CA2026237A1 - Process for the preparation of a polyolefin - Google Patents
Process for the preparation of a polyolefinInfo
- Publication number
- CA2026237A1 CA2026237A1 CA002026237A CA2026237A CA2026237A1 CA 2026237 A1 CA2026237 A1 CA 2026237A1 CA 002026237 A CA002026237 A CA 002026237A CA 2026237 A CA2026237 A CA 2026237A CA 2026237 A1 CA2026237 A1 CA 2026237A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- polymerization
- aluminoxane
- group
- metallocene
- 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.)
- Abandoned
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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 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
- C08F4/63927—Component covered by group C08F4/62 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
ABSTRACT
Process for the preparation ofdie a polyolefin Olefins of the formula Ra-CH=CH-Rb ( Ra, Rb = H or C1-C14-alkyl) are polymerized in the pre-sence of a catalyst comprising an aluminoxane of the formula I
(I) for the linear type and/or of the formula (II)
Process for the preparation ofdie a polyolefin Olefins of the formula Ra-CH=CH-Rb ( Ra, Rb = H or C1-C14-alkyl) are polymerized in the pre-sence of a catalyst comprising an aluminoxane of the formula I
(I) for the linear type and/or of the formula (II)
Description
3J ~ d ~J r ~ ?
HOECHST AKTIENGESELLSCHAFT HOE 89/F 320 Dr. DA/~ch Description Proces~ for the preparation of a polyolefin The invention relates to an ole~in polym r having a high molecular weight and a low residual catalyst content.
The preparation of isotactic PP is achieved with the aid of ethylene-bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride together with an aluminoxane in a su~pension polymerization (cf. EP A 185,918). The polymer has a narrow molecular weight distribution ~M~/M~ 1.6 to 2.6).
By means of a specific preactivation method~ it was possible to achieve a 6ubstantial increase in the acti-vity of the catalyst system (cf. DE 3,726l067). The ~rain morphology of the polymer was also Lmproved by this preactivation method.
The isotaxy ~or syndiotaxy) of the polyolefins can be adjusted by selecting the polymerization temperature (cf. DE 3,~26,075~ or the catalyst (cf. DE 3,826,075, DE 3,726,067~. However, for certain polymerization processes, it i~ desirable ko influence the i~otaxy (or syndiotaxy) by means o~ a further component.
Accordingly, the ob~ect was to ~ind a proc~ss ~or ~he preparation of a high-molecular-weight olefin polymer which can be carrled ou~ in a temperature range ~hich is of industrial interest and at a high cataly~t activity and which make~ it pos~ible to control the isota~y or syndiota~y in a sLmple manner.
It ha~ been found that the object can be achieved by th~
polymexization of olefins in the pre~ence of certain m~tallocene catalyst~ and certain acti~ators~
~J ~ 3 ~J P,~ ~
Accc)rdingly, the invention relates to a proCess for ~he prepara~ion of a polyolefin hy polymeri~a~ion o~ an c: le~in of the ~ormula R~-CH=CH-Rb, in whiCh Ra and Rb are identical or differen~ and are a hydrogen atom or a C~-C14 alkyl radical or R~ and Rb, together with the carbon atom linking khem, form a ring of 4 to 28 carbon atoms, at a temperature of 0C to 150C, at a pre~sure of 0.5 to 100 bar, in solution, in suspension or in the ga3 phase, ; in the presence of a catalyst consisting of a metallocene and an aluminoxane, wherein the aluminoxane i~ a compound of the formula (I3 \ Al - O ~ Al - O ~ Al \ (I) : for the linear type and/or of ~he formula (II) .' _ Al - O ~ ~
. n~2 :
for the cy~lic type, R1 in the fonmulae (I) and (II) being a Cl-C6-alkyl group or a hydrogen atom and n being an inkeger ~rom 2 to 50, 0.01 to 40~ of the radicals R1 being hydrogen akom~.
The cataly~t to be u~ed for the proce~s according to the invention comprise~ a me~allocene and an aluminoxane of th~ formula ~I) Rl Rl Rl Al O ~ ~1-~ O - Al ~I) R1 ~ n \ Rl for the linear type and/or o ~he fonmula (II) Rl _ Al - O (II) . n+2 for the cyclic type. In these formulae, R1 is a Cl C6-alkyl gxoup, preferably methyl, ethyl or isobutyl, in particular methyl, and n is an integer from 2 to 50, S preferably S to 40 or a hydroge~ atom. In the~e formulae, 0.01 to 40%, preferably 0.01 to 35%, of the radical~ R1 are hydrogen atoms. Howevex, the ~act structure of the aluminoxane is not known.
The aluminoxane can be prepared by various methods.
One possibility is the careful addition of water to a dilute solution of a dialkylaluminum hydride by adding the solutio~ of the dialkylaluminum hydride, preferably dLmethylaluminum hydride and the water, each in small portions, to an initially introduced relatively large amount of an inert ol~ent and waiting after each addi-tion until the 0volution o~ ga~ ha~ cea~ed.
In another proces~, finely powdered copper gulfate pentahydrate i~ ~uspended in toluene and dialkylalumlnum hydride is added in a glass flask under an inert ga~ at about -20QC in such an amount that about 1 mvlecule of CuSO~ ~ 5H20 i3 available or every 4 Al atom~. After ~low hydrolysi~ with the elLmination of alkans ~nd hydrogen/
the reaction mixture i5 left at room temperature for 24 to 48 hours; during which it may have to be cooled so that the temperature does not exceed 30~C. The copper sulrate is then filtered off from the alumino~ane dis-solved in toluene, and the solution is concQntrated in vacuo. It i~ assumed that in this pxeparation proce~ the low-molecular-weight aluminoxane~ condense to give higher oligomer~O The ~olu~ion can al o be u ed as such.
