CA2023559C - Process for the preparation of a polyolefin - Google Patents
Process for the preparation of a polyolefin Download PDFInfo
- Publication number
- CA2023559C CA2023559C CA002023559A CA2023559A CA2023559C CA 2023559 C CA2023559 C CA 2023559C CA 002023559 A CA002023559 A CA 002023559A CA 2023559 A CA2023559 A CA 2023559A CA 2023559 C CA2023559 C CA 2023559C
- Authority
- CA
- Canada
- Prior art keywords
- group
- indenyl
- metallocene
- hydrogen atom
- mixture
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Process for the preparation of a polyolefin Olefins of the formula R11-CH=CH-R12 (R11, R12 = H or C1-C14-alkyl) are polymerized in the presence of a catalyst consisting of at least one metallocene of the formula I
Description
':~,r~
..
HOECHST AKTIEIdGESELLSCHAf'T HOE 89/F 266 Dr.DA/sch Description Process for the preparation of a polyolefin The invention relates to an olefin polymer of high molecular weight and low residual catalyst content.
Isotactic PP is prepared with the aid of ethylene-bis-(4,5,6,7)-tetrahydro-1-indenyl)-zirconium dichloride together with an alumino~ane in a suspension polymeriza-tion reaction (cf. EP-A-185,918). The polymer has a narrow molecular weight distribution (z~/I~, 1.6 to 2.6).
It has been possible to achieve a considerable increase in the activity of the catalyst system by a specific :, preactivation method (cf. DE-3,726,067). The particle morphology of the polymer has likewise been improved by this preactivation method.
The molecular weights of the polymers obtained in accor-dance with these two applications are still too low far industrial use.
There was thus the object of discovering a process for the preparatioxi of a high molecular weight olefin polymer which can be carried out in an industrially interesting temperature range with a high catalyst activity.
It has been found that the object can be achieved by polymerization of olefins in the presenee of certain metallocene catalysts.
The invention thus relates to a process for the prepara-tion of a polyolefin by polymerization of an olefin of the formula R11-CH=CH-R12, in which R11 and R12 are identi-cal or different and are a hydrogen atom or a C~-C1w-alkyl radical, or R11 and Rla, together with the carbon atom joining them, form a ring having ~ to 28 carbon atoms, at ~.~ 3' ~a ~-a temperature of OnC to 150°C, under a pressure of 0>5 to 100 bar, in solution, in suspension or in the gas phase and in the presence of a catalyst which consists of a metallocene and an aluminoxane of the formula (II) j ~1 - o ~1- o ~ ~ ~ a. 0 ( I I ) R10 n R
for the linear type, and/or of the f~renula (III) Al - O (III) n-~ a for the cyclic type, in which, in the formulae (II) and ( III ) , R1° is a C1-Cs-alkyl group and n is an integer from 2 to 50, wherein the metallocene is at least one compound of the formula (I) R~
R~ (CR7R~) R~ ~R~
R 1~.~°., i ( I ) M
R2 ~ \ R3 R9 (OR'R6) R4 ~ R~
in which 7M is zirconium or hafnium, R1 and R2 are identical or differewt and are a hydrogen atom, a C1-C1°-alkyl group, a C1-C1°-alkoa~y gxoup, a C6-C1°-aryl group, a C6-Clo-aryloxy group, a C2-C1o-alkenyl group, a C~-C4°-arylalkyl group, a C~-Coo-alkylaryl group, a C8-C4°--arylalkenyl group or a halogen atom, a0 R3 and R4 are identical or different and are a hydrogen r r~ ~lW~ r~ .'~?
-atom, a halogen atom, a C1-Clo-alkyl group or a -PIRi, -SR°, -QR°, -OSiR3, -~iR3 Or -PRi radical, ~.n which R° is a C1-Clo-alkyl group, a C6-Clo-aryl group or, in the case of radicals containing Si or P, also a halogen atom, or in each case two adjacent radicals R' or R'', together with the carbon atoms joining them, form a ring and R5, R6, R' and Ra are identical or different and are a hydrogen atom, a halogen atom, a Cl-C3o-alkyl group, a ZO C1-Clo-fluoroalkyl group, a Cs-Clo-aryl group, a C6-Czo fluoroaryl group, a Cl-Clo-alkoxy group, a CZ-Cao-alkenyl group, a C~-Cao-arylalkyl group, a C8-Cao-arylalkenyl group, a -SiMe3 group, an -oSiMe3 group or a C7-C4o alkylaryl group, or R5 and R6 or R' and R°, in each case toga~ther with the atoms joining them, form a ring.
The catalyst to be used fax the process according to the invention consists of an aluminoxane and at least one metallocene of the formula I
R ( ~~RB ) R R
~I) Rl~ I
M
R2.r~ ~, R3 R3 (CRSR6) R4 R~
in which M is hafnium or zirconium, preferably zirconium, R1 and RZ are identical or different and are a hydrogen atom, a C1-Clo-, preferably C1-C~-alkyl group, a C1~Clo--.
preferably C1-C3-alkoxy group, a Cs-C1o-, preferably CB-CB-aryl group, a CB-Clo-. Preferably C6-CB-aryloxy group, a Cz-Clo-~ Preferably C~-C4-alkenyl group, a C~-C4o-, prefer-ably C,-Clo-arylalkyl group, a C~-Coo-, preferably CT-Clz-alkylaryl group, a CB-Coo-, preferably C8-C12-arylalkenyl R~
..
HOECHST AKTIEIdGESELLSCHAf'T HOE 89/F 266 Dr.DA/sch Description Process for the preparation of a polyolefin The invention relates to an olefin polymer of high molecular weight and low residual catalyst content.
Isotactic PP is prepared with the aid of ethylene-bis-(4,5,6,7)-tetrahydro-1-indenyl)-zirconium dichloride together with an alumino~ane in a suspension polymeriza-tion reaction (cf. EP-A-185,918). The polymer has a narrow molecular weight distribution (z~/I~, 1.6 to 2.6).
It has been possible to achieve a considerable increase in the activity of the catalyst system by a specific :, preactivation method (cf. DE-3,726,067). The particle morphology of the polymer has likewise been improved by this preactivation method.
The molecular weights of the polymers obtained in accor-dance with these two applications are still too low far industrial use.
There was thus the object of discovering a process for the preparatioxi of a high molecular weight olefin polymer which can be carried out in an industrially interesting temperature range with a high catalyst activity.
It has been found that the object can be achieved by polymerization of olefins in the presenee of certain metallocene catalysts.
The invention thus relates to a process for the prepara-tion of a polyolefin by polymerization of an olefin of the formula R11-CH=CH-R12, in which R11 and R12 are identi-cal or different and are a hydrogen atom or a C~-C1w-alkyl radical, or R11 and Rla, together with the carbon atom joining them, form a ring having ~ to 28 carbon atoms, at ~.~ 3' ~a ~-a temperature of OnC to 150°C, under a pressure of 0>5 to 100 bar, in solution, in suspension or in the gas phase and in the presence of a catalyst which consists of a metallocene and an aluminoxane of the formula (II) j ~1 - o ~1- o ~ ~ ~ a. 0 ( I I ) R10 n R
for the linear type, and/or of the f~renula (III) Al - O (III) n-~ a for the cyclic type, in which, in the formulae (II) and ( III ) , R1° is a C1-Cs-alkyl group and n is an integer from 2 to 50, wherein the metallocene is at least one compound of the formula (I) R~
R~ (CR7R~) R~ ~R~
R 1~.~°., i ( I ) M
R2 ~ \ R3 R9 (OR'R6) R4 ~ R~
in which 7M is zirconium or hafnium, R1 and R2 are identical or differewt and are a hydrogen atom, a C1-C1°-alkyl group, a C1-C1°-alkoa~y gxoup, a C6-C1°-aryl group, a C6-Clo-aryloxy group, a C2-C1o-alkenyl group, a C~-C4°-arylalkyl group, a C~-Coo-alkylaryl group, a C8-C4°--arylalkenyl group or a halogen atom, a0 R3 and R4 are identical or different and are a hydrogen r r~ ~lW~ r~ .'~?
-atom, a halogen atom, a C1-Clo-alkyl group or a -PIRi, -SR°, -QR°, -OSiR3, -~iR3 Or -PRi radical, ~.n which R° is a C1-Clo-alkyl group, a C6-Clo-aryl group or, in the case of radicals containing Si or P, also a halogen atom, or in each case two adjacent radicals R' or R'', together with the carbon atoms joining them, form a ring and R5, R6, R' and Ra are identical or different and are a hydrogen atom, a halogen atom, a Cl-C3o-alkyl group, a ZO C1-Clo-fluoroalkyl group, a Cs-Clo-aryl group, a C6-Czo fluoroaryl group, a Cl-Clo-alkoxy group, a CZ-Cao-alkenyl group, a C~-Cao-arylalkyl group, a C8-Cao-arylalkenyl group, a -SiMe3 group, an -oSiMe3 group or a C7-C4o alkylaryl group, or R5 and R6 or R' and R°, in each case toga~ther with the atoms joining them, form a ring.
The catalyst to be used fax the process according to the invention consists of an aluminoxane and at least one metallocene of the formula I
R ( ~~RB ) R R
~I) Rl~ I
M
R2.r~ ~, R3 R3 (CRSR6) R4 R~
in which M is hafnium or zirconium, preferably zirconium, R1 and RZ are identical or different and are a hydrogen atom, a C1-Clo-, preferably C1-C~-alkyl group, a C1~Clo--.
preferably C1-C3-alkoxy group, a Cs-C1o-, preferably CB-CB-aryl group, a CB-Clo-. Preferably C6-CB-aryloxy group, a Cz-Clo-~ Preferably C~-C4-alkenyl group, a C~-C4o-, prefer-ably C,-Clo-arylalkyl group, a C~-Coo-, preferably CT-Clz-alkylaryl group, a CB-Coo-, preferably C8-C12-arylalkenyl R~
3 ('- 3 s ~r4 ~'r s~3 !"' i".' ~ 1 ~L) ~d ..~.,°f ,"~ ~,9 f J
,.. Lk ..
group or a halogen atom, preferably chlorine.
R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C1-Clo-, preferably C1-C3-alkyl group or a -~lRi, -SR9, -ORg, -OSiR3, -SiR3 ox -PRz radical, in which R9 is a Cl-Clo-, preferably Cl-C3-alkyl group or C~-Cxo-.
preferably C6-CB-aryl group, or in the case of radicals containing Si or P also a halogen atom, preferably a chlorine atom, or two adjacent radicals R3 ar R~~ together with the carbon atoms joining them, form a ring. Particu-larly preferred ligands are indenyl, fluorenyl and cyclopentadienyl.
R5, R6, R' and R8 are identical or different and are a hydrogen atom, a halogen atom, a Cl-C3o-, preferably C1-C4_ alkyl group, in particular a methyl group or ethyl group, a C1-Clo-fluoroalkyl group, preferably a CF3 group, a C6-Clo-fluoroaryl group, preferably a pentafluorophenyl group, a C6-Ci9-, preferably Cs-C8-aryl group, in parti-cular -CHz-C6H5 or -C6H5, a C1-Clo°, preferably C1-Cu-alkoxy group, in particular a methoxy group, a Cz-Clo-, prefer-ably Cz-C4-alkenyl group, a C7-Coo-, preferably C~-Clo-arylalkyl group, a CB-Coo-, preferably Cg-C1z-arylalkenyl group or a C?-C~,o'. Preferably C~-Czz-alkylaryl group, or R5 and R6 or R' and R8, in each case together with the atoms 2S joining them, form a ring.
