmol of Al per kg of reactor content~, This enableQ the molar Al/ml ratio to be made -~mall in the synthesi~ of the ~upported catalyst YyStem ~
If inert qolventR are used, the monomers are preferably metered in in ga~eou~ or liquid form.
The specific tran~ition metal compound~ described in the pre~ent invention are suita~le for the preparation of polyolefins. The latter are suitable, in particular, for producing shaped bodies such as filmR, plates or large hollow bodieg (e.g. pipe~) and can al~o be used as plasticizer and lubricant formulations, for melt adhesive applications, coatings, seals, insulatio~, filler compo~itions or ~ound insulation material~.
U6e of hydro~en or increasing ~he polymerization tempera~ure make it p~ssible to obtain polyolefin~ having 15 a low molar ma6~ ~ e . g . waxe~, who~e hardnes~ or melting point can be varied by means of the comonomer content.
Selection of the polymerization proce~ and the type(s) of comonomer(s), ~nd also amount(s) of comonomer(~), enable olefin copolymers having ela~tomeric properties to be prepared, for example ethylene-propylene-1,4-hex~;ene terpolymer~.
The following example~ illus~rate the invention.
Preparation and handling of organometallic compounds were carried out with exclu~io~ of air and moi~ture under protect~ve argon ga~ (Schlenk technique). All solvents r~quired were freed of air and moi~ture ~efore u~e by boiling for a number of hour~ over a suitable desiccant and ~ub~equent di-~tillation under argon.
The Al/CH3 ratio in the al~m;nn~ane was de~ermined by decomposing the sample with HzS04 and determining .the volume of the hydrolysis gase~ formed under standard conditions and by complexometric titration of the aluminum in the then completely dis~olved ~ample by the Schwarzenbach method. The compounds were characterized using ~H-NMR, ~3C-NMR and IR spectroscopy.
Examples Example 1 bis(l-Methylboratabenzene)zirconium dichloride 1 g of zirconium tetrachloride and 0.84 g of (1-methyl-boratabenzene)lithium were ~u~pended in 20 ml of ~oluene and ~tirred for three days at 100~C. The yellow suspension obtained was filtered and the ~olvent wa~
removed under reduced pre~sure. The yellow solid o~tained was washed with 5 ml of hexane. The yield of transition metal compound wa~ O.B9 g (60~ of theory).
'~-NMR (CD2Cl2): 7.6, 6.6, 6.3 (each m, 5H, arom. H), 0.9 (s, 3H, CH3). Mas~ spectrum: 344 Mt~ correct disintegration pattern.
Example 2 di(~-Chloro)tetra[h6-(1-methylboratabenzene)]dititanium 0.48 g of titanium trichloride and 0.~1 g of (1-methyl-boratabenzene)lithium are su~pended in 10 ml of toluene and ~tirred ~or ~hree day-~ at llO~C. The brown suspension obtained is filtered and the filtrate is cooled to -30~C.
The bro~n solid obtained i~ wa~hed with 5 ml of h~x~n~, giving the txansition metal compound in a yield of 60 (0.49 g).
Ma~ ~pectrum: 265 M+, correct disintegration pattern.
Example 3 ~1-Methylboratabenzene)titanium trichloride 1.36 g of 1-~ethyl-6-(trimethylstannyl)-2,4-boracyclo-h~y~nediene are dissol~ed in 10 ml of hexane and 1.1 g of ~ 9S/F 313 K W0 - 21 -titanium tetrachloride are added at -10~C. After ~tirring for 3 hour~, the red-violet ~olution i~ evaporated until crystallization commence~ and stored for 12 hour~ at -300C. The product is obtained in the form of deep violet S cry~tals in a yield of 93~ (1.22 g).
H-NMR (CD2Cl2): 8.1, 7.0, 7.3 (each m, 5H, arom. H), 1.1 (8 , 3H, CH3). Ma~ spectrum: 244 Ml, correct disin-tegration pattern.
Example 4 (1-Methylborataben 2 ene ) c yC lopentadienyltitanium dichloride 0.57 g of cyclopentadienyltitanium trichloride are dissolved in S ml of tetrahydrofuran and admixed at - ~ 0 ~ C
with a solution of 0.65 ~ of 1-methyl-6-(trimethyl-stannyl)-2,4-boracyclohexanediene in 2 ml of tetrahydro-~uran. After ~he Rolu~ion has been warmed to room temperature, the precipitated dark green ery~tal~ are filtered off; yield: 60~ (0.4 g).
lH-NMR (CD2Cl2): 7.8, 6.9, 5.9 ~each m, 5H, arom. H), 6.7 (m, 5H, Cp-H), 1.1 (s, 3H, CH~). Ma~s spe~trum: 274 M+, correct diQintegration pattern.
Example 5 ~ ethylboratabenzene)cyclopentadienyl~iraonium dichloride ~
0.3 g of cyclopentadienylzirconium trichlorida is ~uQpended in 5 ml of toluene and ad~ixed at room temperature with a solution of 0.3~ ~ of 1-methyl-6-(trimethylsilyl)-2,4-boracyclohexanediene in 2 ~ml of toluene. Af~er the solution has been heated for 3 hours at ~OoC, it i~ cooled to -30~C and ~tored for 12 hour~at thi~ temperature. Thi3 gives 0.26 g of the yellow compound (70~).
lH-NMR (~D2C12): 7.7, 6.3, 6.~ (each m, SH, arom. H), 6.
CA 022404~2 l998-06-l9 9~/F 313 K wo - Z2 -(m, 5H, Cp-H), 1.0 ~s, ~H, CH3). ~a~ ~pe~trum: 316 Ml, correct disintegration pattern.
Example 6 bis(l-Methylboratabenzene)hafnium dichloride 0.32 g of hafnium tetrachloride i~ ~uspended in ~ ml of toluene and admixed at room temperature with a solution of 0.33 g of 1-methyl-6-(trimethylsilyl)-2,4-boracyclo-hexanediene in 2 ml of toluene. After the ~olution ha~
been ~eated for 2 hours at 70~C, it is cooled to -30~C
and ~tored for 12 hours at thi~ temperature. ThiQ givee 0.37 g of the yellow compound (88~).
H-NMR (CD2C12): 7.6, 6.3, 6.6 (each m, 5H, arom. H), 5.8 (m, 5H, Cp-H), 1.0 (~, 3H, CH3) . Mas~ ~pectrum: 132 M+, correct di~integration pattern.
Example 7 tl-Methylboratabenzene)(pentamethylcyclopentadienyl)-hafnium dichloride 1.1 g of peneame~hylcyclope~tadienylhafnium trichloride are ~uspended in 10 ml of toluene and admixed at room temperat~re with a ~olution of 0.27 g o$ l-methylborata-benzenelithium in 10 ml of toluene and 2 ml of dimethoxy-ethane. After the ~olution has been heated for 3 hours at 110~C, the suspension is filtered and the filtrate is cooled to -30~C and stored for 12 hours at this temperature. Thi~ give~ 1. 0~ g of the pale yellow compound (85~).
H-NMR (CD2C12): 7.5, 6.2, 6.0 (each m, 5H, arom. H), 1.8 (s, lSH, Cp-CH3), 0.8 (x, 3H, CH3) . Mas~ spectrum 476 M+, correcC di~integration pattern.