Furthermoxe, aluminoxanes ~re ob~a.Lne~ by r~acking _ 4 ~ J r,i dial~ylaluminum hydride, pr0ferably d~ne~h~lalumi.num hydride, dissolved in an iner~ alipha~ic or aromatic 901 vent, preferably hep~ane or toluene, with hydrated aluminum salt~, preferably aluminum sulfa~e at a tempera~
tuxe of -20 to 100C. In thi~ reaction, the volume ra~io of the solvent to the alkylaluminum hydride used i~
to 50:1 - preferably 5:1 - and the reaction tLme, which can be controlled by the elLmin2tion o~ the alkane, i~ 1 to 200 hours - preferably 10 to 40 hour~.
Of the hydrated aluminum salts, in particular tho~e are used which hava a high content of water of crystalliz-ation. Particular preference is given to aluminum sulfate : hydrate, in particular to the compounds Al2~SO4)3 . 16H2O
and Alz( S04 ) 3 . 18H2O, which haYe a particularly high content of water of crystallization of 1~ and 18 mol of H2O/mole of Al2( S04 ~ 3 respectively.
A further variation of preparing aluminoxanes comprises dissolving dialkylaluminum hydride, preferably dimethyl-aluminum hydride, in the su~pending agent, pxeferably in the liquid monsmer, in heptane or toluene, initially introduced into the polymerization boiler, and then reacting the al~minum compound with water.
Apar~ frsm the proce~e~ ~or the preparation of aluminoxane5 de~cribed above, furthar u~abl.e proce~ses exist.
Variou~ compounds of thi~ type can be u~ed a3 metallo-cenc, for example compounds of the formula I~
/ ~ R~
R~ Ml ~
~ 3 In formula III, ~ a m~tal from the group compri~ing titanium, zirconium, hafnium, vanadium, niobium, tantalum 5 - ~'J'~,~J~ J~ ~.J ;~
and chromium, prefera~ly zirconium and hafnium.
R2 and R3 are identical or different and denote a hydrogen atom, a Cl~Clo~r preferably Cl-C3-alkyl group, a Cl-C10-, preferably C1-C3-alkoxy group, a C6-C10 , preferably C6-C~-5 aryl group, a C6-C10-, preferably C6-C8-arylo~y group, a C2-C10-, preferably C2 Cb-alkenyl group, a C7 -C~o~ I
preferably C7-C10 arylalkyl group, a C7 Cl4-, pre~erably C7-C12-alkylaryl group, a C8-C40-, preferably Ca-Cl2-axyl-alkenyl group, or a halogen ~tom, preferably chlorine.
10 R~ and R5 are different and are a mono- or p~lynuclear hydrocarbon radical, which can form a sandwich ~tructure with the central atom M1.
R4 and R5 are preferably fluorenyl and cyclopentadienyl, it being possible for the parent structures to carry 15 additional substituents.
R6 is a bridge comprising one or more members, which links the radicals R4 and R5 and is -M2- _M2_M2_ , -M2_~R9_ , ~C- , -O-M~ C~
R8 R8 R8 R8 RB R8 R8 ~8 =BR7, =AlR7, -Ge-, -Sn-, ~0-, -S-, ~SO, -S2~ =NR7, ~CO, =PR7 or =P(o)R7, in which R7, R~ and R~ are identical or 20 dif~erent and are a hydrogen atom/ a halogen a~om, preferably chlorine, a C1-C10-~ preferably C1-C3-al~yl group, in particular a methyl group, a Cl-C10-fluoroalkyl group, pxeferably CF3 group, a C6-C10-fluoro~ryl group, preferably pentafluorophenyl group, a C~-C10-; preferably : 25 C6-C8~aryl group, a Cl-C10-, preferably Cl-C4 lkoxy group, in particular a methoxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-a~yl~lkyl group, a Ca-C40-, prefera~ly C8-C12-arylalkenyl group or a C7-C40-, preferably C7-C~2-alkylaryl group, or ~6 and R7 or 30 R6 and R8, together with the atoms linXing th~m, each form h glJ ~.. (i ~) 3 ,jl a ring.
M2 is silicon, germanium or tin, prefexably silicon or germanium.
R6 is preferably =CR7Ra, =SiR7Ra, =~eR7Ra, -O-, -S-, =SO, 5 =PR7 or =P(o)R7.
The metallocenes described above can be prepared accor-: ding to ~he following general reaction scheme:
H2R4+ButylLi-~ HR4Li X_R6_X HR4 R6_R5H 2-BUtYl~i R5+ButylLi--HR5L1 LiR4-R5-R5Li MlC14_~
R6 Ml R2Lir R6 M1 ~ ~6 / '1 R5 R5 ~5 (X - Cl, Br, I, O~tosyl) ~J 3~ ~JJ ~ J ~
or H~R4 ~ ButylLi ~HR4Li \ C/ ~L~5 R7R~C\
HOECHST AKTIENGESELLSCHAFT HOE 89/F 320 Dr. DA/~ch Description Proces~ for the preparation of a polyolefin The invention relates to an ole~in polym r having a high molecular weight and a low residual catalyst content.
The preparation of isotactic PP is achieved with the aid of ethylene-bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride together with an aluminoxane in a su~pension polymerization (cf. EP A 185,918). The polymer has a narrow molecular weight distribution ~M~/M~ 1.6 to 2.6).