Especially preferably, R5, Re and R' are a hydrogen atom and RB is a phenyl, benzyl, methyl, ethyl, ~trifluoromethyl or methoxy group, or RS and R' are a hydrogen atom and R6 and RB are a phenyl, benzyl, ethyl, methyl, trifluoro methyl or methoxy group.
The metallocenes described above can be prepared in accordance with the following general equations A ~ r ~ f... ax..
Nj!.~ n,~
Hz R ~~ + But y 1 L i -----~--~ HR aL i X° (CR~RB)m_ (CRSR~)n_X
BZRb + ButylLi --~ HRbLi HRa- (CR~R$)m_ (CR5R6)~_Rbg 2 B~-7 LiRa-(CR~RB)m_(CR5R6)n_RbLi MC1~
---7 8 s (cR R ~~_R (oR7R~, -R~
C1 m i 1 M ~ g R~Li (CRSRf )n_Rb ~ C1 "°'°
(CR'R6) _Rb n (CR7R8)m-Rs i ~ RI.
M
j ~ R~
(CR5R6)n-Rb R3 3 R
R3 R~
(X = C1, Br, J, O-Tosyl, HRa = ~ , HRH' = ) .
gar R~ R~
''rhe aoca~,alys~ is an aluminoxane of the foxznula IT
g10 R7.0 R20 ~'''°- Al - o Al - Al'°/ ( T I ) Rio -,''~ ~ °"~. yo for the linear type, and/or of the foranula (TTT) Rlo d~11 - ~ ( T T T ) n~~
for the cyclic type. In these formulae, R'~° is a Cl~Cs a13cy1 group, preferably me~.hyl, ethyl or isobu~,yl, in ~~ ~ ~ q3 ~ ~r~ J
- ~ -particular methyl, and n is an integer from 2 to 50, preferably 5 to 40. However, the exact structure of the aluminoxane is not known.
The aluminoxane can be prepared in various ways.
One possibility is careful addition of water to a dilute solution of an aluminum trialkyl by introducing the solution of the aluminum trialkyl, preferably aluminum trimethyl, and the water, in each ease in small portions, into a larger amount of an inert solvent initially introduced into the vessel, and awaiting the end of the evalutian of gas between each addition.
Tn another process, finely powdered copper sulfate pentahydrate is suspended in toluene and, in a glass flask under an inert gas at about -20°C, aluminum tri-alkyl is added in an amount so that about 1 mol of CuSOk ~ 5Hz0 is available for eve~.y 4 A1 atoms . After slaw hydrolysis, alkane being split off, the reaction mixture is left at room temperature for 24 to 4~ hours, during which it must be cooled if appropriate, s~ that the temperature does not rise above 30°C. The aluminoxane dissolved in the toluene is then filtered off from the copper sulfate and the solutian is concentrated in vacuo.
Tt is assumed that :Ln this preparation process the low molecular weight aluminoxanes coedense to form higher oligomers, aluminum trialkyl being split off.
Aluminoxanes are furthermore obtained when aluminum tri-alkyl, preferably aluminum trimethyl, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted with aluminum salts containing water of crystallization, preferably aluminum sulfate, at a temperature of -20 to 100°C. In this procedure, the volume ratio between the solvent and the aluminum tri-alkyl used is 1:1 to 50x1 - preferably 5:1 - and the reaction time, which can be monitored by the splitting off of the alkane, is 1 to 200 hours - preferably 10 to ~: ~. ~ ~ ;~. r.
a t:a~ -.~ ,. i c.l -40 hours.
Of the aluminum salts which contain water of crystalliza-tion, those which have a high content of water of crys-tallization are used in particular. Aluminum sulfate hydrate, especial ly the compounds A1z ( S04 ) 3 ~ 16Ha0 and A12 ( S04 ) 3 ~ 18HZ0 with the particularly high water of crystallization content of 16 and, respectively, 18 mot of HZfJ/mol of AlZ ( SQ4 ) 3, is particularly preferred .
Another variant for the preparation of aluminoxanes comprises dissolving an aluminum trialkyl, preferably aluminum trimethyl, in the suspending agent which has been initially introduced into the polymerization kettle, preferably in the liquid monomer flr in heptane or tolu-ene, and then reacting the aluminum compound with water.
In addition to the processes described above for the preparation of aluminoxanes, there are others which can be used.
Regardless of the nature of the preparation, all the aluminoxane solutions have a common feature of a varying content of unreacted aluminum trialkyl which .is present in the free form or as an adduct.
It is possible to preact3va~t~ the metallocene with an ahuninoxane of the formula (TI) andlor (IIT) before use in the polymerization reaction. The polymerization activity is in this way significantly increased and the particle morphology is improved.
The preactivatian of the transition metal compound is carried out in solution. Preferably, in this procedure, the metallocene is dissolved in a solution of the alumin-oxane in an inert hydrocarbon. An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon. Toluene is preferably used.
The concentration of the aluminoxane in the solution is ~~ ~~ f~ ,.~ p Vie! 9~,J ,,y' ~..i , ;1 g -in the range from about 1~ by weight to the saturation limit, preferably 5 to 30~ by weight, in each case based on the total solution. The metallocene can be used in the same concentration, but it is preferably used in an amount of 10-4 - 1 mol per mol of aluminoxane. The pre-activation time is 5 minutes to 60 hours, preferably 5 to 50 minutes. The preactivation is carried out at a tem-perature of -78°C to 100°C, preferably 0 to 70°C.
The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or discontinuously, in one or more stages at a tempera-ture of 0 to 150°C, preferably 30 to 80°C. Olefins of the formula R11-CH=CH-R1z are polymerized. In this formula, Rll and R12 are identical or different and are a hydrogen atom or an alkyl radical having 1 to 28 carbon atoms. However, R11 and R12, together with the carbon atoms joining them, can also form a ring having 4 to 28 carbon atoms.
Examples of such olefins are ethylene, propylene, 1-butene, 1-hexane, ~-methyl-1-pentane, ~.-octane, norborn-ene, norbornadiene, pentane, hexane or octane. Propylene is polymerized in particular.
Hydrogen is added as a molecular weight regulator if necessary. The total pressure in the polymerization system is 0.5 to 100 bar. The polymerization is prefer-ably carried out in the pressure range from 5 to 64 bar, which is of particular interest industrially.
The metallocene compound is used in the polymerization in a concentration, based on the transition metal, of 10-3 to 10-', preferably 10-4 to 106 mol of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminox-ane is used in a concentration of 10-5 to 10-~ mol, prefer-ably 10-4 to 10-Z mol per dm3 of solvent or per dm3 of reactor volume. However, in principle higher concentra-tions are also possible. ~t least one compound of the formula I is used as the metallocene. Mixtures of several compounds of the formula I or mixtures of isomers are ~% ~e a.,3 fg ~,,1 ~1 g also possible.
Tf the polymerization is carried out as suspension or solution polymerization, an inert solvent which is customary for the Ziegler low pressure process is used.
For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of these which may be mentioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
A benzine or hydrogenated diesel oil fraction can furthermore be used. Toluene can also be used. The polymerization is preferably carried out in the liquid monomer.
If inert solvents are used, the monomers are metered in as a gas or in liquid form.
If only one monomer is used as the suspending agent, the comonomer or the comonomers is or are metered in as a gas or in liquid form.
It is furthermore possible to carry out the polymeriza tion in a mixture of different monomers as the suspending agent; another monomer can then be metered in as a liquid or in gaseous form. Tf ethylene is used, it is advantage-ous for some of 'the ethylene to be initially iwtroduced and for the remainder to be metered in during the poly-merization.
The duration of the polymerization can be as desired, since the catalyst system to Sae used according to the invention shows only a slight time-related drop in polymerization activity.
The process according to the invention is distinguished by the fact that the metallocenes used are very heat-stable, so that they can be used with high activity even at temperatures up to 90°G. Tpie aluminoxanes used as cocatalysts can moreover be added in lower concentrations than previously. Finally, it is now possible to prepare random copolymers at temperatures of industrial interest.
The metallocenes or metallocene mixtures to be used according to the invention contain compounds which can polymerize propylene to give polymers having a molecular weight of more than 150,000 g/mol, preferably 200,000 g/mol. This is confirmed by the molecular weight distribution, which has a high M~,/M~, ratio (> 2). The molecular weight distribution is sometimes multimodal.
Synthesis of 1,2-bis(1-indenyl)-1,2-bis(phenyl)ethane (diastereomer mixture) A mixture of 68.64 g (336 mmol) of methylphenyl-benzo-fulvene, 4.92 cm~ (61 mmol) of CC14 and 100 cm3 of tetra-hydrofuran was added to 8.17 g (336 mmol) of magnesium filings in the course of 0.5 hour. The reaction mixture, which was warm because of the reaction which occurred, was then stirred overnight. The resulting Grignard mixture was added to ethereal HC1, and water was then added. The organic phase was separated off, dried over PIaZSO4, filtered and evaporated.
The crude product was purified by column chromatography (50 x 250 mm; 60 ~., 70 - 200 ~sm, starting with pure n--hexane with an increasing HZCC12 content).
Yield 3.1 g ( 7 .55 mmol, 4 . 5~ ) , rF ~ 0. 26 ( 3 volumes of hexane/1 volume of H~CC12), melting point 225 - 230°C.
~x~ample $(~5-1-Indenyl)-CHZ*CHEt-(r~s-1-indenyl)~~rClz (1) 56 cm3 of a 1.6 N (89.6 mmol) solution of butyllithium in hexane were added dropwise to 12.2 g (42.6 mmol) of the ligand (racemate) in 200 cm3 of tetrahydrofuran at room temperature in the course of 1 hour and the mixture was stirred at 60°C for 0.5 hour after the end of the evolution of butane.
The resulting dilithium salt solution was added dropwise, simultaneously with a solu~ta.on of 16.6 g (44 mmol) of c;3 4~ 63 ~') ~.. ;;' h l ZrCl4(tetrahydrofuran)Z in 300 cm3 of tetrahydrofuran, to 50 cm3 of tetrahydrofuran at room temperature in the course of 2 hours. The mixture was then stirred at room temperature for 1.5 hours, and 4 cm3 of a 1.0 N {4 mmol) ethereal solution of HC1 were added. After the dark reaction mixture had spontaneously brightened, an orange color persisted. The mixture was now concentrated to 200 cm3 and the inorganic salts were precipitated by addition of toluene and filtered off.
The filtrate was concentrated further. When the volume was still 100 cm3, a yellow-orange solid was obtained. To bring the precipitation to completion, the mixture was placed in a deep-freeze (-3.5°C) overnight and then filtered and the precipitate was washed with a little cold toluene and then with n-pentane and dried in vacuo.
Yield I: 2.6 g (5.82 mmol - 13.70 ; 1~MR showed a 1:1 mixture of two complexes.
The precipitate which separates out on further concentra tion of the filtrate was treated as described above.
Yield Its 3.3 g (7.39 mmol = 17.40 ; NMR showed a mixture of the complexes from I.
The filtrate was evaporated to dryness. Yield III: 0.2 g.
Fraction II was 'taken up in ether and the mixture was concentrated slowly. The first precipitate ~ obtained shaved an -. 1;3 mixture according to IdMR, the complex which appeared in the five-membered ring proton range in the higher field predominating. When the procedure was repeated with .A, an enrichment to better than 1:4 was obtained (precipitate B, 1.2 g (2.59 mmol = 6.3~).
The filtrate of B evaporated to dryness contained the comgound in resonance in the lower field enriched to more than 4:1 (yield 0.8 g (1.79 mmol = 4.2~)).
Fraction II showed a correct CH analysis: found 58.5 {calculated 59.18) ~ C; 4.6 (4.51)$ H.