Polymerization The catalysts of the formula (I) were used for PE
' CA 02240452 1998-06-19 - ss/F 313 K wo - 23 -polymerization in a su~pen~ion polymerization in an autoclave. Cataly#t I is bisll-methylboratabenzene)-zirconium dichloride. Cataly-qt II i-~ methylborata-benze~e~(pentamethyl~yclopentadienyl)zirconium dichloride. Catalyqt II~ iq ~l-dimethylaminoborata-~enze~e)(pentamethylcyclopen~adienyl)zirconium dichloride.
Example ~
2.0 mg of cataly~t II (0.0052 mmol of Zr) were dissol~ed under argon ~hile ~tirring in 1.5 ml o~ toluene in a Schlenk tube. The ~olution was then activated by ~;n~
3.7 ml of 30~ ~trength MAO (17.69 mmol of Al; 2r:Al =
1:3402) from Witco and thi~ ~olution wa~ added to 750 ml of ~xxsol loo/120. The catalyst solution wa~ tran6ferred to an autoclave. In the autoclave, polymerization wa~
carried out for one hour at a tempera~ure of 70OC and a stirrer ~peed of 750 rpm under an ethylene partial pressure o~ 4 bar. From the yield of 145.72 g of PE, which is formed as a fine p~wder, the catalyst activity is calculated a~ 7006 g PE/mmol Zr/bar C2H~/h.
~mrles 9 to 13 were carried out similarly to Example a.
The changes from Example Y are ~hown in Table 1 below.
Table 1: Polymerization Examples 9 to 13 Example Cat. ~at. Cat. Al Zr:Al Pre~sure rield Cataly~t [mg] ~mmol][mmol~ of C,H, tg] acti~rity~
[bar]
259I 1.8 0.0052 15.77 1:3033 4 12.26 586 10I 2.q 0.007023.89 1:3413 4 17.86 641~
11II 1.7 0.0044 16.72 1:3800 4 69.76 3982 "
12III 2.4 0.005821 99 1:3791 4 41.50 17B9 13III 2.8 0.006723.~9 1:3566 ~ 42.90 1~01 ~Catalyst acti~ity: [g PE/mmol Zr/bar C2H4/h]
~ 95/F 313 K W0 - 24 -Preparation of organoboron compound~
Example 14 1-Dimethylamino-6-(trimethylsilyl)boracyclohexa-2,4-diene 1.5 g of l-dimethylA~;nohoratabenzenelithium ~TMEDA) were suspended in 50 ml o~ pentane and cooled to -75~C. 1.0 ml of chlorotrimethyl~ilane wa~ added to the ~uspension, the ~ixture wa~ allowed to warm up to room temperature and filtered, the pentane was removed under reduced pres~ure and the product wa~ distilled at 103~C/12 mbar. The yield of the organoboron compound wa~ 1.0 g (84~ of theory).
l~_NMR ~CDC13); 6.80, 6.~3, 6.09, 5.97 (each m, 4H, olefin. H), 2.76, 2.64 (each ~, 6H, ~ (CH3) Z), 2.42 (d, 6.1 Hz, lH, CH), 0.1 (s, 9H, Si(CH3)3).
Mass spectrum~ 193 M', correct disintegration pattern.
Example 15 1-Chloro-6-(trimethylsilyl)boracyclohexa-2,4-diene 4.8 gofl-dimethylamino-5-(trimethyl6ilyl)boracyclohexa-2,4-diene were dissol~ed in 10 ml of ~ethylene chloride and cooled to -75~C. 29 ml of a 0.89 molar solution of BCl3 in methylene chloride were added to the a~ove sol~tion, the mixture wa~ allowed to warm up to room temperature, the solvent wa~ removed undèr reduced pressure and the product was distilled at 64-65~C. The yield of the organoboron compound was 3.36 g (-73~ of theory).
~H-NMR (CDCl3, 250 MHz): 7.5, 6.8, 6.45 (each br., 3H, olefin. H), 6.47 (dd, ~.4 Hz, lH, olefin. H), 3.6 ~br., lH, CH), 0.12 (~, ~H, Si (~H3) 3) .
Mass spectrum: 1~4 M , correct disintegration pattern.
~ 95/F 313 K WO - 25 -Example 16 Bis[(6-trimethylsilyl)~oracyclohexa-2,4-dien-1-yl] oxide (ra~ and me~o ~orm) 100 ~l of diethyl ether were cooled to -75~C a~d 0.021 g of water and 0.473 g of 1-chloro-6-(trimethylsilyl)bora-cyclohexa-2,4-diene were added in ~ucce~io~. The mixture waa allowed to warm up to room temperature, the ether was ~ lOved under reduced pressure and the crude product up to 180~C/10-3 mbar wa~ condensed in a cooled receiver. The yield of-the organo~oron compound was 0.32 g (8~ of theory).
lH-NMR (CDCl3~: 7.35, 6.6, 6.3, 6.1 (each m, 8H, olefin.
H), 2.84, 2.78, 2.5~ (each d, 5.2 Hz, 2H, CH), 0.1, 0.9, O.7 (each a, 18H, Si (CH3) 3) .
Mas~ ~pectrum: 314 M , correct di~integration pattern.
~ Rs --O--I Z o-- C
I
RY R~ RY Rr R~
RX RX ~X f~ TX RX
O ~-- - C--~ C C--C--RY ' RY RY ' RY R~ RY
~BRX, ~AIR~, -Ge-, -O-, -S-, ~SO, >SOz, ~NRX, ~CO, ~pRx or ~P(O)RX, where Rx and RY are identical or di~ferent and are each a hydrogen atom, a halogen atom or a Cl-C,O-group ~uch as a C1-C20-alkyl group, a Cl-C1O-fluoroalkyl group, a Cl-C1O-alkoxy group, a C~-Cl,-aryl group, a C6-C1O-fluoroaryl group, a C6-C~O-aryloxy group, a C2-C1O-alkenyl group, a C7-C~O-arylalkyl group, a C~-C40-alkylaryl group or a C~-C~O-arylalkenyl group and M~ i~ silicon, germani~m or ~in.
Examples of bridges are groups (M2RXRY)y~ where Ma i~
carbon, silicon, germanium or tin and Rx and RY are identical or different and are each a Cl-C20-hydrocarbon group such as Cl-C~O-alkyl or c6-C~4-aryl and y is 1 Qr 2, e.g. CH2, CH2CH2, CH ( CH3 ) CH2, C ( CH3 ) ( C6H5 ), C ( C6H5 ) CH(C~H~)C(CH3)z~ C(CH3)2, C(CH3) (C6H5), C(C6H5)2~ (CH3)2$i~
~CH3) 2Ge, tCH3) 2Sn, (C6H5) 2Si, (C6Hs) (CH3) Si, (C6H5) 2Ge, ~C6H5)2Sn, (CH2)~Si, CH2$i(CH3)z~ o-C6H4 or 2,2'-(C6H4)2 95/F 313 K WO - 4 ~
The pre8ent invention accordingly provides a tran~ition metal compound which contains as a ligand at lea~t one substituted or unQubxtituted boratabenzene group and is described by the formula I.
A preferred ~mho~ nt of the invention is a compound in whic~ M i~ an element of group IVb of the Periodic Table of the Elements, in parti~ular zirconium.
A preferred embo~;me~t of the invention i8 a compound in which the radical~ R are identical and are ea~h a hydro-gen atom, a Cl- C4 - alkyl group or ~ C6 - C10 - aryl group and Y
i~ a Cl-C~-alkyl group or NR2Z, where R2 is a C -C4-alkyl group, preferably a Cz-C4-alkyl group.
A preferred embodiment of the in~ention is a compound in which A is a substituted cyclopentadienyl ligand.
A preferred embodi~ent of the invention is a compound in which X is Cl-C1O-alkyl or NRa2, where R2 i-~ a Cl-C4-alkyl group, a C6-C~O-aryl group or a halogen acom, in particular chlorine.
A preferred embodiment of the invention ie a compound in which m - O or 1 when n = 1 and m - O when n ~ 2.
A i~ preferably a ~-ligand ~uch as cyclopentadienyl, indenyl or fluore~yl, which can each be either substituted or unsu~tituted.
~-~igands are preferably an u~ub~tituted cyclopenta-dienyl group or sub~tituted cyclopentadienyl group whichpreferably bear one or more Cl-C~O-hydrocarbon radicals a3 sub~tituents, e.g. 2-methylcyclopentadienyl, methyl-tert-butylcyclopentadienyl, tert-butylcyclopentadienyl, i~opropylcyclopentadienyl, di~ethylcyclopentadie~yl, trimethylethylcyclopent~;enyl, 5-phenylcyclopentadienyl, diphenylcyclopentadienyl, ~n~Anyl, 2-me~hyli n~enyl, ~-ethylin~nyl, 3-methylindenyl, 3-tert-butylin~yl, 2-methyl-4-phenylindenyl, 2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylinde~yl, 2-methyl-4-i~opropylindenyl, benzlnfl~nyl, 2-methyl-4,5-benzindenyl, 2-methyl-a-ace-naphthindenyl, ~-methyl-4,6-dii~opropylindenyl, ~luorenyl, 4-methylfluorenyl or 2,7-di-tert-butyl-fluorenyl.
Particular preference i~ given to compound~ of the formula I in which M i~ zirconium and X are identical and are each a halogen atom, in particular chlorine.
Particular preference is given to compound~ of ~he formula I i~ which L iQ a boratabenzene ligand of the formula II and the radical~ R are preferably identical and are each a hydrogen atom ~nd Y is preferably a C1-C~-alkyl group ~uch aq methyl, ethyl, propyl, isopropyl or butyl, or NRa2 in which R2 i~ a Cl-C,-alkyl group such a~
methyl, ethyl, propyl, isopropyl or butyl. When m i~ 1, A is preferably a cyclopentadienyl ligand s~ch as cyclo-pentadienyl, methylcyclopentadienyl, pentamethylcyclo-pentadienyl or indenyl. Pre~erence i-~ al~o given to compounds of the formula I in which X are identical and are each a Cl-C4-alkyl group, in particular methyl, or a C7-C~O-alkylaryl group, in particular benzyl, or a halogen atom, in particular ch~orine, and n i~ 1 or 2 and m is O
or 1 when n i~ 1 and m is O when n is 2 and the ~um of n+m+k can be 3 or 4.
Example~ of transition metal compound~ of the invention are: -(l-methylboratabenzene)~pentamethylcyclopentadienyl)-zirconium dichloride (1-butylboratabenzene)(pentamethylcyclopentadienyl)-zirconium dichloride (l-methylbora~benzene)(pentamethylcyclopentadien~l)-dimethylzirconium (l-butylboratabenzene)(pentamethylcyclopentadienyl)-dibenzylzirconium [1-(dimethylamino)boratabenzene](pentamethylcyclo-pentadienyl)-zirconium dichloride [1-(diethylamino)boratabenzene](cyclopentadienyl)-zirconium dichloride [l-(dimethylamino)boratabenze~e](pentamethylcyclo-pentadienyl)dimethylzirconium ~1-(diethylamino)boratabenzene](cyclopentadienyl)di-benzylzirconium (1-methylbora~abenzene)(cyclopentadienyl)zirconium dichloride (l-methylborat~h~n~ene)(methylcyclopentadienyl) 2 irconium dichloride (1-methylboratabenzene)(cyclopentadienyl)dimethylzir-conium (1-methylboratabenzene)(methylcyclopentadienyl)di-benzylzirconium bi~ methylboratabenzene)zirconium dichloride bis(1-methylboratabenzene)dimethylzirconium bis(l-methylborata~enzene)hafnium dichloride bis(l-methylboratabenzene)dibenzylzirconium (l-methylboratabenzene)zirconiumtrichloride (1-ethylboratabenzene)zirconium trichloride (l-methylboratabenzene)(indenyl)zirconium dichloride (l-~ethylboratabenzene)(indenyl)dimethyl zirconium (l-me~hylboratabenzene)(indenyl)dibenzyl zirconium [1-(dimethylamino)boratabenzene~(indenyl)zirconium dichloride (1-methylboratabenzene)(pentamethylcyclopentadienyl)-titanium dichloride (1-methylbor~tabenzene)(cyclopentadienyl)titanium dichloride [1-(dimethylamino)boratabenzene](cyclopentadienyl)-titanium chloride bi~(l-methylboratabenzsne)titanium dichloride bi~ methylboratabenzene)titanium chloride (1-methylboratabenzene)titanium ~richloride (1-methylboratabenzene)titanium dichloride (l-methylboratabenzene)(indenyl)titanium dichloride ~ dimethylamino)boratabenzene](indenyl)titanium chloride [l-(diethylamino)boratabenzene](pentamethylcyclopenta-dienyl~titanium dichloride tl-(diethylamino)boratabenzene~lpentamethylcyclopenta-dienyl)hafnium dichloride [1-(diethylamino)boratabenzene]~pentamethylcyclopenta-dienyl)zirconium dichloride ~1-(diethylamino)boratabenzene](pentamethylcyclopenta-dienyl)dimethylzirconium [1-(pyrrolidino)boratabenzene](pentamethylcyclopenta-dienyl)zirconium dichloride [l-(piperidino)borataben~ene](pentamethylcyclopenta-dienyl)zirconium dichloride tl-(pyrrolo)boratabenzene](pentamethylcyclopentadienyl)-zirconium dichloride~1-(bi8trimethylsilylamino)boratabenzene~(pentamethyl-cyclopentadienyl)zirconium dichloxide tl-(diisopropylamino)boratabenzene](pentamethylcy pe~tadienyl)zirconium dichloride [1-(N-methylanilino)bora~Ahen7,~e](pentamethylcyclopenta-dienyl)zirconium dichloride [1-(diphenylamino)boratabenzene~(pentamethylcyclopenta-dienyl)zirconium dichloride tl-(pyrrolidino)borat~h-n7ene]~cyclopentadienyl)zirconium dichloride [l-(piperidino)boratabenzene](cyclopentadienyl)zirconium dic~loride [l-(pyrrolo)boratabenzene](cyclopentadienyl)zirconium dichloride [l-~bi~trimethyl~ilylamino)boratabenzene](cyclopenta-dienyl)zirconium dichloride [1-(diisopropylamino)boratabenzene](cyclopentadienyl)-zirconium dichloride [1-(N-methylanilino)boratabenzene~tcyclopen~adien~l)-zirconium dichloridetl-(diphenylamino)~ora t aben z ene](cycl opent adienyl)-zirconium dichloride [l-(diphenylpho~phino) borat abenzene](pentamethylcyclo-pentadienyl) titanium dichloride [l-(~iphenylphosphino)boratabenzene~(pentamethylcyclo-pentadienyl)zirconium dichloride ~l-(diphenylphosphino)boratabenzene3(pentamethylcyclo-pentadienyl)dimethylzirconium S [l-(di~ethylphosphino)boratabenzene](pen~amethylcyclo-pentadienyl)zirconium dichloride [1-(dibutylphosphino)boratabenzene](pen~amethylcyclo-pentadienyl)zirconium dichloride [1-(dii~opropylphosphino)bora~abenzene](pentamethylcyclo-pentadienyl)zirconiu~ dichloride[1-(dicyclohexylphosphino)boratabenzene](pentamethyl-cyclopentadienyl)zirconium dichloride [1-(diphenylpho8phino)borat~benzene](cyclopentadienyl)-zirconium dichloride [1-(dimethylpho~phino)boratabenzene](cyclopentadienyl)-zirconium dichloride [1-(dibutylphosphino)boratabenzene](cyclopentadienyl)-zirconium dichloride E1-(diisopropylpho~phino)boratabenzene](cyclopenta-dienyl)zirconium dichloride[1-(dicyclohexylphoQphino)boratabenzene]( cyc lopenta-dienyl)zirconium dichlo~ide bis[1-(diethylamino)boratabenzene]zirconium dichloride bistl-(diethylamino)boratabenzene]dimethylzirconium bis[1-(pyrrolidino)boratabenzene]zirconium dichloride bis[1-(diphenylphosphino)boratabenzene~zirconium dichloride bi~[l-(dimethylphosphino)boratabenzene]zirconium dichloride [1-(diethylamino)boratabenzene](indenyl)zirconium dichloride ~1-(diethylamino)boratabenzene](fluorenyl)zirconium dichloride ~l-(~e~hylboratabenzene](fluorenyl)zirconium dichloride [l-(diethylamino)boratabenzene]titanium trichloride ~1-(diethylamino)boratabenzene] titanium dichloride bi~[l-(diethyla~ino)boratabenzene]ti~anium chloride ethylenebis[4~ methylboratabenzene)~zirconium dichloride - 95/F 313 K W0 - ~ -ethylenebi~[3~ methylboratabenzene)~zirconium dichloride ethylenebis[2-~1-methylboratabenzene)]zirconium dichloride ethylenebis(1-boratabenzene)]zirconium dichloride ethylenebi~s-(1-dimethylaminoboratabenzene)~zirconium dichloride ethylenebi~3-(l-dimethylaminoboratabenzene)~zirconium dichloride ethylenebis~2-tl-dimethylaminoboratabenzene)]zirconium dichloride ethylenebis[4-~l-diethylami~oboratabenzene)]zirconium dichloride ethylenebi~[4-(l-diphenylphosphinoboratabenzene)]-zirconium dichlorideethylenebis~4-(1-pyrrolidinoboratabenzene)]zirconium dichloride ethylenebi~[4~ methylboratabenzene)]titanium dichloride ethylenebix[3~ methylboratabenzene)]titanium dichloride ethylenebis~2-(1-methylbora~be~ene)]titanium dichloride ethylenebis(1-boratabenzene)titanium dichloride ethylene~(4-(1-methylboratabenzene))cyclopentadienyl~-zirconium dich-loride ethylene~(4-(1-~ethylboratabenzene))penta~ethylcyclo-pentadienyl~zirconium dichlorideethylene[(4-(1-methylboratabenzene))indenyl]zirconium dichloride ethylene[(4-(1-~ethylboratabenzene))fluorenyl]zirconium dichloride 3~ ethylene[(1-boratabenzene)cyclopentadienyl]zirconium dichloride ethyleneL(l-boratabenzene)indenyl~zirconium dichloride ethylene[(l-boratabenzene)fluorenyl]zirconium dichloride ethylenebis(1-methylaminoboratabenzene)]zirconium dichloride ethylenebis~l-phenylphosphino~oratabenzene)]zirconium dichloride ethylenebis(1-oxyboratabenzene)]zirconium dichloride ethylenebi~l-thioboratabenzene)]zir~onium dichloride dimethylsilanediylbi~4-(1-methylboratabenzene)]zirconium dichloride dimethyl~ilanediylbis~4-(l-dimethylaminoboratabenzene)]-zirconium dichloride dimethylsilanediylbiQ~4-(1-diphenylpho~phinoborata-benzene)]zirconium dichloride dimethylsilanediylbi~[(l methyleneboratabenzene)~-zirconium dichloride dimethyl~ilanediylbi~[(l-methylaminoboratabenzene)~-zirconium dichlo~idedimethylsilanediylbis[(l-oxyboratabenzene)~zirconium dichloride dimethylsilanediyl[(4-(1-methylboratabenzene)) cyclopenta-dienyl]zirconium dichloride lS dimethylsilanediyl[(4-(1-methylboratabenzene))penta-~ethylcyclopentadienyl]zirconium dichloride dimethyl3ilanediyl[(4-(l-methylboratabenzene))indenyl]
zirconium dichloride dimethylsilanediyl[(4-(l-methylborar~hen7.ene))fluorenyl]-zirconium dichloridedimethyl~ilanediyl[(4-(l-dimethylAmjno~oratabenzene)) cyclopentadienyl]zirconium dichloride dimethylsilanediyl[(4-(1-diphenylpho6phinolborata-benzene))cyclopentadienyl]zirconium dichloride dimethylsilanediyl[(3-(1-dime~hylaminoboratabenzene))-cyclopentadienyl~zirconium dichloride dimethylsilanediyl~(2-~l-dimethyl~minohoratabenzene))-cyclopentadienyl]zirconium dichloride dimethylsilanediyl[(l-methylaminoboratabenzene))cyclo-pentadienyl]zirconium dichlorideisopropylidenyl[(4-(1-dimethylaminoboratabenzene))cyclo-pentadienyl]zirconium dichloride isopropylid~nylbi~[s-(l methylboratabenzene)]zirconium dichloride ~
35 The invention provideQ a proce~ for preparing the navel transition metal compound-~ h~ving the formula (I). The process is illustrated by the synthesis schemes below ~or co...~ounds of the formulae IV, v and VI. I~ these ~ormulae, R, Y, M and X are defined as in formulae I and II. A i~ a li~and ~uch as cyclopentadienyl, indenyl or fluorenyl, each of which may be either ~ubstituted or un~u~tituted. Ml i~ a metal of main group Ia of the Periodic Table of the ~lement~.
For example, in a proces~ for preparing a compound havi~g the formula (I), a compound having the formula (III) reacts wi~h MXl where 1 i~ an integer from 3 to 5.
In an alternative proce~s for preparing a compound having the formula (I), a compound having the formul~ ~V) reacts with A-Ml'.
In a further alternative proces~ for preparing a compound having the formula (I), a compou~d having the formula ~III) reacts with AMX~
R~ R
~Q ~ R
~ r ~' R~--r R
In an alternative proce~R for preparing a compound having - 95~F 313 K WO - 12 -the formula ~I), a compound having the formula (VII) reacts with MX, where 1 is an integer from 3 to 5 and Z
is an element of group IVa of the Periodic Table of the Element~ and R3 are identical or different and are each a hydrogen atom, a Cl-C2D-group,- for example a Cl-C20-hydrocarbon radical such as a C1-C20-alkyl group or a C6-C20-aryl group, or ~wo adjacent radical~ R3 together with the atoms connecting them can form a ring y~tem.
Preferably Z i~ ~ilicon, germanium, tin or lead and R3 are identical and are particularly preferably each a Cl-Clc-alkyl group 8uch a~ methyl, ethyl, i~opropyl or butyl or a C~-C1c-aryl group such a~ phenyl.
In an alternative process for preparing a compound having the formula (I), a compound having the formula react~ with AMX1-l R R
R~Y
R R ZR,~ R
R R~~
R~ y t~l ~
R R
~Y
Y
q R
~he compound~ of the formulae III and VII can be prepared ~ 95/F 313 K WO - 13 -by literat~re methods (Organometallics 1995, 14, 471).
The conver~ion of the compound~ of the formula III into the de~ired tran~ition metal complexes i~ k~own in principle. For this purpose, the monoanion of the formula III i~ reacted in an inert solvent with the corresponding metal halide ~uch as zirconium tetrachloride. A is a li~and Yuch aQ cyclopentadienyl, indenyl or fluorenyl which can eac~ be either ~ubstituted or un~ubstituted.
S~itable solvents for the reaction are aliphatic or aromatic ~olvents such as h~nP or toluene, ether solvent~ such as ~etrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons ~uch as o-dichloro-benzene.
The invention provide~ for the use of the compound ha~ing the formula I as a catalyst component in ~he polymerization of olefins. The present invention accordin~ly provides a process for preparing a polyolefin by polymerization of one or more olefin~ in the pre~ence 2 0 of a transition metal compound of the ~ormula I . For the purposes of the invention, the term polymeriza~ion refer~
to both homopolymerization and copolymerization.
In the process of the in~ention, preference is given to polymerizing one or more olefin~ of the formula R'-CH=CH-R~ where R~ and Rb are iden~ical o~ different and are eacha hydrogen atom or a ~ydrocarbon radical having from 1 to 2~ carbon atom~, in particular from 1 to 10 carbon atoms, or Ra and Rb together with the atoms connecting them form one or more rings. Examples of such olefi~ are l-olefins ha~ing 1-20 carbon atom~, for example ethylene, propene, 1-butene, l-pentene, l-hexene, 4-methyl-1-pentene or l-octene, styrene, cyclic or acyclic diene~ ~uch as 1,3-butadiene, isoprene, 1,4-hexadiene, norbornadiene, vinylnorbornene, s-ethylidenenorbornene or cyclic mono-olefins such a~ nor~ornene or tetracyclododecene. In theproceyy o~ the in~ention, pre~erence is given to homopo-lymerizing ethylene or propylene or copolymerizing ethylene with one or more acyclic 1-olefins having ~rom 3 to 20 carbon atoms, for example propylenç, and/or one or more diene~ havi~g from 4 to 20 carbon atoms, for 5 examlple 1, 3-butadiene .
The polymerization i-~ preferably carried out at a temperature of from -60 ~o 250~C, more preferably 20 to 70~C, particularly preferably from 50 to 20~C. The pressure is preferably from 0.5 to 2000 bar, particularly preferably ~rom 4 to 64 bar, very particularly prefera~ly from 5 to 64 bar.
The polymerization can ~e carried out in solution, in bulk, in su~pen~ion or in the gas pha-~e, continuously or batchwise, in one or more ~tage~.
The catalyst used in the proces~ of the invention prefera~ly comprise~ a ~ran~ition metal compound. It i~
also po~sible ~o use mix~ure~ of two or more transition metal compound~ ~r mixture~ with metallocenes, for example for preparing polyolefins having a broad or multimodal molecular weight distribution.
In principle, a suitable cocatalyst in the proce~s of the invention is any compound which, owing to i~ Lewis acidity, can eonvert the neutral transition metal compound in~o a cation and Qtabilize the latter ("labile coordination"). Furthermore, the cocatalyst or the anion formed therefrom 6hould undergo no further reactions with the cation formed (EP-A-427 6g7). A6 cocatalyst, pre~erence i~ given to using an aluminum compound and/or a boron compound.
The boron compound preferably has the formula R5XNH4.xBR~, RsxpH~-xBR6~ R53CBR6~ or BR63, where x i~ from l ~o, 4, preferably 3, and the radical~ R5 are identical or different, preferably identical, and are C~-Cl0-alkyl or C6-ClR-aryl or two radicals R5 together with the atoms connecting them ~orm a ring, and the radicals R6 are identical or different, preferably identical, and are C6-Cl~-aryl which may be sub~tituted by alkyl, haloalkyl or fluorine. In particular R5is ethyl, propyl, butyl or phenyl and R6 is phenyl, pentafluorophènyl, 3,5-bi~-(trifluoromethyl)phenyl, mesityl, xylyl or tolyl (EP-A-2~ 003, EP-A-2~7 004 and EP-A-426 63~).
The cocatalyst used is preferably an all~m~ m compound ~uch as aluminoxane and/or an aluminum alkyl.
The cocataly~t used i~ particularly preferably an aluminoxane, in particular one of the formula VIIa for the linear type and/or the formula VIIb for ~he cyclic type, ~ R~ -¦ ~ R~
~ O- Al O Al ~ ~n~J) R~ _ _ D R4 Al O ~llO) _ _ p~2 where, in the ~ormulae VIIa and VIIb, the radicals R~ are identical or different and are each hydr~gen or a Cl-C20-hydrocarbon group such as a C1-Cle-alkyl group, a C6-C1,-aryl gr~up or benzyl and p is an integer from 2 to 50, preferably from 10 to 35.
The radical~ R4 are p~eferably identical and are hydro-gen, methyl, isobutyl, phenyl or benzyl, particularly preferably methyl I~ the radical~ R4 are different, then they are pre~erably me~hyl and hydro~en or alternati~ely methyl ~ 95/F 313 K W0 - 16 -and isobutyl, with hydrogen or i~obutyl preferably ~eing present in a proportion of from 0.01 to 40~ by number (of the radicals R4).
The methods of preparing the al~mi~o~nes are known. The exact -~patial structure of the al~m~nox~ne~ not known (J. Am. Chem. Soc. (1993) 115, 4971). For example, it i~
concei~able that chains and rings can joi~ to ~or~ larger two-dimen~ional or three-dimen~ional ~tructure~.
Regardless of the method of pr~paration, all al~;nox~e ~olution~ ha~e in common a varying content of unreacted alu~nl~ starting compound which i9 pre-~ent in free form or a~ adduct.
It is pos~ible to preacti~ate the tran~ition metal compound u~ing a cocatalyst, in particular an alumin-oxane, prior to use in the polymerization reaction. Thissignificantly increa~e~ the polymerization acti~ity. The preactivation of the transition metal compound i~
preferably carried out in ~olution. The transition metal compound i~ here preferably di~olved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbo~ are aliphatic or aromatic hydrocarbons.
Preference i~ given to u~ing toluene.
The concentration of the al~ oxane in the solution is in the range from about 1~ by weight to the saturation limit, preferably from 5 to 30~ by weight, in each case ba~ed on the total amount of solution. The transition metal compound can be u~ed in the same concentration, ~ut it is preferably u~ed in an amount of from 10-~ to 1 mol per mol of aluminoxane. The preactivation time i~ from 5 minutes to 60 hours, preferably from 5 to 60 min~te~.
The preactivation is carried out at a temperature of from -78 to 100~C, preferably from o to 70~C.
The tran~ition metal compound i8 preferably u~ed in a concentration, ba-~ed on the ~ran~ition ~etal, of from 10~1 to lO-a mol, pre~erably from lO-' to 10-7 mol, of tran~ition metal per d~ of sol~ent or per dm3 of reactor volume. The aluminoxane is preferably used in a concentration of from 1o-6 to 1o-l mol, preferably fro~ 10-5 to 10-2, mol per dml of solvent or per dm~ of rea~tor volume. The other cocatalysts mentioned are used in approximately equimolar amount~ to the transition metal compound. However, higher concentrations are alRo posYible in principle.
To re~ove catalyst poisons pre~e~t in the ole~in, purification using an aluminum compound, preferably an al~m; ~l~m alkyl such ag trimethyla~lm;nl~m or trie~hyl-al~minum, is advantageous. Thi~ purification can be carried out either in the polymerization system itself or the ole~in i~ brought into contac~ with the aluminum com-pound and sub~equently separated off again before addition to the polymerization system.
In the proceYs of the invention, hydrogen can be added as a molecular weight regulator and/or to increa~e ~he catalyst activity. This enables low molecular weight polyolefin~ ~uch a~ waxe~ to be obtained.
In the process of the pre~ent inve~tion, the tran~ition metal catalyst is preferably reacted with the cocataly~t outside the polymerization reac~or in a separate step using a suitable golvent. Application to a support can also be carried out during thi~ procedure.
In the process of the invention, a prepolymerlzation can be carried out with the aid o~ the transition metal compound. For the prepolymerization, pre~erence is given to using the (or one of the) olefin(s) used in the polymerization.
The catalyst u~ed in the proce~s of the invention can be ~upported. Application to a support enables, for example, the particle morphology of the polyolefin prepared to be controlled. Here, the transition metal compound can be f irst reacted with the ~upport and ~ub~equently wich the cocatalys~. The cocataly~t can al~o be supported ~irst and subsequently reacted with the tran~ition metal co~pound. It is also possible to support t~e reaction product of tran~ition metal compound and cocatalyst.
Suitable ~upport materials are, for example, ~ilica gel~, aluminum oxide~, ~olid aluminoxane or other inorganic ~upport ma~erial~ such as magnesium chloride. Ano~her lo ~uitable Qupport material i~ a polyolefin powder i~
finely di~ided form. The preparation of the ~upported cocatalyst can be carried out, for example, as de~cribed in EP-A-567 952.
If the polymerization is carried out as a ~uspen~ion or solution polymeri~ation, an inert 601vent cu~tomary for the Ziegler low-pres~ure process is used. For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon, for example propane, butane, h~Y~n~, heptane, isooctane, cyclohexane, methylcyclo-hexane. A petroleum or hydrogenated diesel oil fxactioncan al~o be u~ed. It i9 also po~sible to use toluene.
Preference i~ given to carrying out t~e polymerization in the liquid monomer.
Before addition of the cataly~t, in particular the -~upported catalyst system (compri~ing the tran~ition metal compound of the invention and a ~upported cocatalyst), another aluminum alkyl compound such as trimethylaluminum~trie~hylaluminum~triisobutylalllm;nllm~
trioctylaluminum or i~oprenrlaluminum can be introduced into the reactor to make the polymerization sy~te~ inert (for example to remove catalyst poi~ons pre~ent in t~
olefin). ~iQ compound is added to the polymer~zatlo~
sy~tem in a concentration of from 100 to 0.01 mmol o~ Al per kg of reactor conten~. Pre~erence is given, to trii~obutylaluminum and triethylaluminum in a concentration o~ from 10 to o.1 mmol of Al per kg of reactor content~, This enableQ the molar Al/ml ratio to be made -~mall in the synthesi~ of the ~upported catalyst YyStem ~
If inert qolventR are used, the monomers are preferably metered in in ga~eou~ or liquid form.
The specific tran~ition metal compound~ described in the pre~ent invention are suita~le for the preparation of polyolefins. The latter are suitable, in particular, for producing shaped bodies such as filmR, plates or large hollow bodieg (e.g. pipe~) and can al~o be used as plasticizer and lubricant formulations, for melt adhesive applications, coatings, seals, insulatio~, filler compo~itions or ~ound insulation material~.
U6e of hydro~en or increasing ~he polymerization tempera~ure make it p~ssible to obtain polyolefin~ having 15 a low molar ma6~ ~ e . g . waxe~, who~e hardnes~ or melting point can be varied by means of the comonomer content.
Selection of the polymerization proce~ and the type(s) of comonomer(s), ~nd also amount(s) of comonomer(~), enable olefin copolymers having ela~tomeric properties to be prepared, for example ethylene-propylene-1,4-hex~;ene terpolymer~.
The following example~ illus~rate the invention.
Preparation and handling of organometallic compounds were carried out with exclu~io~ of air and moi~ture under protect~ve argon ga~ (Schlenk technique). All solvents r~quired were freed of air and moi~ture ~efore u~e by boiling for a number of hour~ over a suitable desiccant and ~ub~equent di-~tillation under argon.
The Al/CH3 ratio in the al~m;nn~ane was de~ermined by decomposing the sample with HzS04 and determining .the volume of the hydrolysis gase~ formed under standard conditions and by complexometric titration of the aluminum in the then completely dis~olved ~ample by the Schwarzenbach method. The compounds were characterized using ~H-NMR, ~3C-NMR and IR spectroscopy.
Examples Example 1 bis(l-Methylboratabenzene)zirconium dichloride 1 g of zirconium tetrachloride and 0.84 g of (1-methyl-boratabenzene)lithium were ~u~pended in 20 ml of ~oluene and ~tirred for three days at 100~C. The yellow suspension obtained was filtered and the ~olvent wa~
removed under reduced pre~sure. The yellow solid o~tained was washed with 5 ml of hexane. The yield of transition metal compound wa~ O.B9 g (60~ of theory).
'~-NMR (CD2Cl2): 7.6, 6.6, 6.3 (each m, 5H, arom. H), 0.9 (s, 3H, CH3). Mas~ spectrum: 344 Mt~ correct disintegration pattern.
Example 2 di(~-Chloro)tetra[h6-(1-methylboratabenzene)]dititanium 0.48 g of titanium trichloride and 0.~1 g of (1-methyl-boratabenzene)lithium are su~pended in 10 ml of toluene and ~tirred ~or ~hree day-~ at llO~C. The brown suspension obtained is filtered and the filtrate is cooled to -30~C.
The bro~n solid obtained i~ wa~hed with 5 ml of h~x~n~, giving the txansition metal compound in a yield of 60 (0.49 g).
Ma~ ~pectrum: 265 M+, correct disintegration pattern.
Example 3 ~1-Methylboratabenzene)titanium trichloride 1.36 g of 1-~ethyl-6-(trimethylstannyl)-2,4-boracyclo-h~y~nediene are dissol~ed in 10 ml of hexane and 1.1 g of ~ 9S/F 313 K W0 - 21 -titanium tetrachloride are added at -10~C. After ~tirring for 3 hour~, the red-violet ~olution i~ evaporated until crystallization commence~ and stored for 12 hour~ at -300C. The product is obtained in the form of deep violet S cry~tals in a yield of 93~ (1.22 g).
H-NMR (CD2Cl2): 8.1, 7.0, 7.3 (each m, 5H, arom. H), 1.1 (8 , 3H, CH3). Ma~ spectrum: 244 Ml, correct disin-tegration pattern.
Example 4 (1-Methylborataben 2 ene ) c yC lopentadienyltitanium dichloride 0.57 g of cyclopentadienyltitanium trichloride are dissolved in S ml of tetrahydrofuran and admixed at - ~ 0 ~ C
with a solution of 0.65 ~ of 1-methyl-6-(trimethyl-stannyl)-2,4-boracyclohexanediene in 2 ml of tetrahydro-~uran. After ~he Rolu~ion has been warmed to room temperature, the precipitated dark green ery~tal~ are filtered off; yield: 60~ (0.4 g).
lH-NMR (CD2Cl2): 7.8, 6.9, 5.9 ~each m, 5H, arom. H), 6.7 (m, 5H, Cp-H), 1.1 (s, 3H, CH~). Ma~s spe~trum: 274 M+, correct diQintegration pattern.
Example 5 ~ ethylboratabenzene)cyclopentadienyl~iraonium dichloride ~
0.3 g of cyclopentadienylzirconium trichlorida is ~uQpended in 5 ml of toluene and ad~ixed at room temperature with a solution of 0.3~ ~ of 1-methyl-6-(trimethylsilyl)-2,4-boracyclohexanediene in 2 ~ml of toluene. Af~er the solution has been heated for 3 hours at ~OoC, it i~ cooled to -30~C and ~tored for 12 hour~at thi~ temperature. Thi3 gives 0.26 g of the yellow compound (70~).
lH-NMR (~D2C12): 7.7, 6.3, 6.~ (each m, SH, arom. H), 6.
CA 022404~2 l998-06-l9 9~/F 313 K wo - Z2 -(m, 5H, Cp-H), 1.0 ~s, ~H, CH3). ~a~ ~pe~trum: 316 Ml, correct disintegration pattern.
Example 6 bis(l-Methylboratabenzene)hafnium dichloride 0.32 g of hafnium tetrachloride i~ ~uspended in ~ ml of toluene and admixed at room temperature with a solution of 0.33 g of 1-methyl-6-(trimethylsilyl)-2,4-boracyclo-hexanediene in 2 ml of toluene. After the ~olution ha~
been ~eated for 2 hours at 70~C, it is cooled to -30~C
and ~tored for 12 hours at thi~ temperature. ThiQ givee 0.37 g of the yellow compound (88~).
H-NMR (CD2C12): 7.6, 6.3, 6.6 (each m, 5H, arom. H), 5.8 (m, 5H, Cp-H), 1.0 (~, 3H, CH3) . Mas~ ~pectrum: 132 M+, correct di~integration pattern.
Example 7 tl-Methylboratabenzene)(pentamethylcyclopentadienyl)-hafnium dichloride 1.1 g of peneame~hylcyclope~tadienylhafnium trichloride are ~uspended in 10 ml of toluene and admixed at room temperat~re with a ~olution of 0.27 g o$ l-methylborata-benzenelithium in 10 ml of toluene and 2 ml of dimethoxy-ethane. After the ~olution has been heated for 3 hours at 110~C, the suspension is filtered and the filtrate is cooled to -30~C and stored for 12 hours at this temperature. Thi~ give~ 1. 0~ g of the pale yellow compound (85~).
H-NMR (CD2C12): 7.5, 6.2, 6.0 (each m, 5H, arom. H), 1.8 (s, lSH, Cp-CH3), 0.8 (x, 3H, CH3) . Mas~ spectrum 476 M+, correcC di~integration pattern.
Polymerization The catalysts of the formula (I) were used for PE
' CA 02240452 1998-06-19 - ss/F 313 K wo - 23 -polymerization in a su~pen~ion polymerization in an autoclave. Cataly#t I is bisll-methylboratabenzene)-zirconium dichloride. Cataly-qt II i-~ methylborata-benze~e~(pentamethyl~yclopentadienyl)zirconium dichloride. Catalyqt II~ iq ~l-dimethylaminoborata-~enze~e)(pentamethylcyclopen~adienyl)zirconium dichloride.
Example ~
2.0 mg of cataly~t II (0.0052 mmol of Zr) were dissol~ed under argon ~hile ~tirring in 1.5 ml o~ toluene in a Schlenk tube. The ~olution was then activated by ~;n~
3.7 ml of 30~ ~trength MAO (17.69 mmol of Al; 2r:Al =
1:3402) from Witco and thi~ ~olution wa~ added to 750 ml of ~xxsol loo/120. The catalyst solution wa~ tran6ferred to an autoclave. In the autoclave, polymerization wa~
carried out for one hour at a tempera~ure of 70OC and a stirrer ~peed of 750 rpm under an ethylene partial pressure o~ 4 bar. From the yield of 145.72 g of PE, which is formed as a fine p~wder, the catalyst activity is calculated a~ 7006 g PE/mmol Zr/bar C2H~/h.
~mrles 9 to 13 were carried out similarly to Example a.
The changes from Example Y are ~hown in Table 1 below.
Table 1: Polymerization Examples 9 to 13 Example Cat. ~at. Cat. Al Zr:Al Pre~sure rield Cataly~t [mg] ~mmol][mmol~ of C,H, tg] acti~rity~
[bar]
259I 1.8 0.0052 15.77 1:3033 4 12.26 586 10I 2.q 0.007023.89 1:3413 4 17.86 641~
11II 1.7 0.0044 16.72 1:3800 4 69.76 3982 "
12III 2.4 0.005821 99 1:3791 4 41.50 17B9 13III 2.8 0.006723.~9 1:3566 ~ 42.90 1~01 ~Catalyst acti~ity: [g PE/mmol Zr/bar C2H4/h]
~ 95/F 313 K W0 - 24 -Preparation of organoboron compound~
Example 14 1-Dimethylamino-6-(trimethylsilyl)boracyclohexa-2,4-diene 1.5 g of l-dimethylA~;nohoratabenzenelithium ~TMEDA) were suspended in 50 ml o~ pentane and cooled to -75~C. 1.0 ml of chlorotrimethyl~ilane wa~ added to the ~uspension, the ~ixture wa~ allowed to warm up to room temperature and filtered, the pentane was removed under reduced pres~ure and the product wa~ distilled at 103~C/12 mbar. The yield of the organoboron compound wa~ 1.0 g (84~ of theory).
l~_NMR ~CDC13); 6.80, 6.~3, 6.09, 5.97 (each m, 4H, olefin. H), 2.76, 2.64 (each ~, 6H, ~ (CH3) Z), 2.42 (d, 6.1 Hz, lH, CH), 0.1 (s, 9H, Si(CH3)3).
Mass spectrum~ 193 M', correct disintegration pattern.
Example 15 1-Chloro-6-(trimethylsilyl)boracyclohexa-2,4-diene 4.8 gofl-dimethylamino-5-(trimethyl6ilyl)boracyclohexa-2,4-diene were dissol~ed in 10 ml of ~ethylene chloride and cooled to -75~C. 29 ml of a 0.89 molar solution of BCl3 in methylene chloride were added to the a~ove sol~tion, the mixture wa~ allowed to warm up to room temperature, the solvent wa~ removed undèr reduced pressure and the product was distilled at 64-65~C. The yield of the organoboron compound was 3.36 g (-73~ of theory).
~H-NMR (CDCl3, 250 MHz): 7.5, 6.8, 6.45 (each br., 3H, olefin. H), 6.47 (dd, ~.4 Hz, lH, olefin. H), 3.6 ~br., lH, CH), 0.12 (~, ~H, Si (~H3) 3) .
Mass spectrum: 1~4 M , correct disintegration pattern.
~ 95/F 313 K WO - 25 -Example 16 Bis[(6-trimethylsilyl)~oracyclohexa-2,4-dien-1-yl] oxide (ra~ and me~o ~orm) 100 ~l of diethyl ether were cooled to -75~C a~d 0.021 g of water and 0.473 g of 1-chloro-6-(trimethylsilyl)bora-cyclohexa-2,4-diene were added in ~ucce~io~. The mixture waa allowed to warm up to room temperature, the ether was ~ lOved under reduced pressure and the crude product up to 180~C/10-3 mbar wa~ condensed in a cooled receiver. The yield of-the organo~oron compound was 0.32 g (8~ of theory).
lH-NMR (CDCl3~: 7.35, 6.6, 6.3, 6.1 (each m, 8H, olefin.
H), 2.84, 2.78, 2.5~ (each d, 5.2 Hz, 2H, CH), 0.1, 0.9, O.7 (each a, 18H, Si (CH3) 3) .
Mas~ ~pectrum: 314 M , correct di~integration pattern.
Claims (14)
1. A compound having the formula I
LnAmMXk (I), where L is a boratabenzene ligand of the formula II
where the radicals R are identical or different and are each a hydrogen atom, a C1-C10-group such as a C1-C10-alkyl group or a C6-C10-aryl group and two adjacent radicals R together with the atoms connecting them can form a ring system, and Y is a hydrogen atom, a C1-C10-group such as a C1-C10-alkyl group or a C6-C10-aryl group, a halogen atom, an NR22 or PR22 radical, where R2 is a halogen atom, a C1-C10-group such as a C1-C10-alkyl group or a C6-C10-aryl group, A is a .pi.-ligand such as cyclopentadienyl which can be either substituted or unsubstituted and adjacent substituents on the cyclopentadienyl ligand can form a ring, M is a metal of group IVb of the Periodic Table of the Elements and X are identical or different and are each a hydrogen atom, a C1-C40-group such as a C1-C20-alkyl group, a C1-C10-alkoxy group, a C6-C20-aryl group, C2-C12-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, an OH group, a halogen atom or NR2 2, n is 1 or 2, m is 0 or 1 and k is an integer from 1 to 3, where the sum of n+m+k is 3 or 4.
LnAmMXk (I), where L is a boratabenzene ligand of the formula II
where the radicals R are identical or different and are each a hydrogen atom, a C1-C10-group such as a C1-C10-alkyl group or a C6-C10-aryl group and two adjacent radicals R together with the atoms connecting them can form a ring system, and Y is a hydrogen atom, a C1-C10-group such as a C1-C10-alkyl group or a C6-C10-aryl group, a halogen atom, an NR22 or PR22 radical, where R2 is a halogen atom, a C1-C10-group such as a C1-C10-alkyl group or a C6-C10-aryl group, A is a .pi.-ligand such as cyclopentadienyl which can be either substituted or unsubstituted and adjacent substituents on the cyclopentadienyl ligand can form a ring, M is a metal of group IVb of the Periodic Table of the Elements and X are identical or different and are each a hydrogen atom, a C1-C40-group such as a C1-C20-alkyl group, a C1-C10-alkoxy group, a C6-C20-aryl group, C2-C12-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, an OH group, a halogen atom or NR2 2, n is 1 or 2, m is 0 or 1 and k is an integer from 1 to 3, where the sum of n+m+k is 3 or 4.
2. A compound as claimed in claim 1 in which M is an element of group IVb of the Periodic Table of the Elements, in particular zirconium.
3. A compound as claimed in claim 1 or 2 in which the radicals R are identical and are each a hydrogen atom, a C1- C4 -alkyl group or a C6-C10-aryl group and Y is a C1-C4-alkyl group or NR22, where R2 is a C1-C4-alkyl group.
4. A compound as claimed in one or more of claims 1 to 4 in which A is a substituted cyclopentadienyl
5. A compound as claimed in one or more of claims 1 to 5 in which X is NR22, where R2 is a C1-C4-alkyl group, a C6-C10-aryl group or a halogen atom, in particular chlorine.
6. A compound as claimed in one or more of claims 1 to 6, wherein m = 0 or 1 when n = 1 and m = 0 when n = 2.
7. A compound as claimed in one or more of claims 1 to 7, wherein L and A are joined to one another by means of a bridge and L are identical or different when n is 2.
8. A process for preparing a compound having the formula (I) as claimed in any of claims 1 to 7, wherein a compound having the formula (III) reacts with MX1, where 1 is an integer from 3 to 5.
9. A process for preparing a compound having the formula (I) as claimed in any of claims 1 to 7, wherein a compound having the formula (v) reacts with A-M'1.
10. A process for preparing a compound having the formula (I) as claimed in any of claims 1 to 7, wherein a compound having the formula (VII) reacts with AMX1-1.
11. The use of the compound having the formula I as claimed in any of claims 1 to 7 as a catalyst component in the polymerization of olefins.
12. A catalyst comprising a) at least one compound as claimed in one or more of claims 1 to 7 and b) at least one cocatalyst.
13. A process for preparing a polyolefin by polymerization of one or more olefins in the presence of a compound as claimed in one or more of claims 1 to 7.
14. A polyolefin able to be prepared by the process as claimed in claim 13.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19548298 | 1995-12-22 | ||
| DE19548298.0 | 1995-12-22 | ||
| DE19624466.8 | 1996-06-19 | ||
| DE19624466 | 1996-06-19 |
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|---|---|---|---|
| CA002240452A Abandoned CA2240452A1 (en) | 1995-12-22 | 1996-12-19 | Transition metal compound |
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| EP (1) | EP0868441A2 (en) |
| JP (1) | JP2000503001A (en) |
| KR (1) | KR19990076684A (en) |
| CN (1) | CN1209141A (en) |
| BR (1) | BR9612165A (en) |
| CA (1) | CA2240452A1 (en) |
| NO (1) | NO982855L (en) |
| WO (1) | WO1997023512A1 (en) |
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|---|---|---|---|---|
| US6114270A (en) * | 1998-08-07 | 2000-09-05 | Equistar Chemicals, L.P. | Polymerization-stable anionic ancillary ligand containing alkylimido catalysts and method of using the same |
| US6294626B1 (en) | 1999-11-15 | 2001-09-25 | Equistar Chemicals, Lp | Olefin polymerization catalysts containing modified boraaryl ligands |
| US6444765B1 (en) | 2000-06-14 | 2002-09-03 | Equistar Chemicals, Lp | Olefin polymerization process for producing broad MWD polymers |
| US6812304B2 (en) | 2000-06-14 | 2004-11-02 | Equistar Chemicals, Lp | Process for producing improved premixed supported boraaryl catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5468889A (en) * | 1994-06-20 | 1995-11-21 | The University Of Toledo | Boryl zirconocene organic 1,1-dimetallic compounds |
| US5554775A (en) * | 1995-01-17 | 1996-09-10 | Occidental Chemical Corporation | Borabenzene based olefin polymerization catalysts |
-
1996
- 1996-12-19 CN CN96180062A patent/CN1209141A/en active Pending
- 1996-12-19 CA CA002240452A patent/CA2240452A1/en not_active Abandoned
- 1996-12-19 KR KR1019980704796A patent/KR19990076684A/en not_active Application Discontinuation
- 1996-12-19 EP EP96944017A patent/EP0868441A2/en not_active Withdrawn
- 1996-12-19 WO PCT/EP1996/005717 patent/WO1997023512A1/en not_active Application Discontinuation
- 1996-12-19 BR BR9612165-3A patent/BR9612165A/en not_active Application Discontinuation
- 1996-12-19 JP JP9523307A patent/JP2000503001A/en active Pending
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| WO1997023512A1 (en) | 1997-07-03 |
| CN1209141A (en) | 1999-02-24 |
| NO982855D0 (en) | 1998-06-19 |
| JP2000503001A (en) | 2000-03-14 |
| BR9612165A (en) | 1999-12-28 |
| EP0868441A2 (en) | 1998-10-07 |
| KR19990076684A (en) | 1999-10-15 |
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