By means of a specific preactivation method~ it was possible to achieve a 6ubstantial increase in the acti-vity of the catalyst system (cf. DE 3,726l067). The ~rain morphology of the polymer was also Lmproved by this preactivation method.
The isotaxy ~or syndiotaxy) of the polyolefins can be adjusted by selecting the polymerization temperature (cf. DE 3,~26,075~ or the catalyst (cf. DE 3,826,075, DE 3,726,067~. However, for certain polymerization processes, it i~ desirable ko influence the i~otaxy (or syndiotaxy) by means o~ a further component.
Accordingly, the ob~ect was to ~ind a proc~ss ~or ~he preparation of a high-molecular-weight olefin polymer which can be carrled ou~ in a temperature range ~hich is of industrial interest and at a high cataly~t activity and which make~ it pos~ible to control the isota~y or syndiota~y in a sLmple manner.
It ha~ been found that the object can be achieved by th~
polymexization of olefins in the pre~ence of certain m~tallocene catalyst~ and certain acti~ators~
~J ~ 3 ~J P,~ ~
Accc)rdingly, the invention relates to a proCess for ~he prepara~ion of a polyolefin hy polymeri~a~ion o~ an c: le~in of the ~ormula R~-CH=CH-Rb, in whiCh Ra and Rb are identical or differen~ and are a hydrogen atom or a C~-C14 alkyl radical or R~ and Rb, together with the carbon atom linking khem, form a ring of 4 to 28 carbon atoms, at a temperature of 0C to 150C, at a pre~sure of 0.5 to 100 bar, in solution, in suspension or in the ga3 phase, ; in the presence of a catalyst consisting of a metallocene and an aluminoxane, wherein the aluminoxane i~ a compound of the formula (I3 \ Al - O ~ Al - O ~ Al \ (I) : for the linear type and/or of ~he formula (II) .' _ Al - O ~ ~
. n~2 :
for the cy~lic type, R1 in the fonmulae (I) and (II) being a Cl-C6-alkyl group or a hydrogen atom and n being an inkeger ~rom 2 to 50, 0.01 to 40~ of the radicals R1 being hydrogen akom~.
The cataly~t to be u~ed for the proce~s according to the invention comprise~ a me~allocene and an aluminoxane of th~ formula ~I) Rl Rl Rl Al O ~ ~1-~ O - Al ~I) R1 ~ n \ Rl for the linear type and/or o ~he fonmula (II) Rl _ Al - O (II) . n+2 for the cyclic type. In these formulae, R1 is a Cl C6-alkyl gxoup, preferably methyl, ethyl or isobutyl, in particular methyl, and n is an integer from 2 to 50, S preferably S to 40 or a hydroge~ atom. In the~e formulae, 0.01 to 40%, preferably 0.01 to 35%, of the radical~ R1 are hydrogen atoms. Howevex, the ~act structure of the aluminoxane is not known.
The aluminoxane can be prepared by various methods.
One possibility is the careful addition of water to a dilute solution of a dialkylaluminum hydride by adding the solutio~ of the dialkylaluminum hydride, preferably dLmethylaluminum hydride and the water, each in small portions, to an initially introduced relatively large amount of an inert ol~ent and waiting after each addi-tion until the 0volution o~ ga~ ha~ cea~ed.
In another proces~, finely powdered copper gulfate pentahydrate i~ ~uspended in toluene and dialkylalumlnum hydride is added in a glass flask under an inert ga~ at about -20QC in such an amount that about 1 mvlecule of CuSO~ ~ 5H20 i3 available or every 4 Al atom~. After ~low hydrolysi~ with the elLmination of alkans ~nd hydrogen/
the reaction mixture i5 left at room temperature for 24 to 48 hours; during which it may have to be cooled so that the temperature does not exceed 30~C. The copper sulrate is then filtered off from the alumino~ane dis-solved in toluene, and the solution is concQntrated in vacuo. It i~ assumed that in this pxeparation proce~ the low-molecular-weight aluminoxane~ condense to give higher oligomer~O The ~olu~ion can al o be u ed as such.
Furthermoxe, aluminoxanes ~re ob~a.Lne~ by r~acking _ 4 ~ J r,i dial~ylaluminum hydride, pr0ferably d~ne~h~lalumi.num hydride, dissolved in an iner~ alipha~ic or aromatic 901 vent, preferably hep~ane or toluene, with hydrated aluminum salt~, preferably aluminum sulfa~e at a tempera~
tuxe of -20 to 100C. In thi~ reaction, the volume ra~io of the solvent to the alkylaluminum hydride used i~
to 50:1 - preferably 5:1 - and the reaction tLme, which can be controlled by the elLmin2tion o~ the alkane, i~ 1 to 200 hours - preferably 10 to 40 hour~.
Of the hydrated aluminum salts, in particular tho~e are used which hava a high content of water of crystalliz-ation. Particular preference is given to aluminum sulfate : hydrate, in particular to the compounds Al2~SO4)3 . 16H2O
and Alz( S04 ) 3 . 18H2O, which haYe a particularly high content of water of crystallization of 1~ and 18 mol of H2O/mole of Al2( S04 ~ 3 respectively.
A further variation of preparing aluminoxanes comprises dissolving dialkylaluminum hydride, preferably dimethyl-aluminum hydride, in the su~pending agent, pxeferably in the liquid monsmer, in heptane or toluene, initially introduced into the polymerization boiler, and then reacting the al~minum compound with water.
Apar~ frsm the proce~e~ ~or the preparation of aluminoxane5 de~cribed above, furthar u~abl.e proce~ses exist.