Example 2 7.9~ g (27.79 mmol) of ligand (racemate) in 100 cm3 of tetrahydrofuran and 36 cm3 of a 1. 6 N ( 57 . 6 mmol ) solution of butyllithium in hexane were reacted as described in ~.~i~.>,?v Example 1 to give the d:ilithium salt. 10.78 g (28.58 mmol) of ZrClu (tetrahydrofuran)2 in 2fJ0 cm~ of tetrahydrofuran and the dilithium salt solution were added dropwise to 50 cm3 of tetrahydrofuran at room temperature. The procedure followed here was such that a larger amount of zirconium compound was always initially introduced, i.e. the zirconium solution was added in the course of 3 hours and the dilithium salt solution was added in the course of 8.5 hours. .~.fter the mixture had been stirred at room temperature for two hours, 2.5 cm3 of 1. 0 N ( 2 . 5 mmol ) ethereal HCl were added - the mixture brightened immediately - and the mixture was concentrated to about 100 cm3. 150 cm3 of toluene were then added and the mixture was left to stand overnight. The precipitate obtained was separated off and the filtrate was concent-rated. A small amount of oil which occurred during this operation was decanted off and the liquid was evaporated to dryness. The crude product was analyzed by NMR spec-troscopy. The species known from Example 1 was found as the main component, together with at least one other compound. The mixture was extracted with 2 x 120 cm~ of Et2p and the filtrate was evaporated . Tts NMR spectrum shows, in addition to the signals known from Example 1, further resonances in the five-membered ring proton range. The further ether extracts obtained (~ 1 cm~) were evaporated to dryness. 10.5 g of yellow solid were obtained (23.5 mmol = 8~.6~; PdMR: two complexes).
Example 3 ~ ( q5-1-Indenyl ) -C~Ia*CHP~ie- ( r~ 5-1-indenyl ) } ZrClz ( 2 ) ~1 cm3 of a 1.6 N (65.6 mmol) solution of butyllithium in hexane were added dropwise to 7.7 g (30.53 mmol) of ligand (racemate) in 100 cm3 of tetrahydrofuran at room temperature in the course of 1 hour and the mixture was stirred at 60°C for 0.5 hour after the evolution of butane had ended.
11.7 g (31.01 mmol) of ZrCl4(tetrahydrofuran)Z in 250 cm3 of tetrahydrofuran were added, simultaneously with the 6' F !~ r~ r. ~
~; ~~ ~ «~ r~ '..a P~J
dilithiurn salt solution, to 50 cm3 of tetrahydrofuran at roam temperature in the course of 5 hours. After the mixture had been stirred at room temperature for two days, ~ cm3 (4 mmol) of ethereal HC1 were added. The now clear yellow-orange reaction mixture was concentrated to dryness. The orange-red evaporation residue was extracted with 6 x 80 cm3 of toluene and the mixture was filtered and concentrated. An oil which was obtained during concentration to 200 cm3 was decanted off and the filtrate was concentrated further to 80 cm~. The precipitate A
obtained by this procedure was filtered off, washed with a little n-pentane and dried in vacuo. Yield A: 1.85 g (4.28 mmol = 14~); ldP~R shows two complexes.
The filtrate was concentrated further to 30 cm3 and placed at a low temperature (-35°C) overnight, decanted off from precipitate B and evaporated to dryness (0.1 g; I~7MR
showed starting materials i.e. ligand and ZxCI~,(tetra-hydrofuran)2, toluene and probably four complexes).
Precipitate B was washed with pentane and dried in vacuo.
Yield B: 0.7 g (1.62 mmol = 5.3~); IdMR showed the pre-sence of a four-component mixture.
Elemental analysis gave the following result:
found 57.9 (calculated 58.32) C, 4.2~ (4.4) H~
Example 4 ~ ( r~5-1-Indenyl ) -CHz*CH ( benzyl ) - ( r~5-1-indenyl ) }ZrCl2 (3) 17.25 cm3 of a 1.6 13 (27.6 mmol) solution of butyllithium in hexane were added dropwise to 4.53 g (13 mmol) of ligand in 75 crn3 of tetrahydrofuran and the mixture was then stirred at 55°C for 0.5 hour after the evolu-tion of gas had ended.
This dilithium salt solution was added, simultaneously with 4.9 g (12.99 mmol) of ZrCl4(tetrahydrofuranjz in 100 cm3 of tetrahydrofuran, to 30 cm3 of tetrahydrofuran at room temperature in the course of 6 hours, 'the mixture was evaporated to dryness, the residue was taken up in toluene and the mixture was filtered. After the solvent had been stripped off, the residue was digested several times with n-pentane, the pentane being decanted off . The residue now obtained was dried. Yield: 2.28 g (about 4.47 mmol - 34.40; NMR confirmed the presence of at least three complexes, contaminated with tetrahydrofuran and pentane.
Example 5 .((~5-1-Indenyl)_*CHPh*CHPh-(q5-1-indenyi)~ZxCl2 (4) 6.25 cm3 of a 1.6 N (10 mmol) solution of butyllithium in hexane were added dropwise to 2.04 g (4.97 mmol) of ligand (diastereomer mixture) in 40 cm3 of tetrahydrofuran at room temperature. During this procedure, a white-green precipitate separated out after abo~.at half the solution had been added. After the mixture had been stirred at 60°C fox two hours, the dilithium salt obtained was added in portions to 1.88 g (4.98 mmol) of ~xCl,,(tetrahydro-furan)2, dissolved in 40 cm3 of te~trahydrofuran, at 0°C.
Thereafter, the mixture was stirred at room temperature for 4 hours and concentrated 'to dryness, the residue was extracted with a warm (about 40°C) n-pentane/toluene mixture (2:1 by volume), the mixture was fia.tered and the .clear yellow solution obtained was concentrated. A yellow precipitate A obtained by this procedure was filtered off, washed with a little cold Et20 and dried in vacuo.
Yield A: 0 . 45 g ( about 0 . 86 mmoi = 17 . 70 ; PIMR showed, in addition to solvents ( EtaO, tetrahydrofuran, n-pentane, toluene), signals having cleavage patterns of at least two complex compounds, which patterns are characteristic of indenyl complex five-membered ring protons. 25 cm3 of n-pentane were added to the filtrate and precipitate B
which had separated out was filtered off, washed with a little cold Et20 and dried in vacuo. Yield B: 1. 08 g ( 1.57 mmol = 31.5~j; NPY~t showed, in addition to the signals of toluene and pentane, the probable presence of a single complex species which was not present in A.
,.~ r ~,.e sJ . ~ =.~a The fil~tra~te of H was evaporated to dryness. :Cts I~MR
showed, in addition to Et20, pentane and toluene, probably signals of the complex from precipitate B and the ligand.
Rxample 6 ~ ( ~~-1-Indenyl )-CHZ*CHMe-( r~5°1-indenyl ) ~HfCl2 ( 6 ) 34 cm3 of a 1.6 P7 (54.4 mmol) solution of butyllithium in hexane were added dropwise to 7.2 g (26.95 mmol) of ligand (racemate) in 200 cm3 of tetrahydrofuran at room temperature in the course of one hour and the mixture was then stirred at 60°C for 1 hour. The dilithium salt was then added dropwise, simultaneously together with 13 g (28 mmol) of HfCl4(tetrahydrofuran)2 in 200 cm3 of tetra-hydrofuran, to 50 cm3 of tetrahydrofuran, the procedure being such that an Hf excess was present in the reactor vessel. After 2/3 of the reaction partners had been added, the mixture was left to stand overnight and the remainder of the reaction partners was added in the course of 4 hours. The mixture was then stirred overnight and 4 cm3 of 1.0 N (4.0 mmol) ethereal HC1 were added, a brightening in color being observed.
The yellow-brown evaporation residue was extracted with toluene and the mixture was filtered and evaporated to dryness. The resulting residue T was digested with n-pentane, the filtered soleent was stripped off and the remainder of about 25 cm~ was separated of:~ from the precipitate obtained.
Yield A: 0.61 g (1.14 mmol - 4.2~); ~7MR showed, in addition to the signals of the ligand, resonances in the indenyl five-membered ring proton range, which demon-strata the presence of three complex compounds, two being present as main components.
Residue 2 was further extracted with pentane/Et20 (1:2 by volume), the mixture was filtered and the filtrate was concentrated. Yield Bs 0.26 g (0.49 mmol - 1.8~); I~lR
demonstrated the presence of a complex mixture, evidently of four compound: (faur methyl group triplets of the ethyl group in the range from 1.25 to 0.85 ppm).
~J ~ a;~ ~) ~a 1 '.the following elemental analysis was found: calculated 49.5 (found 50.9) ~ C; 3.78 (~.1)~ H.
Example 7 ~ ( r~ $-1-Indenyl ) -CHZCHEt- ( ,~ 5-1-indenyl ) } Z n ( CH3 ) 2 ( 5 ) 4.1 cm~ of a 1.6 N (6.56 mmol) solution of methyllithium in ether were added dropwise to 1.45 g (3.25 mmol) of a suspension of two complex compounds in 50 cm3 of EtzO at -40°C. when a relatively large proportion of the compon-ents had dissolved and a dirty white precipitate had formed, the mixture was evaporated to dryness. after extraction with 200 em3 of n-pentane and filtration, the solvent was stripped off and the residue was dried in vacuo.
3~ield: 1.15 g (about 2.83 mnnol = 87.00; NMR showed, in addition to a few impurities, probably monomethylated compounds, two main components with the resonances typical of CH3Zr species in the high field range, i.e. as expected two resonances fox the syn-form, at -0.76 and -0.88 ppm, and two signals at an almost identical shift of -1.02 ppm for the anti-form, which no longer has CZ
symmetry because of the unsymmetric C2 bridge.
Examuples 7 to 10 and Comparison Example A
A dry 7.6 dm3 kettle was flushed with nitrogen and filled with 10 drn3 of a benzine (boiling range 100-120°C) at 20°C. The gas space in the kettle was then flushed free from nitrogen by forcing in 2 bar of ethylene and letting down S times. Thereafter, 30 cm3 of a toluene solution of methylaluminoxane (10.5 by weight of methylaluminoxane, molecular weight according to cryoscopic determination:
750 g/mol ) were added. The contents of the kettle were heated up to 60°C in the course of 15 minutes, while stirring. The total pressure was then adjusted to 5 bar by feeding in ethylene, while stirring at 250 revolutions per minute. In parallel with this, 3.1 mg of metallocene were dissolved in 20 cm~ of a toluene solution of methyl-aluminoxane (concentration and quality as above) and were ";,~ ~ ') preactivated by being left to stand for 15 minutes. The solution was then introduced into the kettle. The poly-merization system was brought to a temperature of 65°C
and then kept at this temperature for 1 hour by approp-riate cooling. During this period, the total pressure was kept at 5 bar by appropriately feeding in ethylene. The amounts shown in Table 1 were obtained.
The following abbreviations have been used in the tables:
~i'~I = viscosity number in cma/g, Mw = weight-average molecular weight in g/mol Mw/Mn - polydispersity determined by gel permeation chromatography (GPC) II = isotaxy, determined by 13C-NMR spectroscopy, BD = bulk density, T8 = glass transition temperature.
Examples 11 and 12 and Coaa~para.son Example 1B
A clean, dry 1.5 dm3 polymerization reactor with a stirrer was flushed with nitrogen and then with ethylene and fil-led with a solution of norbornene in 750 cm3 of toluene.
The reactor was then brought to a temperature of 20°C, while stirring, and 1 bar of ethylene was forced in. 20 cm~ of a toluene solution of methylaluminoxane (10.1 by weight of methylaluminoxane of molecular we,igla~t 1300 g/mol, cryoscopic determination) were then metered into the reactox and tha mixture was stirred at 20°C for 15 minutes, the ethylene pressure being kept at 1 bar by topping up (saturation of the toluene with ethylene). In parallel with this, the metallocene was dissolved in 10 cm3 of a toluene solution of methylaluminoxane (con-centration and quality see above) and was preactivated by being left to stand for 15 minutes. The solution of the complex was then metered into 'the reactor. Polymerization was subsequently carxied out at 20°C for 1 hour, while stirring (750 revolutions per minute), the ethylene pressure being kept under 1 bar by topping up. The contents of the reactor were then drained rapidly into a stirred vessel into which 100 cm3 of isopropanol had been ~~~~'~)'~''~~~~
K~ ~ 1 7i) TJt '.~) i_ m ~~ -initially introduced. 2 dm3 of acetone were added to this mixture, 'the mixture was stirred for 10 minutes and the suspended polymeric solid was then filtered off, The polymer filtered off was then added to 600 cm3 of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol and this suspension was stirred for 2 hours. The polymer was then filtered off again, washed neutral with water and dried at 80°C under 0.2 bar for 15 hours.
The results of the experiments are summarized in Table 2.
J~xamples 13 to 15 and Comparison Example C
A clean, dry 1.5 dm3 polymerization reactor with a stirrer was flushed with nitrogen and then with propylene and filled with a solution of 30 g of norbornene in 750 cm3 of toluene. The reactor was then brought to a temperature of 20°C, while stirring, and 1 bar of propylene was forced in. 20 cm3 of a toluene solution of methylaluminoxane (10.1 by weight of methylaluminoxane having a molecular weight of 1300 g/mol) were then metered into the reactor and the mixture was stirred at 20°C for 15 minutes, the propylene pressure being kept at 1 bar by topping up (saturation of the toluene with propylene). In parallel with this the metallocene was dissolved in 10 cm' of a toluene solution of methylaluminoxane (concentration and guality see above) and preactivated by being left to stand fox 15 minutes. The solution of the complex was then metered into the reactor. Polymerization was sub-sequently carried out at 20°C for 3 hours, while stirring (750 revolutions per minute), the propylene pressure being kept at 1 bar by topping up. The contents of the reactor were then drained rapidly into a stirred vessel into which 100 cm3 of isopropanol had been initially introduced. 2 dm3 of acetone were added to this mixture, the mixture was stirred for 30 minutes and the suspended polymeric solid was filtered off. The polymer filtered off was then added to 600 cm3 of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol and I
~~~3~~
this suspension was stirred for 2 hours. 200 cm3 of toluene were then added to the mixture and, after the mixture had been stirred for a further 5 minutes, the toluene phase was separated off and 1 dm3 of acetone was added. The polymer which had been dissolved in toluene by extraction of the hydrochloric acid mixture was precipi-tated during this procedure. The polymeric solid precipi-tated was filtered off and dried at 80°C under 0.2 bar for 15 hours.
The experimental results are summarized in Table 3.
Examples 16 to ~7 A dry 16 dm~ kettle was flushed with nitrogen and then filled with 10 dm3 of liquid propylene. Two thirds of the amount of methylaluminoxane stated in Table ~ for the particular experiment were then added as a solution in toluene and the mixture was stirred at 30°C for 15 minutes. In para11e1 with this a solution of the metallo-cene in one third of the amount of methylaluminoxane stated in Table 4 was prepared and was preactivated by being left to stand for 15 minutes. The metallocene (Examples 1 to '7) were used as mixtures of compounds or as isomer mixtures, without further purification.
This solution was then introduced into the kettle. The polymerization system was brought to th~a appropriate polymerization temperature and the polymerization was started. After 60 minutes, the polymerization was stopped by cooling the reactor and letting down. The resulting polymer yield and the analytical data determined can be seen from Table 4.
r-i ri .-.
' o a o 0 0 ~ cV
N ~ N ~ c c1 n U
.-, O o o to 0 L~ U N tt7 M 0~ u1 I:f.1 w .-i .-i 'p W
r-1 W ~-. o O o o p N tn M wf o ~o ' N N
O .iaO
~ N ~ rn ,-I t~ o-I
r- tn ;
I
a ~ a ~ ~r ~, an ~
I ~ O ~ i F;
N U N U
U
r P- ~~
i J f~
~ I ~ ~
~ ~ ~ ~
I .~i ~ ff ~; - H 7 U ~ ~ Ial r r p ~, O
i r -II
Qi QI~.i >-I ~ .--Irl sl1 e-i ~C..' U ,...1 o~Y r-! 'a~
.-I 3Y r'"~Y i U
N ~ r9 ~
.N N ,I-> ~.,~ p r-1 C~ 'Py tt1 QI N N
N a1 ~ p ~ ~ ,fit ~ ~ '~ ~! ;h ~ "d 1 . 0 ~i ~ ~ '~ ~
0 "~ O O
p p ~ ~ L r-I .-.r ~.. I
1 r-1 as c~ v a ~ 9ro zi .~ I .~ U
.~ ,~
U U U tp U .~.:i~
I t~ U i.d U U
tit ft1 iL1 (i~ .-i PI rI rl .i.) rl rl rl r-I
ii i-I 1-I a-I
'-~'p .R ,.4 O
'b 'CJ N
A!
t0 ~ t-. ao rn U
~
E,~ 1'" !,..' 9 ~1~~~.~~.~e -- ZZ
v ~ .-ia;~;
o, a ~ N
U
b fU ~ ~ Q N
'"'6t1 00M L7 N N
d O
t~
W
O O
O
M M M M
H
O
4a O .!~O
~ N A'~~-I
t~ r~ Q1~ M N M N
t ~i U
N
U V 'k ~N
O N ~N N
r'I
p.j W rWw n , r~ r~r~r~
d w .r ar N N N N
O
td~
M O ya r-! (d y W ~ ~ n-1r1ri ~~~ ~wr -- 2 3 -.
~t tC t0 CO IS7 eP CO N t,~ et C>7 CO ~ et SD O) 6p M ~9 h N C ip 90 M to O ~ tr ~
cr M M C' et M 6t! ~ M M ~~t CO St N N N N
~ ~ct Ln N Id7 6D (C N c~' N ~ ~ 6t7 r~ O O O O O O O O O O O O O O O O O O O O
O O O O O O O O C
O
Q O O O O O O O O O O O O O O C? O O O O O
O O O O O O O O G
O
O O O O O lt7 Lt9 O LA O O O O O O tJ O
O O O O O !17 O O O C
O 6l! O
6t7 CO N 00 N 68 tJt M cf~ t0 ip 6D C~ 6~ O
'~' iwa h ,-~ 6L7 h M 60 ~ O ~ O Q.
~ VI
a ~ lff et CL7 N N M 00 dp ~ ~ h M OD CO h c> t0 (~
h O h 6L7 t<7 M tp a? is Lff ~ c1 M ~ ~ O CJ O taa N iD h O N Off W~ rr CO
O N O O M W M h P tt7 ttf M N Or 6 b' h h ~ h i8 ~' ~ O h . On u7 ITi ~ tD 00 tp uT 6n c~ t~;
U
da m AO N 6f7 O O Ld7 C,7 tD ~ d' t7 O O
e-t O Ll7 '~ ~t (D
ri N ~tD h tA N O (~ O C9 OTf . ~ ct IA CO M M O M N h h f, h N ~ N vb r-a N w N M ~ N rr .-s M w in M ~
et b ..r O ra ~-1 ~ 00 O OOD n OD 000 CO CO AO CO Op0 OpD 00 Op0 CO I~~, n ~ ~ OoD CO 000 ~ h ~
~ ~
W
~ Wit'.~ P cC ' ~ Iw t17 . . M ct h Ln O M lp h O M O c0 C9 M
4-i ~ N Pw M !t CO ~t O cfi M
a a ~1 CD C97 d' P. r4 Pa, ~ In N 6D h O .~nM.-~
Q f N O M f\ M t17 Cn N ld7 ~ a CD ep N ip 00 L67 tp PI h-11_ O '~ N M tp 1.c7 r-t N M l11 CT ~w ~ M (C) On Cf~\ 4 O M ~' w N
(O
.u . a ,. .~' '' x r .~
\
.
i ,Q
U
~ 00 O Y h W 617 N M O ~ f~ N O (~ O O Ll7 QI h IW .-H N LLy~ O G7 Rf' O 07 CT ' ' O O v-9 GD .-~ tn .-i 00 ~. cD CO 6c7 t0 O 6d7 Ca C17 tn M 0 .-~ Cn et et (Ot CO h.. .-4 CO n 1 6d7 .-~ (C1 6I7 d N
h h h r-a h O p In N l0 -1 M N M ~&t .-4 ' OD (~ N N C7tQ tD On er 05 N ~t M t ~w CO
pit r1 .-1 N .-~ n1 r-1 r1 v-9 .-f r-1 N .-1 N
W
'rat.-.
O CC~ 0 0 0 Cl O O t6'f0 6.C1Ca 0 O O 0 0 0 a C~ 0 6n M O 0 0 0 0 0 M ~Y 0 .. ., ., ., .. ., ., ., ., ., ., .. ., ., O ., tt7 (O ., ., ., .. ., ., ., d ., 6~ Qp ., 6d7 O .. ., Ln tc1 O to O Lff ., !l7 C7 O O 6Y! O G7 ~ tp O
!L'7 6Cf ' r~ .~ .~ ~-1 .-1 7 r-i N M N lL1 M .-1 tn 667 U .-d .-i M '-1 N 117 .-f tl7 .-i N .-1 N !tJ .-r u7 N r-1 66'7 I,C
oC
N
~
O G7 O O O O O CI ~ G1 O C9 O O O ~ O
f O O O O O O t~ O 00 C9 O O
60 Lt l O O
' tD O
' ' W ha l L67 ~ 1~ ~ l~ ~' 6l9 0.'p' h Il~
7 e? 7 ~f (~ l0 h ~D IO lt7 (D
I h. f'w CU PW P'~.
w ~
Q
H
ro ro ~ ~ ~
d-1 ~ N r w r qvy a -a N N N
U
~1 ~
N N N N .
c a w w ia ~ ~
u ,, a:
,6 L
U N ~ ~ ~ ~ + ~
. e .
Q 6-~ sa v kJ 6tJ 6L ud UJ 6JJ 16.i eJJ
N N N N N N N N N
r, ~ rr sr /~. v~1 a1 /9 n a~a 6B1 '~ '~ '~ a 'C9 't7 '~ 'li7 'O
C C C C C C Sr C C
F-1 H C.~I i~1 7~i 1..1 IW YW hf ss v v v v v w ,.n an r'~e L L L L L L L L L
N N N N PJ N N hl N
Q
i"1rl 6D h 00 .-~ N tl7 C17 O M ~' 40 h O r4 ~ !l7 C~ M et LO wl N Lf9 Ct1 N M CD
O h, C77 I~
Cp ,.-~~ .-~ N N N N N M M M M M M ct 'et ~~ eY
.-~ N N M M M M eY ~ et N N et N
,.. Lk ..
group or a halogen atom, preferably chlorine.
R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C1-Clo-, preferably C1-C3-alkyl group or a -~lRi, -SR9, -ORg, -OSiR3, -SiR3 ox -PRz radical, in which R9 is a Cl-Clo-, preferably Cl-C3-alkyl group or C~-Cxo-.
preferably C6-CB-aryl group, or in the case of radicals containing Si or P also a halogen atom, preferably a chlorine atom, or two adjacent radicals R3 ar R~~ together with the carbon atoms joining them, form a ring. Particu-larly preferred ligands are indenyl, fluorenyl and cyclopentadienyl.