Variou~ compounds of thi~ type can be u~ed a3 metallo-cenc, for example compounds of the formula I~
/ ~ R~
R~ Ml ~
~ 3 In formula III, ~ a m~tal from the group compri~ing titanium, zirconium, hafnium, vanadium, niobium, tantalum 5 - ~'J'~,~J~ J~ ~.J ;~
and chromium, prefera~ly zirconium and hafnium.
R2 and R3 are identical or different and denote a hydrogen atom, a Cl~Clo~r preferably Cl-C3-alkyl group, a Cl-C10-, preferably C1-C3-alkoxy group, a C6-C10 , preferably C6-C~-5 aryl group, a C6-C10-, preferably C6-C8-arylo~y group, a C2-C10-, preferably C2 Cb-alkenyl group, a C7 -C~o~ I
preferably C7-C10 arylalkyl group, a C7 Cl4-, pre~erably C7-C12-alkylaryl group, a C8-C40-, preferably Ca-Cl2-axyl-alkenyl group, or a halogen ~tom, preferably chlorine.
10 R~ and R5 are different and are a mono- or p~lynuclear hydrocarbon radical, which can form a sandwich ~tructure with the central atom M1.
R4 and R5 are preferably fluorenyl and cyclopentadienyl, it being possible for the parent structures to carry 15 additional substituents.
R6 is a bridge comprising one or more members, which links the radicals R4 and R5 and is -M2- _M2_M2_ , -M2_~R9_ , ~C- , -O-M~ C~
R8 R8 R8 R8 RB R8 R8 ~8 =BR7, =AlR7, -Ge-, -Sn-, ~0-, -S-, ~SO, -S2~ =NR7, ~CO, =PR7 or =P(o)R7, in which R7, R~ and R~ are identical or 20 dif~erent and are a hydrogen atom/ a halogen a~om, preferably chlorine, a C1-C10-~ preferably C1-C3-al~yl group, in particular a methyl group, a Cl-C10-fluoroalkyl group, pxeferably CF3 group, a C6-C10-fluoro~ryl group, preferably pentafluorophenyl group, a C~-C10-; preferably : 25 C6-C8~aryl group, a Cl-C10-, preferably Cl-C4 lkoxy group, in particular a methoxy group, a C2-C10-, preferably C2-C4-alkenyl group, a C7-C40-, preferably C7-C10-a~yl~lkyl group, a Ca-C40-, prefera~ly C8-C12-arylalkenyl group or a C7-C40-, preferably C7-C~2-alkylaryl group, or ~6 and R7 or 30 R6 and R8, together with the atoms linXing th~m, each form h glJ ~.. (i ~) 3 ,jl a ring.
M2 is silicon, germanium or tin, prefexably silicon or germanium.
R6 is preferably =CR7Ra, =SiR7Ra, =~eR7Ra, -O-, -S-, =SO, 5 =PR7 or =P(o)R7.
The metallocenes described above can be prepared accor-: ding to ~he following general reaction scheme:
H2R4+ButylLi-~ HR4Li X_R6_X HR4 R6_R5H 2-BUtYl~i R5+ButylLi--HR5L1 LiR4-R5-R5Li MlC14_~
R6 Ml R2Lir R6 M1 ~ ~6 / '1 R5 R5 ~5 (X - Cl, Br, I, O~tosyl) ~J 3~ ~JJ ~ J ~
or H~R4 ~ ButylLi ~HR4Li \ C/ ~L~5 R7R~C\
2 Butyll.i [ R7~8~ ~ L1 MlCl"
\ 1 5 R
R2Li /1 1~ ~ \, /Ml~
R5 E~5 Examples of ~uitable metallocene~ are bi~(indenyl)~thyl-eneæirconium dichloride, bis ( indenyl ) ethylenehafnium di-chlorids, bi3 ( indenyl ) dimethyl~ilylene~irconium dichlo-ride, bis(indenyl)dimethylæilyleneha~nium dichloride, furthermore (arylalkylidene)(9-fluorellyl)(cyclopentadi~
enyl~zirconiu~ dichlsride, (diarylmethylene)(9-fluoren-yl)(cyclopentadienyl)zirconium dichlori~e, and (dial~yl-methylene)(9-fluorenyl)~cyclopentadienyl)zirconium dichloride, and the corresponding hafnium compounds.
Before its use in the polymerization reaction, i~ i~
possible to preactivate the metallocene with an alumin-oxane of the formula (I) and/or (II). This substantially increases the polymerization activity and Lmprove~ the grain morphology.
The preactivation of the transition metal compound is carried out in solution Preferably, the metallocene is dissolved in a solution of the aluminoxane in an i~ert hydrocarbon. Suitable inert hydrocarbons are aliphatic or ~5 aromatic hydrocarbons.
Preferably, toluene is used.
The concentration of the aluminoxane in the solution is in the range of about 1% by weight up to the saturakion lLmit, preferably 5 to 30% by weight, in each case relative to the entire solution. The metallocene can b~
used in the ~me concentration, but preferably it i~ u~ed in an amount of 10-4-1 mol per mole of aluminox~ne~ The preactivation tlme is 5 mlnutes to 60 hours, preferabl~
5 to 60 minutes. qlhe preactivation is carriad out at temperature o~ -78~C to 100C, pre~erably 0 to 70C.