R5, R6, R' and R8 are identical or different and are a hydrogen atom, a halogen atom, a Cl-C3o-, preferably C1-C4_ alkyl group, in particular a methyl group or ethyl group, a C1-Clo-fluoroalkyl group, preferably a CF3 group, a C6-Clo-fluoroaryl group, preferably a pentafluorophenyl group, a C6-Ci9-, preferably Cs-C8-aryl group, in parti-cular -CHz-C6H5 or -C6H5, a C1-Clo°, preferably C1-Cu-alkoxy group, in particular a methoxy group, a Cz-Clo-, prefer-ably Cz-C4-alkenyl group, a C7-Coo-, preferably C~-Clo-arylalkyl group, a CB-Coo-, preferably Cg-C1z-arylalkenyl group or a C?-C~,o'. Preferably C~-Czz-alkylaryl group, or R5 and R6 or R' and R8, in each case together with the atoms 2S joining them, form a ring.
Especially preferably, R5, Re and R' are a hydrogen atom and RB is a phenyl, benzyl, methyl, ethyl, ~trifluoromethyl or methoxy group, or RS and R' are a hydrogen atom and R6 and RB are a phenyl, benzyl, ethyl, methyl, trifluoro methyl or methoxy group.
The metallocenes described above can be prepared in accordance with the following general equations A ~ r ~ f... ax..
Nj!.~ n,~
Hz R ~~ + But y 1 L i -----~--~ HR aL i X° (CR~RB)m_ (CRSR~)n_X
BZRb + ButylLi --~ HRbLi HRa- (CR~R$)m_ (CR5R6)~_Rbg 2 B~-7 LiRa-(CR~RB)m_(CR5R6)n_RbLi MC1~
---7 8 s (cR R ~~_R (oR7R~, -R~
C1 m i 1 M ~ g R~Li (CRSRf )n_Rb ~ C1 "°'°
(CR'R6) _Rb n (CR7R8)m-Rs i ~ RI.
M
j ~ R~
(CR5R6)n-Rb R3 3 R
R3 R~
(X = C1, Br, J, O-Tosyl, HRa = ~ , HRH' = ) .
gar R~ R~
''rhe aoca~,alys~ is an aluminoxane of the foxznula IT
g10 R7.0 R20 ~'''°- Al - o Al - Al'°/ ( T I ) Rio -,''~ ~ °"~. yo for the linear type, and/or of the foranula (TTT) Rlo d~11 - ~ ( T T T ) n~~
for the cyclic type. In these formulae, R'~° is a Cl~Cs a13cy1 group, preferably me~.hyl, ethyl or isobu~,yl, in ~~ ~ ~ q3 ~ ~r~ J
- ~ -particular methyl, and n is an integer from 2 to 50, preferably 5 to 40. However, the exact structure of the aluminoxane is not known.
The aluminoxane can be prepared in various ways.
One possibility is careful addition of water to a dilute solution of an aluminum trialkyl by introducing the solution of the aluminum trialkyl, preferably aluminum trimethyl, and the water, in each ease in small portions, into a larger amount of an inert solvent initially introduced into the vessel, and awaiting the end of the evalutian of gas between each addition.
Tn another process, finely powdered copper sulfate pentahydrate is suspended in toluene and, in a glass flask under an inert gas at about -20°C, aluminum tri-alkyl is added in an amount so that about 1 mol of CuSOk ~ 5Hz0 is available for eve~.y 4 A1 atoms . After slaw hydrolysis, alkane being split off, the reaction mixture is left at room temperature for 24 to 4~ hours, during which it must be cooled if appropriate, s~ that the temperature does not rise above 30°C. The aluminoxane dissolved in the toluene is then filtered off from the copper sulfate and the solutian is concentrated in vacuo.
Tt is assumed that :Ln this preparation process the low molecular weight aluminoxanes coedense to form higher oligomers, aluminum trialkyl being split off.
Aluminoxanes are furthermore obtained when aluminum tri-alkyl, preferably aluminum trimethyl, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or toluene, is reacted with aluminum salts containing water of crystallization, preferably aluminum sulfate, at a temperature of -20 to 100°C. In this procedure, the volume ratio between the solvent and the aluminum tri-alkyl used is 1:1 to 50x1 - preferably 5:1 - and the reaction time, which can be monitored by the splitting off of the alkane, is 1 to 200 hours - preferably 10 to ~: ~. ~ ~ ;~. r.
a t:a~ -.~ ,. i c.l -40 hours.
Of the aluminum salts which contain water of crystalliza-tion, those which have a high content of water of crys-tallization are used in particular. Aluminum sulfate hydrate, especial ly the compounds A1z ( S04 ) 3 ~ 16Ha0 and A12 ( S04 ) 3 ~ 18HZ0 with the particularly high water of crystallization content of 16 and, respectively, 18 mot of HZfJ/mol of AlZ ( SQ4 ) 3, is particularly preferred .
Another variant for the preparation of aluminoxanes comprises dissolving an aluminum trialkyl, preferably aluminum trimethyl, in the suspending agent which has been initially introduced into the polymerization kettle, preferably in the liquid monomer flr in heptane or tolu-ene, and then reacting the aluminum compound with water.
In addition to the processes described above for the preparation of aluminoxanes, there are others which can be used.
Regardless of the nature of the preparation, all the aluminoxane solutions have a common feature of a varying content of unreacted aluminum trialkyl which .is present in the free form or as an adduct.
It is possible to preact3va~t~ the metallocene with an ahuninoxane of the formula (TI) andlor (IIT) before use in the polymerization reaction. The polymerization activity is in this way significantly increased and the particle morphology is improved.
The preactivatian of the transition metal compound is carried out in solution. Preferably, in this procedure, the metallocene is dissolved in a solution of the alumin-oxane in an inert hydrocarbon. An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon. Toluene is preferably used.
The concentration of the aluminoxane in the solution is ~~ ~~ f~ ,.~ p Vie! 9~,J ,,y' ~..i , ;1 g -in the range from about 1~ by weight to the saturation limit, preferably 5 to 30~ by weight, in each case based on the total solution. The metallocene can be used in the same concentration, but it is preferably used in an amount of 10-4 - 1 mol per mol of aluminoxane. The pre-activation time is 5 minutes to 60 hours, preferably 5 to 50 minutes. The preactivation is carried out at a tem-perature of -78°C to 100°C, preferably 0 to 70°C.
The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or discontinuously, in one or more stages at a tempera-ture of 0 to 150°C, preferably 30 to 80°C. Olefins of the formula R11-CH=CH-R1z are polymerized. In this formula, Rll and R12 are identical or different and are a hydrogen atom or an alkyl radical having 1 to 28 carbon atoms. However, R11 and R12, together with the carbon atoms joining them, can also form a ring having 4 to 28 carbon atoms.
Examples of such olefins are ethylene, propylene, 1-butene, 1-hexane, ~-methyl-1-pentane, ~.-octane, norborn-ene, norbornadiene, pentane, hexane or octane. Propylene is polymerized in particular.
Hydrogen is added as a molecular weight regulator if necessary. The total pressure in the polymerization system is 0.5 to 100 bar. The polymerization is prefer-ably carried out in the pressure range from 5 to 64 bar, which is of particular interest industrially.
The metallocene compound is used in the polymerization in a concentration, based on the transition metal, of 10-3 to 10-', preferably 10-4 to 106 mol of transition metal per dm3 of solvent or per dm3 of reactor volume. The aluminox-ane is used in a concentration of 10-5 to 10-~ mol, prefer-ably 10-4 to 10-Z mol per dm3 of solvent or per dm3 of reactor volume. However, in principle higher concentra-tions are also possible. ~t least one compound of the formula I is used as the metallocene. Mixtures of several compounds of the formula I or mixtures of isomers are ~% ~e a.,3 fg ~,,1 ~1 g also possible.
Tf the polymerization is carried out as suspension or solution polymerization, an inert solvent which is customary for the Ziegler low pressure process is used.
For example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of these which may be mentioned are butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane.
A benzine or hydrogenated diesel oil fraction can furthermore be used. Toluene can also be used. The polymerization is preferably carried out in the liquid monomer.
If inert solvents are used, the monomers are metered in as a gas or in liquid form.
If only one monomer is used as the suspending agent, the comonomer or the comonomers is or are metered in as a gas or in liquid form.
It is furthermore possible to carry out the polymeriza tion in a mixture of different monomers as the suspending agent; another monomer can then be metered in as a liquid or in gaseous form. Tf ethylene is used, it is advantage-ous for some of 'the ethylene to be initially iwtroduced and for the remainder to be metered in during the poly-merization.
The duration of the polymerization can be as desired, since the catalyst system to Sae used according to the invention shows only a slight time-related drop in polymerization activity.
The process according to the invention is distinguished by the fact that the metallocenes used are very heat-stable, so that they can be used with high activity even at temperatures up to 90°G. Tpie aluminoxanes used as cocatalysts can moreover be added in lower concentrations than previously. Finally, it is now possible to prepare random copolymers at temperatures of industrial interest.
The metallocenes or metallocene mixtures to be used according to the invention contain compounds which can polymerize propylene to give polymers having a molecular weight of more than 150,000 g/mol, preferably 200,000 g/mol. This is confirmed by the molecular weight distribution, which has a high M~,/M~, ratio (> 2). The molecular weight distribution is sometimes multimodal.
Synthesis of 1,2-bis(1-indenyl)-1,2-bis(phenyl)ethane (diastereomer mixture) A mixture of 68.64 g (336 mmol) of methylphenyl-benzo-fulvene, 4.92 cm~ (61 mmol) of CC14 and 100 cm3 of tetra-hydrofuran was added to 8.17 g (336 mmol) of magnesium filings in the course of 0.5 hour. The reaction mixture, which was warm because of the reaction which occurred, was then stirred overnight. The resulting Grignard mixture was added to ethereal HC1, and water was then added. The organic phase was separated off, dried over PIaZSO4, filtered and evaporated.
The crude product was purified by column chromatography (50 x 250 mm; 60 ~., 70 - 200 ~sm, starting with pure n--hexane with an increasing HZCC12 content).
Yield 3.1 g ( 7 .55 mmol, 4 . 5~ ) , rF ~ 0. 26 ( 3 volumes of hexane/1 volume of H~CC12), melting point 225 - 230°C.
~x~ample $(~5-1-Indenyl)-CHZ*CHEt-(r~s-1-indenyl)~~rClz (1) 56 cm3 of a 1.6 N (89.6 mmol) solution of butyllithium in hexane were added dropwise to 12.2 g (42.6 mmol) of the ligand (racemate) in 200 cm3 of tetrahydrofuran at room temperature in the course of 1 hour and the mixture was stirred at 60°C for 0.5 hour after the end of the evolution of butane.
The resulting dilithium salt solution was added dropwise, simultaneously with a solu~ta.on of 16.6 g (44 mmol) of c;3 4~ 63 ~') ~.. ;;' h l ZrCl4(tetrahydrofuran)Z in 300 cm3 of tetrahydrofuran, to 50 cm3 of tetrahydrofuran at room temperature in the course of 2 hours. The mixture was then stirred at room temperature for 1.5 hours, and 4 cm3 of a 1.0 N {4 mmol) ethereal solution of HC1 were added. After the dark reaction mixture had spontaneously brightened, an orange color persisted. The mixture was now concentrated to 200 cm3 and the inorganic salts were precipitated by addition of toluene and filtered off.
The filtrate was concentrated further. When the volume was still 100 cm3, a yellow-orange solid was obtained. To bring the precipitation to completion, the mixture was placed in a deep-freeze (-3.5°C) overnight and then filtered and the precipitate was washed with a little cold toluene and then with n-pentane and dried in vacuo.
Yield I: 2.6 g (5.82 mmol - 13.70 ; 1~MR showed a 1:1 mixture of two complexes.
The precipitate which separates out on further concentra tion of the filtrate was treated as described above.
Yield Its 3.3 g (7.39 mmol = 17.40 ; NMR showed a mixture of the complexes from I.
The filtrate was evaporated to dryness. Yield III: 0.2 g.
Fraction II was 'taken up in ether and the mixture was concentrated slowly. The first precipitate ~ obtained shaved an -. 1;3 mixture according to IdMR, the complex which appeared in the five-membered ring proton range in the higher field predominating. When the procedure was repeated with .A, an enrichment to better than 1:4 was obtained (precipitate B, 1.2 g (2.59 mmol = 6.3~).
The filtrate of B evaporated to dryness contained the comgound in resonance in the lower field enriched to more than 4:1 (yield 0.8 g (1.79 mmol = 4.2~)).
Fraction II showed a correct CH analysis: found 58.5 {calculated 59.18) ~ C; 4.6 (4.51)$ H.
Example 2 7.9~ g (27.79 mmol) of ligand (racemate) in 100 cm3 of tetrahydrofuran and 36 cm3 of a 1. 6 N ( 57 . 6 mmol ) solution of butyllithium in hexane were reacted as described in ~.~i~.>,?v Example 1 to give the d:ilithium salt. 10.78 g (28.58 mmol) of ZrClu (tetrahydrofuran)2 in 2fJ0 cm~ of tetrahydrofuran and the dilithium salt solution were added dropwise to 50 cm3 of tetrahydrofuran at room temperature. The procedure followed here was such that a larger amount of zirconium compound was always initially introduced, i.e. the zirconium solution was added in the course of 3 hours and the dilithium salt solution was added in the course of 8.5 hours. .~.fter the mixture had been stirred at room temperature for two hours, 2.5 cm3 of 1. 0 N ( 2 . 5 mmol ) ethereal HCl were added - the mixture brightened immediately - and the mixture was concentrated to about 100 cm3. 150 cm3 of toluene were then added and the mixture was left to stand overnight. The precipitate obtained was separated off and the filtrate was concent-rated. A small amount of oil which occurred during this operation was decanted off and the liquid was evaporated to dryness. The crude product was analyzed by NMR spec-troscopy. The species known from Example 1 was found as the main component, together with at least one other compound. The mixture was extracted with 2 x 120 cm~ of Et2p and the filtrate was evaporated . Tts NMR spectrum shows, in addition to the signals known from Example 1, further resonances in the five-membered ring proton range. The further ether extracts obtained (~ 1 cm~) were evaporated to dryness. 10.5 g of yellow solid were obtained (23.5 mmol = 8~.6~; PdMR: two complexes).
Example 3 ~ ( q5-1-Indenyl ) -C~Ia*CHP~ie- ( r~ 5-1-indenyl ) } ZrClz ( 2 ) ~1 cm3 of a 1.6 N (65.6 mmol) solution of butyllithium in hexane were added dropwise to 7.7 g (30.53 mmol) of ligand (racemate) in 100 cm3 of tetrahydrofuran at room temperature in the course of 1 hour and the mixture was stirred at 60°C for 0.5 hour after the evolution of butane had ended.
11.7 g (31.01 mmol) of ZrCl4(tetrahydrofuran)Z in 250 cm3 of tetrahydrofuran were added, simultaneously with the 6' F !~ r~ r. ~
~; ~~ ~ «~ r~ '..a P~J
dilithiurn salt solution, to 50 cm3 of tetrahydrofuran at roam temperature in the course of 5 hours. After the mixture had been stirred at room temperature for two days, ~ cm3 (4 mmol) of ethereal HC1 were added. The now clear yellow-orange reaction mixture was concentrated to dryness. The orange-red evaporation residue was extracted with 6 x 80 cm3 of toluene and the mixture was filtered and concentrated. An oil which was obtained during concentration to 200 cm3 was decanted off and the filtrate was concentrated further to 80 cm~. The precipitate A
obtained by this procedure was filtered off, washed with a little n-pentane and dried in vacuo. Yield A: 1.85 g (4.28 mmol = 14~); ldP~R shows two complexes.
The filtrate was concentrated further to 30 cm3 and placed at a low temperature (-35°C) overnight, decanted off from precipitate B and evaporated to dryness (0.1 g; I~7MR
showed starting materials i.e. ligand and ZxCI~,(tetra-hydrofuran)2, toluene and probably four complexes).
Precipitate B was washed with pentane and dried in vacuo.
Yield B: 0.7 g (1.62 mmol = 5.3~); IdMR showed the pre-sence of a four-component mixture.
Elemental analysis gave the following result:
found 57.9 (calculated 58.32) C, 4.2~ (4.4) H~
Example 4 ~ ( r~5-1-Indenyl ) -CHz*CH ( benzyl ) - ( r~5-1-indenyl ) }ZrCl2 (3) 17.25 cm3 of a 1.6 13 (27.6 mmol) solution of butyllithium in hexane were added dropwise to 4.53 g (13 mmol) of ligand in 75 crn3 of tetrahydrofuran and the mixture was then stirred at 55°C for 0.5 hour after the evolu-tion of gas had ended.
This dilithium salt solution was added, simultaneously with 4.9 g (12.99 mmol) of ZrCl4(tetrahydrofuranjz in 100 cm3 of tetrahydrofuran, to 30 cm3 of tetrahydrofuran at room temperature in the course of 6 hours, 'the mixture was evaporated to dryness, the residue was taken up in toluene and the mixture was filtered. After the solvent had been stripped off, the residue was digested several times with n-pentane, the pentane being decanted off . The residue now obtained was dried. Yield: 2.28 g (about 4.47 mmol - 34.40; NMR confirmed the presence of at least three complexes, contaminated with tetrahydrofuran and pentane.
Example 5 .((~5-1-Indenyl)_*CHPh*CHPh-(q5-1-indenyi)~ZxCl2 (4) 6.25 cm3 of a 1.6 N (10 mmol) solution of butyllithium in hexane were added dropwise to 2.04 g (4.97 mmol) of ligand (diastereomer mixture) in 40 cm3 of tetrahydrofuran at room temperature. During this procedure, a white-green precipitate separated out after abo~.at half the solution had been added. After the mixture had been stirred at 60°C fox two hours, the dilithium salt obtained was added in portions to 1.88 g (4.98 mmol) of ~xCl,,(tetrahydro-furan)2, dissolved in 40 cm3 of te~trahydrofuran, at 0°C.
Thereafter, the mixture was stirred at room temperature for 4 hours and concentrated 'to dryness, the residue was extracted with a warm (about 40°C) n-pentane/toluene mixture (2:1 by volume), the mixture was fia.tered and the .clear yellow solution obtained was concentrated. A yellow precipitate A obtained by this procedure was filtered off, washed with a little cold Et20 and dried in vacuo.
Yield A: 0 . 45 g ( about 0 . 86 mmoi = 17 . 70 ; PIMR showed, in addition to solvents ( EtaO, tetrahydrofuran, n-pentane, toluene), signals having cleavage patterns of at least two complex compounds, which patterns are characteristic of indenyl complex five-membered ring protons. 25 cm3 of n-pentane were added to the filtrate and precipitate B
which had separated out was filtered off, washed with a little cold Et20 and dried in vacuo. Yield B: 1. 08 g ( 1.57 mmol = 31.5~j; NPY~t showed, in addition to the signals of toluene and pentane, the probable presence of a single complex species which was not present in A.
,.~ r ~,.e sJ . ~ =.~a The fil~tra~te of H was evaporated to dryness. :Cts I~MR
showed, in addition to Et20, pentane and toluene, probably signals of the complex from precipitate B and the ligand.
Rxample 6 ~ ( ~~-1-Indenyl )-CHZ*CHMe-( r~5°1-indenyl ) ~HfCl2 ( 6 ) 34 cm3 of a 1.6 P7 (54.4 mmol) solution of butyllithium in hexane were added dropwise to 7.2 g (26.95 mmol) of ligand (racemate) in 200 cm3 of tetrahydrofuran at room temperature in the course of one hour and the mixture was then stirred at 60°C for 1 hour. The dilithium salt was then added dropwise, simultaneously together with 13 g (28 mmol) of HfCl4(tetrahydrofuran)2 in 200 cm3 of tetra-hydrofuran, to 50 cm3 of tetrahydrofuran, the procedure being such that an Hf excess was present in the reactor vessel. After 2/3 of the reaction partners had been added, the mixture was left to stand overnight and the remainder of the reaction partners was added in the course of 4 hours. The mixture was then stirred overnight and 4 cm3 of 1.0 N (4.0 mmol) ethereal HC1 were added, a brightening in color being observed.
The yellow-brown evaporation residue was extracted with toluene and the mixture was filtered and evaporated to dryness. The resulting residue T was digested with n-pentane, the filtered soleent was stripped off and the remainder of about 25 cm~ was separated of:~ from the precipitate obtained.
Yield A: 0.61 g (1.14 mmol - 4.2~); ~7MR showed, in addition to the signals of the ligand, resonances in the indenyl five-membered ring proton range, which demon-strata the presence of three complex compounds, two being present as main components.
Residue 2 was further extracted with pentane/Et20 (1:2 by volume), the mixture was filtered and the filtrate was concentrated. Yield Bs 0.26 g (0.49 mmol - 1.8~); I~lR
demonstrated the presence of a complex mixture, evidently of four compound: (faur methyl group triplets of the ethyl group in the range from 1.25 to 0.85 ppm).
~J ~ a;~ ~) ~a 1 '.the following elemental analysis was found: calculated 49.5 (found 50.9) ~ C; 3.78 (~.1)~ H.
Example 7 ~ ( r~ $-1-Indenyl ) -CHZCHEt- ( ,~ 5-1-indenyl ) } Z n ( CH3 ) 2 ( 5 ) 4.1 cm~ of a 1.6 N (6.56 mmol) solution of methyllithium in ether were added dropwise to 1.45 g (3.25 mmol) of a suspension of two complex compounds in 50 cm3 of EtzO at -40°C. when a relatively large proportion of the compon-ents had dissolved and a dirty white precipitate had formed, the mixture was evaporated to dryness. after extraction with 200 em3 of n-pentane and filtration, the solvent was stripped off and the residue was dried in vacuo.
3~ield: 1.15 g (about 2.83 mnnol = 87.00; NMR showed, in addition to a few impurities, probably monomethylated compounds, two main components with the resonances typical of CH3Zr species in the high field range, i.e. as expected two resonances fox the syn-form, at -0.76 and -0.88 ppm, and two signals at an almost identical shift of -1.02 ppm for the anti-form, which no longer has CZ
symmetry because of the unsymmetric C2 bridge.
Examuples 7 to 10 and Comparison Example A
A dry 7.6 dm3 kettle was flushed with nitrogen and filled with 10 drn3 of a benzine (boiling range 100-120°C) at 20°C. The gas space in the kettle was then flushed free from nitrogen by forcing in 2 bar of ethylene and letting down S times. Thereafter, 30 cm3 of a toluene solution of methylaluminoxane (10.5 by weight of methylaluminoxane, molecular weight according to cryoscopic determination:
750 g/mol ) were added. The contents of the kettle were heated up to 60°C in the course of 15 minutes, while stirring. The total pressure was then adjusted to 5 bar by feeding in ethylene, while stirring at 250 revolutions per minute. In parallel with this, 3.1 mg of metallocene were dissolved in 20 cm~ of a toluene solution of methyl-aluminoxane (concentration and quality as above) and were ";,~ ~ ') preactivated by being left to stand for 15 minutes. The solution was then introduced into the kettle. The poly-merization system was brought to a temperature of 65°C
and then kept at this temperature for 1 hour by approp-riate cooling. During this period, the total pressure was kept at 5 bar by appropriately feeding in ethylene. The amounts shown in Table 1 were obtained.