The pol~merization is carried ou~ in a known manner i~
solution, in suspension or in the ga~ phase, continuously or batchwise, in one or more step~ at a temperatuxe of 30 to 150C, preferably 30 to 80~C. The olefin~ w.hich are pol~meri~ed are those of the for~la RU-C~-CH~Rb. In thi~
formula, R~ and R~ are identical or different and are a hydrogen atom or an alkyl radical of 1 to 28 carbon atoms. However, Ra and Rb, together with the carbon a~om~
linking them, can also form a ring of 4 ~o 28 car~on ~J i~ ~J
9 _ atoms. Exa~ples of olefin of thi~ type are ethylene, propylene, 1-bu~ene, 1-hexene, 4-methyl-1-pentene, l-octene, norbornene, norbornadiene, pentene, hexene or octene. Especially propylene is polymerized.
If neces~ary, hydrogen is added as a mvlecular weight xegulator. The total pressure in the polymerization system is 0.5 to 100 bar. The polymerization in the pressure range of 5 to 64 bar, which is of particular industrial interest, is preferr~d.
The metallocene compound is u~ed in a concentration~
relative to the transition metal, of 10-3 to 10-7, preferably 10-4 to 10-6, mol of transi~ion metal per d~3 of solvent or per dm9 of reactor volume. The aluminoxane is used in a concentration of 10-5 to 10~1 mol, preferably 10-4 to 10-2 mol, per dm3 of solvent or per dm3 of reactor volume. However, in principle, higher concentrations are also possible. At least one compound of the formula III
is used a~ the metallocene. Mixtures of ~everal compounds of the formula III or mixtures of isomers are also po~sible.
If the polymerization is carried out a~ suspension or solution polymeriæation~ an inert ~ol~ent cus~omary ~or the Ziegler low-pressure proces~ is used. For oxampla~
the polymerization i^~ carried out in an aliphatic or cycloaliphatic hydrocarbon; exz~rnples of ~uch a hydro-carbon are ~utane, pentane, hexane, heptane, isooc~ane, cyclohexane, methylcyclohexane~
Furthermore, a benzine or hydrogenated diesQl oil frac-tion can be used. Toluene i8 also u able. Preferably, the polymerization i6 ca.rried out in ~he liguid mo~omer. If inert sol~ent~ are used, the monomers are metered in as a gas or a liquid. If only one monomer is used a3 su~pen ding agent, the comonomer or-comonomer~ are metered in a~
a gas or li~uid. Furthermore, it i8 posslble to carry out the polymerization in a mixture of different monomer~ as - 19 ~ "7 suspending agent; a further monomer can ~hen be metered in as a liquid or a gas. If ethylene is used, it i~
advantayeous to introduce initially a portion of the ethylene and meter in the remainder during the polymerization.
The duration of th~ polymerization i5 as desired, since the catalyst system to be used according to the invention shows only a small time-dependent drop in pol~merization activi~y.
Tha process according to the invention is distinguished by the ~ ct that the metallocenes used are very tempera-ture stable, so that ~hey can be used with high activity even at temperatures of up to 90C. Furthermore, the aluminoxanes which serve a~ cocatalysts can be added in smaller concentrations than previously. Finally, it i~
now possible to prepare random copol~mers at tempera~ures which ar~ of industrial intexest.
A further advantage of the proce~s accoxding to the invention i8 that ~he mixture of methylaluminoxane and hydridomethylaluminoxane offer~ tha po~ibility ko control the i otaxy or syndiotaxy of the pol~er.
The example~ which follow are intended to illu~trat0 tha invention. The ~ymbol8 have the following meanings s VN = visco~ity number in cm3 5 SI = ~yndiotactic index/ dete.rmined by l3C-NMR
speckro~copy II = isotactic index, determined by '3 spectroscopy E:~ample 1 A dry 16 dm3reactor wa~ flu~hed with nitrogen and filled wikh 10 clm3 of liquid propylene. 68 cm3 of a hydrido-me~hylaluminoxane ~olution in toluene (= XM~O, corres~
ponding to 40 mmol of Al, mean oligomerizatlon degree ~ 13 ~3J ~
n = 30) were then added, and the batch was stirred at 30C for 15 minutes.
':
At the same t~, 50 mg of bis(indenyl)ethylenehafnium dichloride were dissolved in 34 cm3 MAO (= 20 mmol Al) and preactivated by letting it stand for 15 minutes.
This solution was then poured into the reactor. The polymarization system was brought to a temperature of 70C, and the polymerization began. The polymeri~ation wa~ stopped after 60 minuteq by cooling the reactor and releasiny the pressure. 0.16 kg of polypropylene was obtained. The activity was therefore 3.2 kg of PP/g of metallocene/h.
The following analytical data of the polymer were determined:
VN = 73 cm3/g~ II = 92%.
~ xample 2 .~
A dry 16 dm3 reactor wa~ flushed with nitrogen and filled with 10 dm3 of liquid propylene. 68 cm3 of a hydri~o-methylaluminoxane ~olution in toluene (= HMAO, corre~pondLng to 40 mmol o~ Al, mean oligomerization degree n = 30~ were then added, and the batch wa~ 3tixred at 30C for 15 minutesO
~t the same ~, 7 mg of bi~(indenyl)dimethyl~ilylene-zirconium dichloride were di3solved in lS cm3 MAO
~= 20 mmol Al~ and preactivated by letting it stand for 15 minutes.
This so1u~ion was then poured into the reacto~- The polymerization system was brought to a ~emperature of 70C, and the polymerization began. ~he polymerization was ~topped after 60 minu~es by cooling the reactor and releasing the pressure. 0.88 kg of polypropylene W~5 obtained. The activity was therefore 126 kg of PP~g of ~2~,~", 1 metallocene/h.
The followlng analytical data of ~he polymer were determined:
VN = 49 cm3/g~ II = 85%.
E2ampl~ 3 A dry 16 dm3 reactorwas flu~hed with nitrogen and filled with 10 dm3 of liquid propylene. 68 cm3 of a hydrido-methylaluminoxane solution in toluene (= HMA0, oorres-ponding to 40 mmol of Al, mean oligomerizati~n degree n = 30) were then added, and the batch was ~tirred at 30C for 15 minutes.
At the same t ~ , 60 mg of fluorenylisopropylidenecyclo-pen~adienylhafnium dichloride were dissolved in 34 cm3 HMAO (= 20 mmol Al) and preactivated by letting it stand for 15 minutes.
This solution was then poured into the reactor. The polymerization system wa~ brought to ~ temperature of 60C, and the polymerization began. The polymerization was ~topped after 60 minutes by cooling the reactor and relea~ing the pres~uxe. 1.45 kg of polypropylene were obtainad. Th~ actiYity wa~ thexefore 11.9 kg of PP/g o~
metallocene/h.
The following analytical data o~ the polymer were determined~
~S VN = 51~ cm3/g, SI = 92%.
~ample 4 A dry 16 dm3 rea~torwa~ flu~hed with nitrogen and illed with 10 dm3 of liquid propylene. 68 cm3 of a hydrido-methylaluminoxane solution in toluene ~= H~A0, corr2s-ponding to 40 mmol of Al, mean oli~omeriza~ion degreen = 30) were then added~ and the batch wa~ . irrsd at - 13 ~ 3 ~
30C ~or lS minutes.
At the same t ~ , 20 mg of fluoxenylisopropylidenecyclo-pentadienylzirconium dichloride were dissol~ed in 34 cm3 HMAO (= 20 mmol Al) and preactivated by letting it stand for 15 minutes.
This solution was then poured into the reactor. The polymerization system was brought to a temp~rature of 50C, and the polymerization bPgan. The polymerizat.ion was stopped after 60 minutes by cooling the reactor and releasing the pressure. 0.68 kg of polypropylene was obtained. The activi y wa~ therefore 34 kg of PP/g of metallocene/h.
The following analytical data of the polymer were determined:
lS VN = 123 cm3/g, 5I = 89%.
\ 1 5 R
R2Li /1 1~ ~ \, /Ml~
R5 E~5 Examples of ~uitable metallocene~ are bi~(indenyl)~thyl-eneæirconium dichloride, bis ( indenyl ) ethylenehafnium di-chlorids, bi3 ( indenyl ) dimethyl~ilylene~irconium dichlo-ride, bis(indenyl)dimethylæilyleneha~nium dichloride, furthermore (arylalkylidene)(9-fluorellyl)(cyclopentadi~
enyl~zirconiu~ dichlsride, (diarylmethylene)(9-fluoren-yl)(cyclopentadienyl)zirconium dichlori~e, and (dial~yl-methylene)(9-fluorenyl)~cyclopentadienyl)zirconium dichloride, and the corresponding hafnium compounds.
Before its use in the polymerization reaction, i~ i~
possible to preactivate the metallocene with an alumin-oxane of the formula (I) and/or (II). This substantially increases the polymerization activity and Lmprove~ the grain morphology.
The preactivation of the transition metal compound is carried out in solution Preferably, the metallocene is dissolved in a solution of the aluminoxane in an i~ert hydrocarbon. Suitable inert hydrocarbons are aliphatic or ~5 aromatic hydrocarbons.
Preferably, toluene is used.
The concentration of the aluminoxane in the solution is in the range of about 1% by weight up to the saturakion lLmit, preferably 5 to 30% by weight, in each case relative to the entire solution. The metallocene can b~
used in the ~me concentration, but preferably it i~ u~ed in an amount of 10-4-1 mol per mole of aluminox~ne~ The preactivation tlme is 5 mlnutes to 60 hours, preferabl~
5 to 60 minutes. qlhe preactivation is carriad out at temperature o~ -78~C to 100C, pre~erably 0 to 70C.
The pol~merization is carried ou~ in a known manner i~
solution, in suspension or in the ga~ phase, continuously or batchwise, in one or more step~ at a temperatuxe of 30 to 150C, preferably 30 to 80~C. The olefin~ w.hich are pol~meri~ed are those of the for~la RU-C~-CH~Rb. In thi~
formula, R~ and R~ are identical or different and are a hydrogen atom or an alkyl radical of 1 to 28 carbon atoms. However, Ra and Rb, together with the carbon a~om~
linking them, can also form a ring of 4 ~o 28 car~on ~J i~ ~J
9 _ atoms. Exa~ples of olefin of thi~ type are ethylene, propylene, 1-bu~ene, 1-hexene, 4-methyl-1-pentene, l-octene, norbornene, norbornadiene, pentene, hexene or octene. Especially propylene is polymerized.
If neces~ary, hydrogen is added as a mvlecular weight xegulator. The total pressure in the polymerization system is 0.5 to 100 bar. The polymerization in the pressure range of 5 to 64 bar, which is of particular industrial interest, is preferr~d.
The metallocene compound is u~ed in a concentration~
relative to the transition metal, of 10-3 to 10-7, preferably 10-4 to 10-6, mol of transi~ion metal per d~3 of solvent or per dm9 of reactor volume. The aluminoxane is used in a concentration of 10-5 to 10~1 mol, preferably 10-4 to 10-2 mol, per dm3 of solvent or per dm3 of reactor volume. However, in principle, higher concentrations are also possible. At least one compound of the formula III
is used a~ the metallocene. Mixtures of ~everal compounds of the formula III or mixtures of isomers are also po~sible.
If the polymerization is carried out a~ suspension or solution polymeriæation~ an inert ~ol~ent cus~omary ~or the Ziegler low-pressure proces~ is used. For oxampla~
the polymerization i^~ carried out in an aliphatic or cycloaliphatic hydrocarbon; exz~rnples of ~uch a hydro-carbon are ~utane, pentane, hexane, heptane, isooc~ane, cyclohexane, methylcyclohexane~
Furthermore, a benzine or hydrogenated diesQl oil frac-tion can be used. Toluene i8 also u able. Preferably, the polymerization i6 ca.rried out in ~he liguid mo~omer. If inert sol~ent~ are used, the monomers are metered in as a gas or a liquid. If only one monomer is used a3 su~pen ding agent, the comonomer or-comonomer~ are metered in a~
a gas or li~uid. Furthermore, it i8 posslble to carry out the polymerization in a mixture of different monomer~ as - 19 ~ "7 suspending agent; a further monomer can ~hen be metered in as a liquid or a gas. If ethylene is used, it i~
advantayeous to introduce initially a portion of the ethylene and meter in the remainder during the polymerization.
The duration of th~ polymerization i5 as desired, since the catalyst system to be used according to the invention shows only a small time-dependent drop in pol~merization activi~y.
Tha process according to the invention is distinguished by the ~ ct that the metallocenes used are very tempera-ture stable, so that ~hey can be used with high activity even at temperatures of up to 90C. Furthermore, the aluminoxanes which serve a~ cocatalysts can be added in smaller concentrations than previously. Finally, it i~
now possible to prepare random copol~mers at tempera~ures which ar~ of industrial intexest.
A further advantage of the proce~s accoxding to the invention i8 that ~he mixture of methylaluminoxane and hydridomethylaluminoxane offer~ tha po~ibility ko control the i otaxy or syndiotaxy of the pol~er.
The example~ which follow are intended to illu~trat0 tha invention. The ~ymbol8 have the following meanings s VN = visco~ity number in cm3 5 SI = ~yndiotactic index/ dete.rmined by l3C-NMR
speckro~copy II = isotactic index, determined by '3 spectroscopy E:~ample 1 A dry 16 dm3reactor wa~ flu~hed with nitrogen and filled wikh 10 clm3 of liquid propylene. 68 cm3 of a hydrido-me~hylaluminoxane ~olution in toluene (= XM~O, corres~
ponding to 40 mmol of Al, mean oligomerizatlon degree ~ 13 ~3J ~
n = 30) were then added, and the batch was stirred at 30C for 15 minutes.
':
At the same t~, 50 mg of bis(indenyl)ethylenehafnium dichloride were dissolved in 34 cm3 MAO (= 20 mmol Al) and preactivated by letting it stand for 15 minutes.
This solution was then poured into the reactor. The polymarization system was brought to a temperature of 70C, and the polymerization began. The polymeri~ation wa~ stopped after 60 minuteq by cooling the reactor and releasiny the pressure. 0.16 kg of polypropylene was obtained. The activity was therefore 3.2 kg of PP/g of metallocene/h.
The following analytical data of the polymer were determined:
VN = 73 cm3/g~ II = 92%.
~ xample 2 .~
A dry 16 dm3 reactor wa~ flushed with nitrogen and filled with 10 dm3 of liquid propylene. 68 cm3 of a hydri~o-methylaluminoxane ~olution in toluene (= HMAO, corre~pondLng to 40 mmol o~ Al, mean oligomerization degree n = 30~ were then added, and the batch wa~ 3tixred at 30C for 15 minutesO
~t the same ~, 7 mg of bi~(indenyl)dimethyl~ilylene-zirconium dichloride were di3solved in lS cm3 MAO
~= 20 mmol Al~ and preactivated by letting it stand for 15 minutes.
This so1u~ion was then poured into the reacto~- The polymerization system was brought to a ~emperature of 70C, and the polymerization began. ~he polymerization was ~topped after 60 minu~es by cooling the reactor and releasing the pressure. 0.88 kg of polypropylene W~5 obtained. The activity was therefore 126 kg of PP~g of ~2~,~", 1 metallocene/h.
The followlng analytical data of ~he polymer were determined:
VN = 49 cm3/g~ II = 85%.
E2ampl~ 3 A dry 16 dm3 reactorwas flu~hed with nitrogen and filled with 10 dm3 of liquid propylene. 68 cm3 of a hydrido-methylaluminoxane solution in toluene (= HMA0, oorres-ponding to 40 mmol of Al, mean oligomerizati~n degree n = 30) were then added, and the batch was ~tirred at 30C for 15 minutes.
At the same t ~ , 60 mg of fluorenylisopropylidenecyclo-pen~adienylhafnium dichloride were dissolved in 34 cm3 HMAO (= 20 mmol Al) and preactivated by letting it stand for 15 minutes.
This solution was then poured into the reactor. The polymerization system wa~ brought to ~ temperature of 60C, and the polymerization began. The polymerization was ~topped after 60 minutes by cooling the reactor and relea~ing the pres~uxe. 1.45 kg of polypropylene were obtainad. Th~ actiYity wa~ thexefore 11.9 kg of PP/g o~
metallocene/h.
The following analytical data o~ the polymer were determined~
~S VN = 51~ cm3/g, SI = 92%.
~ample 4 A dry 16 dm3 rea~torwa~ flu~hed with nitrogen and illed with 10 dm3 of liquid propylene. 68 cm3 of a hydrido-methylaluminoxane solution in toluene ~= H~A0, corr2s-ponding to 40 mmol of Al, mean oli~omeriza~ion degreen = 30) were then added~ and the batch wa~ . irrsd at - 13 ~ 3 ~
30C ~or lS minutes.
At the same t ~ , 20 mg of fluoxenylisopropylidenecyclo-pentadienylzirconium dichloride were dissol~ed in 34 cm3 HMAO (= 20 mmol Al) and preactivated by letting it stand for 15 minutes.
This solution was then poured into the reactor. The polymerization system was brought to a temp~rature of 50C, and the polymerization bPgan. The polymerizat.ion was stopped after 60 minutes by cooling the reactor and releasing the pressure. 0.68 kg of polypropylene was obtained. The activi y wa~ therefore 34 kg of PP/g of metallocene/h.
The following analytical data of the polymer were determined:
lS VN = 123 cm3/g, 5I = 89%.
Claims (4)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A process for the preparation of a polyolefin by poly-merization of an olefin of the formula Ra-CH=CH-Rb, in which Ra and Rb are identical or different and axe a hydrogen atom or a C1-C14-alkyl radical or Ra and Rb, together with the carbon atom linking them, form a ring of 4 to 28 carbon atoms, at a temperature of 0°C to 150°C, at a pressure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst consisting of a metallocene and an aluminoxane, wherein the aluminoxane is a compound of the formula (I) (I) for the linear type and/or of the formula (II) (II) for the cyclic type, R1 in the formulae (I) and (II) being a C1-C6-alkyl group or a hydrogen atom and n being an integer from 2 to 50, 0.01 to 40% of the radicals R1 being hydrogen atoms. - 2. The process as claimed in claim 1, wherein the alumin-oxane is a mixture of methylaluminoxane and hydridomethylaluminoxane.
- 3. The process as claimed in claim 1, wherein the alumin-oxane is hydridomethylaluminoxane.
- 4. The process as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3932181.9 | 1989-09-27 | ||
| DE3932181A DE3932181A1 (en) | 1989-09-27 | 1989-09-27 | METHOD FOR PRODUCING A POLYOLEFIN |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2026237A1 true CA2026237A1 (en) | 1991-03-28 |
Family
ID=6390271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002026237A Abandoned CA2026237A1 (en) | 1989-09-27 | 1990-09-26 | Process for the preparation of a polyolefin |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0421209B1 (en) |
| JP (1) | JP2948642B2 (en) |
| AU (1) | AU631928B2 (en) |
| CA (1) | CA2026237A1 (en) |
| DE (2) | DE3932181A1 (en) |
| ES (1) | ES2075103T3 (en) |
| ZA (1) | ZA907683B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5436305A (en) * | 1991-05-09 | 1995-07-25 | Phillips Petroleum Company | Organometallic fluorenyl compounds, preparation, and use |
| US8895466B2 (en) | 2004-10-21 | 2014-11-25 | Total Research & Technology Feluy | Activating agents for hafnium-based metallocene components |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2067525C (en) | 1991-05-09 | 1998-09-15 | Helmut G. Alt | Organometallic fluorenyl compounds, preparation and use |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3242099A (en) * | 1964-03-27 | 1966-03-22 | Union Carbide Corp | Olefin polymerization catalysts |
| JP2538588B2 (en) * | 1987-04-03 | 1996-09-25 | 三井石油化学工業株式会社 | Method for producing solid catalyst for olefin polymerization |
| DE3726067A1 (en) * | 1987-08-06 | 1989-02-16 | Hoechst Ag | METHOD FOR PRODUCING 1-OLEFIN POLYMERS |
| US4772736A (en) * | 1987-11-23 | 1988-09-20 | Union Carbide Corporation | Process for the preparation of aluminoxanes |
-
1989
- 1989-09-27 DE DE3932181A patent/DE3932181A1/en not_active Withdrawn
-
1990
- 1990-09-22 EP EP90118227A patent/EP0421209B1/en not_active Expired - Lifetime
- 1990-09-22 DE DE59009281T patent/DE59009281D1/en not_active Expired - Fee Related
- 1990-09-22 ES ES90118227T patent/ES2075103T3/en not_active Expired - Lifetime
- 1990-09-26 JP JP2254362A patent/JP2948642B2/en not_active Expired - Lifetime
- 1990-09-26 CA CA002026237A patent/CA2026237A1/en not_active Abandoned
- 1990-09-26 ZA ZA907683A patent/ZA907683B/en unknown
- 1990-09-26 AU AU63178/90A patent/AU631928B2/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5436305A (en) * | 1991-05-09 | 1995-07-25 | Phillips Petroleum Company | Organometallic fluorenyl compounds, preparation, and use |
| US8895466B2 (en) | 2004-10-21 | 2014-11-25 | Total Research & Technology Feluy | Activating agents for hafnium-based metallocene components |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59009281D1 (en) | 1995-07-27 |
| ZA907683B (en) | 1991-06-26 |
| DE3932181A1 (en) | 1991-04-04 |
| JP2948642B2 (en) | 1999-09-13 |
| JPH03139503A (en) | 1991-06-13 |
| EP0421209A3 (en) | 1992-08-05 |
| AU631928B2 (en) | 1992-12-10 |
| EP0421209A2 (en) | 1991-04-10 |
| ES2075103T3 (en) | 1995-10-01 |
| EP0421209B1 (en) | 1995-06-21 |
| AU6317890A (en) | 1991-04-11 |
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