The following abbreviations have been used in the tables:
~i'~I = viscosity number in cma/g, Mw = weight-average molecular weight in g/mol Mw/Mn - polydispersity determined by gel permeation chromatography (GPC) II = isotaxy, determined by 13C-NMR spectroscopy, BD = bulk density, T8 = glass transition temperature.
Examples 11 and 12 and Coaa~para.son Example 1B
A clean, dry 1.5 dm3 polymerization reactor with a stirrer was flushed with nitrogen and then with ethylene and fil-led with a solution of norbornene in 750 cm3 of toluene.
The reactor was then brought to a temperature of 20°C, while stirring, and 1 bar of ethylene was forced in. 20 cm~ of a toluene solution of methylaluminoxane (10.1 by weight of methylaluminoxane of molecular we,igla~t 1300 g/mol, cryoscopic determination) were then metered into the reactox and tha mixture was stirred at 20°C for 15 minutes, the ethylene pressure being kept at 1 bar by topping up (saturation of the toluene with ethylene). In parallel with this, the metallocene was dissolved in 10 cm3 of a toluene solution of methylaluminoxane (con-centration and quality see above) and was preactivated by being left to stand for 15 minutes. The solution of the complex was then metered into 'the reactor. Polymerization was subsequently carxied out at 20°C for 1 hour, while stirring (750 revolutions per minute), the ethylene pressure being kept under 1 bar by topping up. The contents of the reactor were then drained rapidly into a stirred vessel into which 100 cm3 of isopropanol had been ~~~~'~)'~''~~~~
K~ ~ 1 7i) TJt '.~) i_ m ~~ -initially introduced. 2 dm3 of acetone were added to this mixture, 'the mixture was stirred for 10 minutes and the suspended polymeric solid was then filtered off, The polymer filtered off was then added to 600 cm3 of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol and this suspension was stirred for 2 hours. The polymer was then filtered off again, washed neutral with water and dried at 80°C under 0.2 bar for 15 hours.
The results of the experiments are summarized in Table 2.
J~xamples 13 to 15 and Comparison Example C
A clean, dry 1.5 dm3 polymerization reactor with a stirrer was flushed with nitrogen and then with propylene and filled with a solution of 30 g of norbornene in 750 cm3 of toluene. The reactor was then brought to a temperature of 20°C, while stirring, and 1 bar of propylene was forced in. 20 cm3 of a toluene solution of methylaluminoxane (10.1 by weight of methylaluminoxane having a molecular weight of 1300 g/mol) were then metered into the reactor and the mixture was stirred at 20°C for 15 minutes, the propylene pressure being kept at 1 bar by topping up (saturation of the toluene with propylene). In parallel with this the metallocene was dissolved in 10 cm' of a toluene solution of methylaluminoxane (concentration and guality see above) and preactivated by being left to stand fox 15 minutes. The solution of the complex was then metered into the reactor. Polymerization was sub-sequently carried out at 20°C for 3 hours, while stirring (750 revolutions per minute), the propylene pressure being kept at 1 bar by topping up. The contents of the reactor were then drained rapidly into a stirred vessel into which 100 cm3 of isopropanol had been initially introduced. 2 dm3 of acetone were added to this mixture, the mixture was stirred for 30 minutes and the suspended polymeric solid was filtered off. The polymer filtered off was then added to 600 cm3 of a mixture of two parts of 3 normal hydrochloric acid and one part of ethanol and I
~~~3~~
this suspension was stirred for 2 hours. 200 cm3 of toluene were then added to the mixture and, after the mixture had been stirred for a further 5 minutes, the toluene phase was separated off and 1 dm3 of acetone was added. The polymer which had been dissolved in toluene by extraction of the hydrochloric acid mixture was precipi-tated during this procedure. The polymeric solid precipi-tated was filtered off and dried at 80°C under 0.2 bar for 15 hours.
The experimental results are summarized in Table 3.
Examples 16 to ~7 A dry 16 dm~ kettle was flushed with nitrogen and then filled with 10 dm3 of liquid propylene. Two thirds of the amount of methylaluminoxane stated in Table ~ for the particular experiment were then added as a solution in toluene and the mixture was stirred at 30°C for 15 minutes. In para11e1 with this a solution of the metallo-cene in one third of the amount of methylaluminoxane stated in Table 4 was prepared and was preactivated by being left to stand for 15 minutes. The metallocene (Examples 1 to '7) were used as mixtures of compounds or as isomer mixtures, without further purification.
This solution was then introduced into the kettle. The polymerization system was brought to th~a appropriate polymerization temperature and the polymerization was started. After 60 minutes, the polymerization was stopped by cooling the reactor and letting down. The resulting polymer yield and the analytical data determined can be seen from Table 4.
r-i ri .-.
' o a o 0 0 ~ cV
N ~ N ~ c c1 n U
.-, O o o to 0 L~ U N tt7 M 0~ u1 I:f.1 w .-i .-i 'p W
r-1 W ~-. o O o o p N tn M wf o ~o ' N N
O .iaO
~ N ~ rn ,-I t~ o-I
r- tn ;
I
a ~ a ~ ~r ~, an ~
I ~ O ~ i F;
N U N U
U
r P- ~~
i J f~
~ I ~ ~
~ ~ ~ ~
I .~i ~ ff ~; - H 7 U ~ ~ Ial r r p ~, O
i r -II
Qi QI~.i >-I ~ .--Irl sl1 e-i ~C..' U ,...1 o~Y r-! 'a~
.-I 3Y r'"~Y i U
N ~ r9 ~
.N N ,I-> ~.,~ p r-1 C~ 'Py tt1 QI N N
N a1 ~ p ~ ~ ,fit ~ ~ '~ ~! ;h ~ "d 1 . 0 ~i ~ ~ '~ ~
0 "~ O O
p p ~ ~ L r-I .-.r ~.. I
1 r-1 as c~ v a ~ 9ro zi .~ I .~ U
.~ ,~
U U U tp U .~.:i~
I t~ U i.d U U
tit ft1 iL1 (i~ .-i PI rI rl .i.) rl rl rl r-I
ii i-I 1-I a-I
'-~'p .R ,.4 O
'b 'CJ N
A!
t0 ~ t-. ao rn U
~
E,~ 1'" !,..' 9 ~1~~~.~~.~e -- ZZ
v ~ .-ia;~;
o, a ~ N
U
b fU ~ ~ Q N
'"'6t1 00M L7 N N
d O
t~
W
O O
O
M M M M
H
O
4a O .!~O
~ N A'~~-I
t~ r~ Q1~ M N M N
t ~i U
N
U V 'k ~N
O N ~N N
r'I
p.j W rWw n , r~ r~r~r~
d w .r ar N N N N
O
td~
M O ya r-! (d y W ~ ~ n-1r1ri ~~~ ~wr -- 2 3 -.
~t tC t0 CO IS7 eP CO N t,~ et C>7 CO ~ et SD O) 6p M ~9 h N C ip 90 M to O ~ tr ~
cr M M C' et M 6t! ~ M M ~~t CO St N N N N
~ ~ct Ln N Id7 6D (C N c~' N ~ ~ 6t7 r~ O O O O O O O O O O O O O O O O O O O O
O O O O O O O O C
O
Q O O O O O O O O O O O O O O C? O O O O O
O O O O O O O O G
O
O O O O O lt7 Lt9 O LA O O O O O O tJ O
O O O O O !17 O O O C
O 6l! O
6t7 CO N 00 N 68 tJt M cf~ t0 ip 6D C~ 6~ O
'~' iwa h ,-~ 6L7 h M 60 ~ O ~ O Q.
~ VI
a ~ lff et CL7 N N M 00 dp ~ ~ h M OD CO h c> t0 (~
h O h 6L7 t<7 M tp a? is Lff ~ c1 M ~ ~ O CJ O taa N iD h O N Off W~ rr CO
O N O O M W M h P tt7 ttf M N Or 6 b' h h ~ h i8 ~' ~ O h . On u7 ITi ~ tD 00 tp uT 6n c~ t~;
U
da m AO N 6f7 O O Ld7 C,7 tD ~ d' t7 O O
e-t O Ll7 '~ ~t (D
ri N ~tD h tA N O (~ O C9 OTf . ~ ct IA CO M M O M N h h f, h N ~ N vb r-a N w N M ~ N rr .-s M w in M ~
et b ..r O ra ~-1 ~ 00 O OOD n OD 000 CO CO AO CO Op0 OpD 00 Op0 CO I~~, n ~ ~ OoD CO 000 ~ h ~
~ ~
W
~ Wit'.~ P cC ' ~ Iw t17 . . M ct h Ln O M lp h O M O c0 C9 M
4-i ~ N Pw M !t CO ~t O cfi M
a a ~1 CD C97 d' P. r4 Pa, ~ In N 6D h O .~nM.-~
Q f N O M f\ M t17 Cn N ld7 ~ a CD ep N ip 00 L67 tp PI h-11_ O '~ N M tp 1.c7 r-t N M l11 CT ~w ~ M (C) On Cf~\ 4 O M ~' w N
(O
.u . a ,. .~' '' x r .~
\
.
i ,Q
U
~ 00 O Y h W 617 N M O ~ f~ N O (~ O O Ll7 QI h IW .-H N LLy~ O G7 Rf' O 07 CT ' ' O O v-9 GD .-~ tn .-i 00 ~. cD CO 6c7 t0 O 6d7 Ca C17 tn M 0 .-~ Cn et et (Ot CO h.. .-4 CO n 1 6d7 .-~ (C1 6I7 d N
h h h r-a h O p In N l0 -1 M N M ~&t .-4 ' OD (~ N N C7tQ tD On er 05 N ~t M t ~w CO
pit r1 .-1 N .-~ n1 r-1 r1 v-9 .-f r-1 N .-1 N
W
'rat.-.
O CC~ 0 0 0 Cl O O t6'f0 6.C1Ca 0 O O 0 0 0 a C~ 0 6n M O 0 0 0 0 0 M ~Y 0 .. ., ., ., .. ., ., ., ., ., ., .. ., ., O ., tt7 (O ., ., ., .. ., ., ., d ., 6~ Qp ., 6d7 O .. ., Ln tc1 O to O Lff ., !l7 C7 O O 6Y! O G7 ~ tp O
!L'7 6Cf ' r~ .~ .~ ~-1 .-1 7 r-i N M N lL1 M .-1 tn 667 U .-d .-i M '-1 N 117 .-f tl7 .-i N .-1 N !tJ .-r u7 N r-1 66'7 I,C
oC
N
~
O G7 O O O O O CI ~ G1 O C9 O O O ~ O
f O O O O O O t~ O 00 C9 O O
60 Lt l O O
' tD O
' ' W ha l L67 ~ 1~ ~ l~ ~' 6l9 0.'p' h Il~
7 e? 7 ~f (~ l0 h ~D IO lt7 (D
I h. f'w CU PW P'~.
w ~
Q
H
ro ro ~ ~ ~
d-1 ~ N r w r qvy a -a N N N
U
~1 ~
N N N N .
c a w w ia ~ ~
u ,, a:
,6 L
U N ~ ~ ~ ~ + ~
. e .
Q 6-~ sa v kJ 6tJ 6L ud UJ 6JJ 16.i eJJ
N N N N N N N N N
r, ~ rr sr /~. v~1 a1 /9 n a~a 6B1 '~ '~ '~ a 'C9 't7 '~ 'li7 'O
C C C C C C Sr C C
F-1 H C.~I i~1 7~i 1..1 IW YW hf ss v v v v v w ,.n an r'~e L L L L L L L L L
N N N N PJ N N hl N
Q
i"1rl 6D h 00 .-~ N tl7 C17 O M ~' 40 h O r4 ~ !l7 C~ M et LO wl N Lf9 Ct1 N M CD
O h, C77 I~
Cp ,.-~~ .-~ N N N N N M M M M M M ct 'et ~~ eY
.-~ N N M M M M eY ~ et N N et N
Claims (8)
1. A process for the preparation of a polyolefin by polymerization of an olefin of the formula R11-CH=CH-R12, in which R11 and R12 are identical or different and are a hydrogen atom or a C1-C14-alkyl radical, or R11 and R12, together with the carbon atom joining them, form a ring having 4 to 28 carbon atoms, at a tempera-ture of 0°C to 150°C, under a pressure of 0.5 to 100 bar, in solution, in suspension or in the gas phase and in the presence of a catalyst which consists of a metallocene and an aluminoxane of the formula (II) for the linear type, and/or of the formula (III) for the cyclic type, in which, in the formulae (II) and (III), R10 is a C1-C6-alkyl group and n is an integer from 2 to 50, wherein the metallocene is at least one compound of the formula (I) in which M is zirconium or hafnium, R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C4-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group or a -NR~, -SR9, -OR9, -OSiR~, -SiR~ or -PR~ radical, in which R9 is a C1-C10-alkyl group, a C6-C10-aryl group or, in the case of radicals containing Si or P, also a halogen atom, or in each case two adjacent radicals R3 or R4, to-gether with the carbon atoms joining them, form a ring and R5, R6 and R7 are a hydrogen atom and R8 is a phenyl, benzyl, methyl, ethyl, trifluoromethyl or methoxy group, or R5 and R7 are a hydrogen atom and R6 and R8 are a phenyl, benzyl, ethyl, methyl, trifluoromethyl or methoxy group.
2. The metallocene of formula (I) in which M is zirconium or hafnium, R1 and R2 are identical or different and are a hydrogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C6-C10-aryl group, a C6-C10-aryloxy group, a C2-C10-alkenyl group, a C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C1-C10-alkyl group or a -NR~, -SR9, -OR9, -OSiR~, -SiR~ or -PR~ radical, in which R9 is a C1-C10-alkyl group, a C6-C10-aryl group or, in the case of radicals containing Si or P, also a halogen atom, or in each case two ad jacent radicals R3 or R4, to-gether with the carbon atoms joining them, form a ring and R5, R6 and R7 are a hydrogen atom and R8 is a phenyl, benzyl, methyl, ethyl, trifluoromethyl or methoxy group, or R5 and R7 are a hydrogen atom and R6 and R8 are a phenyl, benzyl, ethyl, methyl, trifluoromethyl or methoxy group.
3. The metallocene {(~5-1-Indenyl)-CH2*CHEt-(~5-1-indenyl)}ZrCl2.
4. The metallocene {(~5-1-Indenyl)-CH2*CHMe-(~5-1-indenyl)}ZrCl2.
5. The metallocene {(~5-1-Indenyl)-CH2*CH(benzyl)-(~5-1-indenyl)}ZrCl2.
6. The metallocene {(~5-1-Indenyl)-*CHPh*CHPh-(~5-1-indenyl)}ZrCl2.
7. The metallocene {(~5-1-Indenyl)-CH2CHEt-(~5-1-indenyl)}Z~(CH3)2.
8. The metallocene {(~5-1-Indenyl)-CH2*CHMe-(~5-1-indenyl)}HfCl2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3927257A DE3927257A1 (en) | 1989-08-18 | 1989-08-18 | METHOD FOR PRODUCING A POLYOLEFIN |
| DEP3927257.5 | 1989-08-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2023559A1 CA2023559A1 (en) | 1991-02-19 |
| CA2023559C true CA2023559C (en) | 2001-10-30 |
Family
ID=6387348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023559A Expired - Fee Related CA2023559C (en) | 1989-08-18 | 1990-08-17 | Process for the preparation of a polyolefin |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0413326B1 (en) |
| JP (1) | JP2948634B2 (en) |
| AU (1) | AU622826B2 (en) |
| CA (1) | CA2023559C (en) |
| DE (2) | DE3927257A1 (en) |
| ES (1) | ES2071716T3 (en) |
| ZA (1) | ZA906536B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4015254A1 (en) * | 1990-05-12 | 1991-11-14 | Hoechst Ag | METHOD FOR PRODUCING A POLYOLEFIN |
| DE59210001D1 (en) * | 1991-10-15 | 2005-02-17 | Basell Polyolefine Gmbh | Process for the preparation of an olefin polymer using metallocenes with specifically substituted indenyl ligands |
| DE4139261A1 (en) * | 1991-11-29 | 1993-06-03 | Basf Ag | LOW DENSITY ETHYLENE COPOLYMERISATE |
| DE69220675T2 (en) * | 1991-12-13 | 1997-10-23 | Exxon Chemical Patents, Inc., Baytown, Tex. | ETHYLENE / HIGHER ALPHA OLEFIN COPOLYMERS |
| TW314467B (en) * | 1993-03-31 | 1997-09-01 | Hoechst Ag | |
| US5486585A (en) * | 1993-08-26 | 1996-01-23 | Exxon Chemical Patents Inc. | Amidosilyldiyl bridged catalysts and method of polymerization using said catalysts. |
| DE4402192A1 (en) * | 1994-01-26 | 1995-07-27 | Witco Gmbh | Process for the preparation of biscyclopentadienyl compounds |
| DE4406110A1 (en) * | 1994-02-25 | 1995-08-31 | Witco Gmbh | Bridged cyclopentadienyl magnesium compounds and process for their preparation and their use in the production of metallocenes |
| US6242545B1 (en) | 1997-12-08 | 2001-06-05 | Univation Technologies | Polymerization catalyst systems comprising substituted hafinocenes |
| US8497330B2 (en) | 1997-12-08 | 2013-07-30 | Univation Technologies, Llc | Methods for polymerization using spray dried and slurried catalyst |
| US6936675B2 (en) | 2001-07-19 | 2005-08-30 | Univation Technologies, Llc | High tear films from hafnocene catalyzed polyethylenes |
| BR0211286B1 (en) | 2001-07-19 | 2012-10-02 | films with improved physical properties. | |
| US7683140B2 (en) | 2004-05-20 | 2010-03-23 | Univation Technologies, Llc | Method for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring |
| US7754830B2 (en) | 2004-05-20 | 2010-07-13 | Univation Technologies, Llc | Polymerization reaction monitoring with determination of induced condensing agent concentration for preventing discontinuity events |
| US7795194B2 (en) | 2004-11-26 | 2010-09-14 | Mitsui Chemicals, Inc. | Synthetic lubricating oil and lubricating oil composition |
| US7078467B1 (en) | 2005-06-14 | 2006-07-18 | Univation Technologies, Llc | Single catalyst low, medium and high density polyethylenes |
| EP2059540B1 (en) | 2006-09-07 | 2012-12-26 | Univation Technologies, LLC | Methods for on-line determination of degree of resin stickiness using a model for depression of melt initiation temperature |
| MX2009002494A (en) | 2006-09-07 | 2009-05-22 | Univation Tech Llc | Methods for determining temperature value indicative of resin stickiness from data generated by polymerization reaction monitoring. |
| CN102405240B (en) | 2009-04-21 | 2014-05-21 | 三井化学株式会社 | Method for producing olefin polymer |
| US20120135903A1 (en) | 2010-05-11 | 2012-05-31 | Mitsui Chemicals, Inc. | Lubricating oil composition |
| US9676879B2 (en) | 2013-02-08 | 2017-06-13 | Mitsui Chemicals, Inc. | Solid polyaluminoxane composition, olefin polymerization catalyst, olefin polymer production method and solid polyaluminoxane composition production method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3726067A1 (en) * | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
| IT1221653B (en) * | 1987-11-27 | 1990-07-12 | Ausimonti Spa | PROPYLENE CRYSTALLINE COPOLYMERS |
| DE3904469A1 (en) * | 1989-02-15 | 1990-08-16 | Hoechst Ag | METHOD FOR PRODUCING A STATISTICAL PROPYLENE COPOLYMER |
| DE3904468A1 (en) * | 1989-02-15 | 1990-08-16 | Hoechst Ag | POLYPROPYLENE WAX AND METHOD FOR THE PRODUCTION THEREOF |
-
1989
- 1989-08-18 DE DE3927257A patent/DE3927257A1/en not_active Withdrawn
-
1990
- 1990-08-16 ES ES90115672T patent/ES2071716T3/en not_active Expired - Lifetime
- 1990-08-16 DE DE59008625T patent/DE59008625D1/en not_active Expired - Fee Related
- 1990-08-16 JP JP2215082A patent/JP2948634B2/en not_active Expired - Fee Related
- 1990-08-16 EP EP90115672A patent/EP0413326B1/en not_active Expired - Lifetime
- 1990-08-17 AU AU61106/90A patent/AU622826B2/en not_active Ceased
- 1990-08-17 ZA ZA906536A patent/ZA906536B/en unknown
- 1990-08-17 CA CA002023559A patent/CA2023559C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE59008625D1 (en) | 1995-04-13 |
| ZA906536B (en) | 1991-05-29 |
| EP0413326B1 (en) | 1995-03-08 |
| CA2023559A1 (en) | 1991-02-19 |
| JP2948634B2 (en) | 1999-09-13 |
| EP0413326A2 (en) | 1991-02-20 |
| ES2071716T3 (en) | 1995-07-01 |
| DE3927257A1 (en) | 1991-02-21 |
| EP0413326A3 (en) | 1992-09-02 |
| AU622826B2 (en) | 1992-04-16 |
| JPH03106907A (en) | 1991-05-07 |
| AU6110690A (en) | 1991-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2023559C (en) | Process for the preparation of a polyolefin | |
| KR100348379B1 (en) | Uncrosslinked indenyl-containing metallocene | |
| KR100390258B1 (en) | Thermoplastic Elastomeric Stereoblock Olefin Polymers Methods and Metallocene Catalysts | |
| AU649821B2 (en) | Process for preparing fluorenyl containing metallocenes | |
| CA1319784C (en) | Process for the preparation of a 1-olefin polymer | |
| EP0666267B1 (en) | Organometallic fluorenyl compounds, preparation, and use | |
| US5627117A (en) | Olefin polymerization catalyst and process for olefin polymerization | |
| US6020444A (en) | Process for preparing a cycloolefin copolymer | |
| EP0672675B1 (en) | Organometallic fluorenyl compounds, preparation, and use | |
| CA2198954C (en) | Substituded indenyl unbridged metallocenes | |
| CA2020640C (en) | Process for the preparation of cycloolefin polymers | |
| KR950009197B1 (en) | Novel transition metal compound and process for polymerizing olefin by using the same | |
| JP3285370B2 (en) | Method for producing polyolefin | |
| EP0628565A1 (en) | Bis fluorenyl metallocenes and use thereof | |
| JPH0278687A (en) | Production of benzene-insoluble organoaluminumoxy compound | |
| JPH04268308A (en) | Preparation of olefin polymer | |
| US5627247A (en) | Organometallic fluorenyl compounds and use thereof in olefin polymerization | |
| JPH11510203A (en) | Improved method for preparing metallocene catalyst systems | |
| NO310874B1 (en) | Metallocene compound and process for its use in the production of olefin polymer | |
| CA2051886A1 (en) | Homogeneous catalysts and olefin polymerization process | |
| CA2219652A1 (en) | Metallocenes containing partially hydrogenated p-ligands | |
| JP2837246B2 (en) | New syndiotactic polypropylene | |
| JP2641459B2 (en) | Process for producing α-olefin polymer | |
| JPH05202124A (en) | Production of olefin polymer | |
| JP2948642B2 (en) | Method for producing polyolefin, catalyst used therefor, and aluminoxane component of the catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |