WO2000049029A1 - Polyolefin production - Google Patents

Polyolefin production Download PDF

Info

Publication number
WO2000049029A1
WO2000049029A1 PCT/EP1999/001094 EP9901094W WO0049029A1 WO 2000049029 A1 WO2000049029 A1 WO 2000049029A1 EP 9901094 W EP9901094 W EP 9901094W WO 0049029 A1 WO0049029 A1 WO 0049029A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst component
component according
chosen
substituent
cyclopentadienyl
Prior art date
Application number
PCT/EP1999/001094
Other languages
French (fr)
Inventor
Abbas Razavi
Original Assignee
Fina Research S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fina Research S.A. filed Critical Fina Research S.A.
Priority to PCT/EP1999/001094 priority Critical patent/WO2000049029A1/en
Priority to AU31411/99A priority patent/AU3141199A/en
Priority to JP51283599A priority patent/JP4864176B2/en
Priority to RU2001124801/04A priority patent/RU2244721C2/en
Priority to EP00906358A priority patent/EP1169356B1/en
Priority to AU28062/00A priority patent/AU2806200A/en
Priority to PCT/EP2000/001378 priority patent/WO2000049056A1/en
Priority to ES00906358T priority patent/ES2223460T3/en
Priority to BRPI0008312-7A priority patent/BR0008312B1/en
Priority to US09/506,943 priority patent/US6515086B1/en
Priority to AT00906358T priority patent/ATE271071T1/en
Priority to KR1020017010519A priority patent/KR100663788B1/en
Priority to DE60012166T priority patent/DE60012166T2/en
Priority to CA2371835A priority patent/CA2371835C/en
Priority to CNB008059535A priority patent/CN1152056C/en
Publication of WO2000049029A1 publication Critical patent/WO2000049029A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/15—Isotactic
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to a etallocene catalyst component for use in preparing polyolefins, especially polypropylenes .
  • the invention further relates to a catalyst system which incorporates the metallocene catalyst component and a process for preparing such polyolefins.
  • Olefins having 3 or more carbon atoms can be polymerised to produce a polymer with an isotactic stereochemical configuration.
  • the isotactic structure is typically described as having methyl groups attached to the tertiary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the main chain of the polymer. This can be described using the Fischer projection formula as follows:
  • Bovey's NMR nomenclature for an isotactic pentad is ... mmmm with each "m” representing a “meso" diad or successive methyl groups on the same side in the plane.
  • syndiotactic polymers are those in which the methyl groups attached to the tertiary carbon atoms of successive monomeric units in the chain lie on alternate sides of the plane of the polymer.
  • Fischer projection formula the structure of a syndiotactic polymer is described as follows : - 2 -
  • an atactic polymer In contrast to isotactic and syndiotactic polymers, an atactic polymer exhibits no regular order of repeating unit. Unlike syndiotactic or isotactic polymers, an atactic polymer is not crystalline and forms essentially a waxy product.
  • C 2 -symmetric metallocene catalysts are known in the production of the polyolefins.
  • C2 symmetric bis indenyl type zirconocenes which can produce high molecular weight high melting isotactic polypropylene.
  • the preparation of this metallocene catalyst is costly and time-consuming, however.
  • the final catalyst consists of a mixture of racemic and meso iso ers in an often unfavourable ratio. The meso stereoiso er has to be separated to avoid the formation of atactic polypropylene during the polymerisation reaction.
  • EP-A-0426644 relates to syndiotactic copolymers of olefin ⁇ such as propylene obtainable using as a catalyst component isopropyl (fluorenyl) (cyclopentadienyl) zirconium dichloride. Syndiotacticity, as measured by the amount of syndiotactic pentads, rrrr was found to be 73-80%.
  • EP 747406 relates to the polymerisation of an olefin monomer to form a syndiotactic/isotactic block polyolefin, particularly a block polypropylene.
  • a component of the polymerisation catalyst was a 3-trimethylsilyl cyclopentadienyl-9-fluorenyl zirconium or hafnium dichloride having an isopropylidene or diphenylmethylidene bridge.
  • EP-A-0537130 discloses the use of a Cl symmetric metallocene catalysts for the production of isotactic polypropylene.
  • a preferred catalyst is isopropylidine (3-tert butyl- cyclopentadienyl-fluorenyl) ZrCl 2 .
  • This catalyst has a bulky t-butyl group positioned on the cyclopentadienyl ring distal to the isopropylidine bridge.
  • This catalyst has the advantage that it consists of only one stereoiso er and so no isomeric metallocene separation is required at the final stage of its synthesis. Whilst polypropylene preparation using this catalyst produces isotactic polypropylene, the polymer product has poor mechanical properties because of the presence of regiodef ct ⁇ and relatively low molecular weight .
  • EP-A-088236 addresses this problem by providing isopropylidene (5-methyl-3t-butyl cyclopentadienyl fluorene) zirconium dichloride as part of a polymerisation catalyst.
  • polypropylenes obtained using this catalyst have molecular weights (Mw) in the range 213900 to 458500 and a microtacticity characterised by the mmmm pentad in the range 82.8% to 86.8%.
  • the melting temperature of these polymers is in the range 139.3 to 143.8.
  • the present invention aims to overcome the disadvantages of the prior art.
  • the present invention provides a metallocene catalyst component for use in preparing polyolefins having a monomer length of up to CIO, which component has the general formula:
  • C p is a substituted or unsubstituted cyclopentadienyl ring,- C p ' is a substituted fluorenyl ring;
  • R" is a structural bridge imparting stereorigidity to the component;
  • x is optionally a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR* 3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms,
  • R 2 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is of the formula YR# 3 in which Y is chosen from group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms
  • R 3 is
  • Polyolefins produced using the metallocene catalyst component of the present invention are surprisingly found to have very good microtacticity, especially as determined by pentad distribution levels in 13C nmr.
  • the polyolefins are also found to be substantially free of regiodefects. Accordingly, the polyolefins produced thereby have improved mechanical properties including a high weight average molecular weight typically in excess of 500,000 and melting point elevated by at least 10°C as compared with prior art values.
  • the fluorenyl ring may be substituted by radicals of general formula: AR'' ⁇ where A is preferably carbon or silicon and is more preferably carbon.
  • AR' * ' may be a hydrocarbyl selected from alkyl, aryl, alkenyl, alkyl aryl or aryl alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, a yl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl .
  • A is silicon
  • AR''' 3 may be Si(CH 3 ) 3 .
  • at least one of E ⁇ and R' 2 is t-butyl. More preferably both R' x and R' j are the same.
  • catalysts of the invention when used to produce polypropylene, they show melting points generally higher than 150°C and which may even reach 165"C which is a considerable improvement over the prior art .
  • the structural bridge R" is preferably alkylidene having 1 to 20 aliphatic or aromatic carbon atoms, a dialkyl germanium or silicon or siloxane, alkyl phosphene or amine bridging the two C j , rings .
  • R" is preferably isopropylidene in which the two C-, rings are bridged at position 2 of the isopropylidene.
  • R' ' is diphenylmethylidene .
  • M is preferably zirconium or titanium, most preferably zironiu .
  • Q may be a hydrocarbyl such as alkyl, aryl, alkenyl, alkylaryl or aryl alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl.
  • Q is preferably a halogen.
  • the selection of the substitution pattern on the cyclopentadienyl ring depends on the desired stereochemistry of the polyolefin product.
  • the metallocene catalyst component of the present invention may be used to produce syndiotactic polyolefins, isotactic polyolefins or syndiotactic/isotactic block polyolefins.
  • the polyolefins can be homopolymers or copolymers. Where a syndiotactic polyolefin is required, it is preferred that the cyclopentadienyl ring is unsubstituted.
  • R x is therefore not hydrogen but is instead a substituent on the cyclopentadienyl ring. It is preferred that R x is a bulky distal substituent group.
  • R 1( X is preferably C or Si.
  • R* may be a hydrocarbyl such as alkyl, aryl, alkenyl, alkylaryl or aryl alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl.
  • R ⁇ may comprise a hydrocarbyl which is attached to a single carbon atom in the cyclopentadienyl ring or may be bonded to two carbon atoms in that ring.
  • A is C(CH 3 ) 3 , C ⁇ CH 3 ) 2 Ph, CPh 3 or Si(CH j ) 3 , most preferably C(CH 3 ) 3 .
  • Ri and R 2 are not hydrogen.
  • R 2 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and preferably comprises a CH 3 group.
  • the cyclopentadienyl ring may also be substituted by R 3 in isotactic polyolefin production.
  • R 3 is preferably CH 3 .
  • the present invention provides a metallocene catalyst component for use in preparing polyolefins, which comprises (i) a catalyst component as defined above; and (ii) a regioiso er thereof in which Rj is proximal to the bridge and positioned vicinal to the distal substituent .
  • a metallocene catalyst component for use in preparing polyolefins, which comprises (i) a catalyst component as defined above; and (ii) a regioiso er thereof in which Rj is proximal to the bridge and positioned vicinal to the distal substituent .
  • Such regioisomers are frequently relatively easy to prepare because they are formed as a "by-product" during the synthetic route by which the catalyst component (i) may be made.
  • the present invention provides a catalyst system for use in preparing polyolefins, which comprises (a) a catalyst component as defined above,- and (b) an aluminium- or boron-containing cocatalyst capable of activating the catalyst component.
  • a catalyst component as defined above,- and (b) an aluminium- or boron-containing cocatalyst capable of activating the catalyst component.
  • Suitable aluminium- containing cocatalysts comprise an alumoxane, an alkyl aluminium and/or a Lewis acid.
  • alumoxanes usable in the process of the present invention are well known and preferably comprise oligomeric linear and/or cyclic alkyl alumoxanes represented by the formula:
  • n 1-40, preferably 10-20, m is 3-40, preferably 3- 20 and R is a C ⁇ C,, alkyl group and preferably methyl.
  • alumoxanes from, for example, aluminium trimethyl and water, a mixture of linear and cyclic compounds is obtained.
  • Suitable boron-containing cocatalysts may comprise a triphenylcarbenium boronate such as tetrakis- pentafluorophenyl-borato-triphenylcarbeniu as described in EP-A-0427696, or those of the general formula [L -H] + [B Ar. Ar 2 X 3 X,]- as described in EP-A-0277004 (page 6, line 30 to page 7, line 7) .
  • triphenylcarbenium boronate such as tetrakis- pentafluorophenyl-borato-triphenylcarbeniu as described in EP-A-0427696, or those of the general formula [L -H] + [B Ar. Ar 2 X 3 X,]- as described in EP-A-0277004 (page 6, line 30 to page 7, line 7) .
  • the catalyst system may be employed in a solution polymerisation process, which is homogeneous, or a slurry process, which is heterogeneous.
  • typical solvents include hydrocarbons with 4 to 7 carbon atoms such as heptane, toluene or cyclohexane .
  • a slurry process it is necessary to immobilise the catalyst system on an inert support, particularly a porous solid support such as talc, inorganic oxides and resinous support materials such as polyolefin.
  • the support material is an inorganic oxide in its finally divided form.
  • the amount of alumoxane and metallocenes usefully employed in the preparation of the solid support catalyst can vary over a wide range.
  • the aluminium to transition metal mole ratio is in the range between 1:1 and 100:1, preferably in the range 5 -.1 and 50:1.
  • Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperature and which do not react with the individual ingredients .
  • Illustrative examples of the useful solvents include the alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane; cycloalkanes such as cyclopentane and cyclohexane, and aro atics such as benzene, toluene, ethylbenzene and diethylbenzene .
  • the support material is slurried in toluene and the metallocene and alumoxane are dissolved in toluene prior to addition to the support material .
  • the present invention provides a process for preparing polyolefins, especially polypropylenes, which comprises contacting a catalyst system as defined above with at least one olefin, preferably propylene, in a reaction zone under polymerisation conditions .
  • the catalyst component may be prepared by any suitable method known in the art. Generally, the preparation of the catalyst component comprises forming and isolating bridged dicyclopentadiene, which is then reacted with a halogenated metal to form the bridged metallocene catalyst .
  • the process for preparing the bridged metallocene catalyst components comprises contacting the cyclopentadiene with a substituted fluorene under reaction conditions sufficient to produce a bridged dicyclopentadiene .
  • the process further comprises contacting the bridged substituted dicyclopentadiene with a metal compound of the formula MQ k as defined above under reaction conditions sufficient to complex the bridged dicyclopentadiene to produce a bridged metallocene wherein M and Q are each defined as above and 0 ⁇ k ⁇ .
  • the process step of contacting the bridged substituted dicyclopentadiene with a metal compound can be performed in a chlorinated solvent.
  • the process comprises contacting the cyclopentadiene with an alkyl ⁇ ilyl chloride of the formula R ⁇ 2 Si Hal 2 wherein R ⁇ is a hydrocarbyl having 1 to 20 carbon atoms and Hal is a halogen.
  • R ⁇ is a hydrocarbyl having 1 to 20 carbon atoms and Hal is a halogen.
  • a second equivalent of a substituted fluorene is added to produce a silicon bridged cyclopentadienyl-substituent fluorenyl ligand.
  • the subsequent steps are similar to th ⁇ 9e above for producing a bridged substituted cyclopentadienyl-fluroenyl ligand coordinated to metals such as Zr, Hf and Ti.
  • the process comprises contacting the substituted cyclopentadiene with a fulvene producing agent such as acetone to produce a substituted fulvene.
  • a fulvene producing agent such as acetone
  • the fulvene is reacted with a fluorene substituted in position 3 and/or 6, and preferably both 3 and 6 , to produce a carbon bridged substituted cyclopentadienyl-fluorenyl ligand that will produce the desired metallocene catalysts after reacting with MC1 4 , in which M is Zr, Hf or Ti.
  • the present invention provides an isotactic polyolefin having a monomer length of up to CIO and a pentad distribution comprising greate than 80% and preferably at least 87% mmmm as measured by 13C n r.
  • the pentad distribution preferably comprises at least 90%, more preferably at least 95% mmmm as measured by 13C nmr.
  • the amount 2-1 and 1-3 monomer insertions in the polyolefin is less than 0.5%, more preferably, less than 0.2 and most preferably undetectable.
  • FIGURES 1 to 12 show illustrations of the structures of preferred catalyst components of the present invention.
  • FIGURE 13 shows the results of differential scanning calorimetry analysis on isotactic polypropylene produced at 40°C using the catalyst shown in Figure 1.
  • step D The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2-[(3- methyl-cyclopentadienyl) - (3, 6-di-tertbutyl-fluorenyl) ] - propane .
  • step D The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2, 2- [(3- tertbutyl-cyclopentadienyl) - (3, 6-di- tertbutyl-fluorenyl) ] -propane prepared as below.
  • step B The synthetic procedure according to Example 1, step B, is followed, but the 3, 6, 6-trimethylfulvene is replaced by 6,6- dimethylfulven .
  • step D The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the diphenyl [ (3-trimethylsilyl-cyclopentadienyl) - (3, 6-di- tertbutyl-fluorenyl) Imethylene.
  • step D The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the diphenyl [ (3-trimethylsilyl-cyclopentadienyl) - (3, 6-di- tertbutyl-fluorenyl) ] methylene.
  • the reaction mixture is heated at 40°C for 10 minutes.
  • the orange solution is filtered (to remove LiCl, 1.40 g of residue), concentrated to 100 ml, and cooled down to crystallise the product 2,2- (3-trimethylsilyl-cyclopentadienyl) (3,6-di- tertbutyl fluorenyl) propane .
  • the raw product has a beige colour.
  • the crystallised product has a white colour/ 65-70% yield.
  • the product was stored under N2.
  • step D The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2- [ (3, 5-dimethyl-cyclopentadienyl) - (3, 6-di-tertbutyl- fluorenyl) ] -propane.
  • step D The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2- diphenyl [ (3-methyl-cyclopentadienyl) - (3, 6-di-tertbutyl- fluorenyl) ] propane.
  • step D The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the diphenyl [ (3-terbutyl-cyclopentadienyl) - (3, 6-di-tertbutyl- fluorenyl) ] methylene .
  • Example 10 The preparation of this fulvene is the same as described in Example 1, step A, except that the acetone is replaced by the benzophenone and the methylcyclopentadiene is replaced by the tert-butylcyclopentadiene (the synthetic procedure is described in Example 4, step C) .
  • Example 10 The preparation of this fulvene is the same as described in Example 1, step A, except that the acetone is replaced by the benzophenone and the methylcyclopentadiene is replaced by the tert-butylcyclopentadiene (the synthetic procedure is described in Example 4, step C) .
  • Example 10 The preparation of this fulvene is the same as described in Example 1, step A, except that the acetone is replaced by the benzophenone and the methylcyclopentadiene is replaced by the tert-butylcyclopentadiene (the synthetic procedure is described in Example 4, step C) .
  • Example 10 The preparation of this fulvene is the same as described in Example 1, step A
  • step D The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2- diphenylf (3-trimethylsilyl-cyclopentadienyl) - (3, 6-di- tertbutyl-fluorenyl) ] propane
  • Table la shows figures for production of syndiotactic polypropylene using as a catalyst component described in Example 2.
  • Table lb shows corresponding figures for the metallocene described in Example 7.
  • Syndiotactic polypropylene made using isopropylidene bridge catalyst
  • Table 2 shows the microtacticity of the polymer obtained using the catalyst according to Example 1 under polymerisation conditions as defined by the corresponding entries in Table 1. The results were obtained using "c NMR spectroscopy. It will be apparent that the polypropylene contained more than 95% of pentads in the purely isotactic form (mmmm) . The molecular weight (Mw) of the polypropylene was 530,000 and the melting point was 153°C. Melting point was determined by DSC analysis as shown in Figure 13. A sample was held at 25°C for 1 min, heated from 25°C to 220°C at 20°C/min and held for 5 mins at 220°C. The sample was then cooled from 220°C to 25°C at 20°C/min, held at 25°C for 3 mins and heated from 25°C to 220°C at 20°C/min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Organic Insulating Materials (AREA)

Abstract

A metallocene catalyst component for use in preparing polyolefins having a monomer length of up to C10, which component has the general formula: R'(CpR1R2R3)(Cp'R1'R2')MQ2 wherein Cp is a substituted or unsubstituted cyclopentadienyl ring; Cp' is a substituted fluorenyl ring; R' is a structural bridge imparting stereorigidity to the component; R1 is optionally a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocabyl of from 1 to 20 carbon atoms, R2 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is of the formula YR#3 in which Y is chosen from group IVA, and each R# is the same or different and chosen from hydrogen or hydrocabyl of 1 to 7 carbon atoms, R3 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$3, in which Z is chosen from group IVA, and each R$ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R1' and R2' are each independently substituent groups on the fluorenyl ring, one of which is a group of the formula AR'''3, in which A is chosen from Group IVA, and each R''' is independently hydrogen or a hydrocarbyl having 1 to 20 carbon atoms and the other is hydrogen or a second group of the formula AR'''3; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen.

Description

POLYOLEFIN PRODUCTION
Field of the Invention
The present invention relates to a etallocene catalyst component for use in preparing polyolefins, especially polypropylenes . The invention further relates to a catalyst system which incorporates the metallocene catalyst component and a process for preparing such polyolefins.
Background to the Invention
Olefins having 3 or more carbon atoms can be polymerised to produce a polymer with an isotactic stereochemical configuration. For example, in the polymerisation of propylene to form polypropylene, the isotactic structure is typically described as having methyl groups attached to the tertiary carbon atoms of successive monomeric units on the same side of a hypothetical plane through the main chain of the polymer. This can be described using the Fischer projection formula as follows:
Figure imgf000003_0001
Another way of describing the structure is through the use of NMR spectroscopy. Bovey's NMR nomenclature for an isotactic pentad is ... mmmm with each "m" representing a "meso" diad or successive methyl groups on the same side in the plane.
In contrast to the isotactic structure, syndiotactic polymers are those in which the methyl groups attached to the tertiary carbon atoms of successive monomeric units in the chain lie on alternate sides of the plane of the polymer. Using the Fischer projection formula, the structure of a syndiotactic polymer is described as follows : - 2 -
Figure imgf000004_0001
In NMR nomenclature, a syndiotactic pentad is described as ...rrrr... in which "r" represents a "racemic" diad with successive methyl groups on alternate sides of the plane.
In contrast to isotactic and syndiotactic polymers, an atactic polymer exhibits no regular order of repeating unit. Unlike syndiotactic or isotactic polymers, an atactic polymer is not crystalline and forms essentially a waxy product.
While it is possible for a catalyst to produce all three types of polymer, it is desirable for a catalyst to produce predominantly an isotactic or syndiotactic polymer with very little atactic polymer. C2-symmetric metallocene catalysts are known in the production of the polyolefins. For example, C2 symmetric bis indenyl type zirconocenes which can produce high molecular weight high melting isotactic polypropylene. The preparation of this metallocene catalyst is costly and time-consuming, however. Most importantly, the final catalyst consists of a mixture of racemic and meso iso ers in an often unfavourable ratio. The meso stereoiso er has to be separated to avoid the formation of atactic polypropylene during the polymerisation reaction.
EP-A-0426644 relates to syndiotactic copolymers of olefinε such as propylene obtainable using as a catalyst component isopropyl (fluorenyl) (cyclopentadienyl) zirconium dichloride. Syndiotacticity, as measured by the amount of syndiotactic pentads, rrrr was found to be 73-80%. EP 747406 relates to the polymerisation of an olefin monomer to form a syndiotactic/isotactic block polyolefin, particularly a block polypropylene. A component of the polymerisation catalyst was a 3-trimethylsilyl cyclopentadienyl-9-fluorenyl zirconium or hafnium dichloride having an isopropylidene or diphenylmethylidene bridge.
EP-A-0537130 discloses the use of a Cl symmetric metallocene catalysts for the production of isotactic polypropylene. A preferred catalyst is isopropylidine (3-tert butyl- cyclopentadienyl-fluorenyl) ZrCl2. This catalyst has a bulky t-butyl group positioned on the cyclopentadienyl ring distal to the isopropylidine bridge. This catalyst has the advantage that it consists of only one stereoiso er and so no isomeric metallocene separation is required at the final stage of its synthesis. Whilst polypropylene preparation using this catalyst produces isotactic polypropylene, the polymer product has poor mechanical properties because of the presence of regiodef ctε and relatively low molecular weight .
Regiodefects occur in the polymer chain when, instead of producing a perfect isotactic polyolefin in which each monomeric unit is positioned head-to-tail in relation to the next, mis-insertions of the monomers occur so as to give either a head-to-head or tail-to-tail mis-match. These so called (2-1) regiodefects are partially transferred to the so called (1-3) insertion through an iso erisation process leaving units of four CH2 groups in the backbone of the polypropylene chain. This has a deleterious effect on the physical and mechanical properties of the polymer and results in low molecular weight isotactic polypropylene with a low melting point. EP-A-088236 addresses this problem by providing isopropylidene (5-methyl-3t-butyl cyclopentadienyl fluorene) zirconium dichloride as part of a polymerisation catalyst. However, polypropylenes obtained using this catalyst have molecular weights (Mw) in the range 213900 to 458500 and a microtacticity characterised by the mmmm pentad in the range 82.8% to 86.8%. The melting temperature of these polymers is in the range 139.3 to 143.8.
Sramtary of the Invention
The present invention aims to overcome the disadvantages of the prior art.
In a first aspect, the present invention provides a metallocene catalyst component for use in preparing polyolefins having a monomer length of up to CIO, which component has the general formula:
R" (CpRαR3R3) (Cp'R1'R2')MQ2 (I)
wherein Cp is a substituted or unsubstituted cyclopentadienyl ring,- Cp' is a substituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component; x is optionally a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is of the formula YR#3 in which Y is chosen from group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$3, in which Z is chosen from group IVA, and each R$ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms , R: ' and R2 ' are each independently substituent groups on the fluorenyl ring, one of which is a group of the formula AR' ' '3, in which A is chosen from Group IVA, and each R' ' ' is independently hydrogen or a hydrocarbyl having 1 to 20 carbon atoms and the other is hydrogen or a second group of the formula AR' ' '3; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen.
Polyolefins produced using the metallocene catalyst component of the present invention are surprisingly found to have very good microtacticity, especially as determined by pentad distribution levels in 13C nmr. The polyolefins are also found to be substantially free of regiodefects. Accordingly, the polyolefins produced thereby have improved mechanical properties including a high weight average molecular weight typically in excess of 500,000 and melting point elevated by at least 10°C as compared with prior art values.
The applicants have unexpectedly found that if in the metallocene catalysts the fluorenyl ring is substituted in certain specific positions, preferably in position 3 and/or 6, there is a significant improvement in the tacticity of the produced polymer, and a dramatic drop in the regio-def cts of said polymer.
According to the present invention, the fluorenyl ring may be substituted by radicals of general formula: AR''^ where A is preferably carbon or silicon and is more preferably carbon. Where A is carbon, AR' * ' may be a hydrocarbyl selected from alkyl, aryl, alkenyl, alkyl aryl or aryl alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, a yl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl . Where A is silicon, AR'''3 may be Si(CH3)3. Preferably at least one of E^ and R'2 is t-butyl. More preferably both R'x and R'j are the same.
In addition, the applicants have also found that when catalysts of the invention are used to produce polypropylene, they show melting points generally higher than 150°C and which may even reach 165"C which is a considerable improvement over the prior art .
The structural bridge R" is preferably alkylidene having 1 to 20 aliphatic or aromatic carbon atoms, a dialkyl germanium or silicon or siloxane, alkyl phosphene or amine bridging the two Cj, rings . R" is preferably isopropylidene in which the two C-, rings are bridged at position 2 of the isopropylidene. Alternatively, R' ' is diphenylmethylidene .
M is preferably zirconium or titanium, most preferably zironiu . Q may be a hydrocarbyl such as alkyl, aryl, alkenyl, alkylaryl or aryl alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl. Q is preferably a halogen.
The selection of the substitution pattern on the cyclopentadienyl ring depends on the desired stereochemistry of the polyolefin product. The metallocene catalyst component of the present invention may be used to produce syndiotactic polyolefins, isotactic polyolefins or syndiotactic/isotactic block polyolefins. The polyolefins can be homopolymers or copolymers. Where a syndiotactic polyolefin is required, it is preferred that the cyclopentadienyl ring is unsubstituted. where a syndiotactic/isotactic polyolefin is required, it is preferred that the cyclopentadienyl ring is substituted at a position distal to the bridge. Rx is therefore not hydrogen but is instead a substituent on the cyclopentadienyl ring. It is preferred that Rx is a bulky distal substituent group.
In the bulky distal substituent group R1( X is preferably C or Si. R* may be a hydrocarbyl such as alkyl, aryl, alkenyl, alkylaryl or aryl alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl. Rλ may comprise a hydrocarbyl which is attached to a single carbon atom in the cyclopentadienyl ring or may be bonded to two carbon atoms in that ring. Preferably, A is C(CH3)3, C{CH3)2Ph, CPh3 or Si(CHj)3, most preferably C(CH3)3.
Where an isotactic polyolefin is required, it is preferred that both Ri and R2 are not hydrogen. R2 is a substituent on the cyclopentadienyl ring which is proximal to the bridge and preferably comprises a CH3 group.
The cyclopentadienyl ring may also be substituted by R3 in isotactic polyolefin production. R3 is preferably CH3.
In a further aspect, the present invention provides a metallocene catalyst component for use in preparing polyolefins, which comprises (i) a catalyst component as defined above; and (ii) a regioiso er thereof in which Rj is proximal to the bridge and positioned vicinal to the distal substituent . Such regioisomers are frequently relatively easy to prepare because they are formed as a "by-product" during the synthetic route by which the catalyst component (i) may be made.
Surprisingly, it has been found that catalyst components including both regioisomers can be used in the preparation of polyolefins which have a ultimodal, especially a bimodal, molecular weight distribution.
In a further aspect, the present invention provides a catalyst system for use in preparing polyolefins, which comprises (a) a catalyst component as defined above,- and (b) an aluminium- or boron-containing cocatalyst capable of activating the catalyst component. Suitable aluminium- containing cocatalysts comprise an alumoxane, an alkyl aluminium and/or a Lewis acid.
The alumoxanes usable in the process of the present invention are well known and preferably comprise oligomeric linear and/or cyclic alkyl alumoxanes represented by the formula:
(I) R-(Al-0h-AlR2
R for oligomeric, linear alumoxanes and
(ID (-Al-O-h
for oligomeric, cyclic alumoxane, wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3- 20 and R is a C^C,, alkyl group and preferably methyl. Generally, in the preparation of alumoxanes from, for example, aluminium trimethyl and water, a mixture of linear and cyclic compounds is obtained.
Suitable boron-containing cocatalysts may comprise a triphenylcarbenium boronate such as tetrakis- pentafluorophenyl-borato-triphenylcarbeniu as described in EP-A-0427696, or those of the general formula [L -H] + [B Ar. Ar2 X3 X,]- as described in EP-A-0277004 (page 6, line 30 to page 7, line 7) .
The catalyst system may be employed in a solution polymerisation process, which is homogeneous, or a slurry process, which is heterogeneous. In a solution process, typical solvents include hydrocarbons with 4 to 7 carbon atoms such as heptane, toluene or cyclohexane . In a slurry process it is necessary to immobilise the catalyst system on an inert support, particularly a porous solid support such as talc, inorganic oxides and resinous support materials such as polyolefin. Preferably, the support material is an inorganic oxide in its finally divided form.
Suitable inorganic oxide materials which are desirably employed in accordance with this invention include Group 2a, 3a, 4a or 4b metal oxides such as silica, alumina and mixtures thereof . Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, zirconia, and the like. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins such as finely divided polyethylene. Preferably, the support is a silica having a surface area comprised between 200 and 700 m2/g and a pore volume comprised between 0.5 and 3 ml/g.
The amount of alumoxane and metallocenes usefully employed in the preparation of the solid support catalyst can vary over a wide range. Preferably the aluminium to transition metal mole ratio is in the range between 1:1 and 100:1, preferably in the range 5 -.1 and 50:1.
The order of addition of the metallocenes and alumoxane to the support material can vary. In accordance with a preferred embodiment of the present invention alumoxane dissolved in a suitable inert hydrocarbon solvent is added to the support material slurried in the same or other suitable hydrocarbon liquid and thereafter a mixture of the metallocene catalyst component is added to the slurry.
Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperature and which do not react with the individual ingredients . Illustrative examples of the useful solvents include the alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane; cycloalkanes such as cyclopentane and cyclohexane, and aro atics such as benzene, toluene, ethylbenzene and diethylbenzene .
Preferably the support material is slurried in toluene and the metallocene and alumoxane are dissolved in toluene prior to addition to the support material .
In a further aspect, the present invention provides use of a catalyst component as defined above and a cocatalyst which activates the catalyst component, for the preparation of polyolefins, preferably polypropylenes . Although the present invention is dedicated to the use of metallocene catalysts, the fluorenyl ring of which has been substituted in positions 3 and/or 6, it has been noted that by using a metallocene catalyst component comprising (i) the catalyic component and
(ii) a regioisomer thereof, in which R2 is proximal to the bridge and positioned vicina.1 to the distal substituent, for the preparation of polyolefins, especially polypropylenes, having a multimodal molecular weight distribution, preferably a bimodal molecular weight distribution.
In a further aspect, the present invention provides a process for preparing polyolefins, especially polypropylenes, which comprises contacting a catalyst system as defined above with at least one olefin, preferably propylene, in a reaction zone under polymerisation conditions .
The catalyst component may be prepared by any suitable method known in the art. Generally, the preparation of the catalyst component comprises forming and isolating bridged dicyclopentadiene, which is then reacted with a halogenated metal to form the bridged metallocene catalyst .
In one embodiment, the process for preparing the bridged metallocene catalyst components comprises contacting the cyclopentadiene with a substituted fluorene under reaction conditions sufficient to produce a bridged dicyclopentadiene . The process further comprises contacting the bridged substituted dicyclopentadiene with a metal compound of the formula MQk as defined above under reaction conditions sufficient to complex the bridged dicyclopentadiene to produce a bridged metallocene wherein M and Q are each defined as above and 0 < k < . The process step of contacting the bridged substituted dicyclopentadiene with a metal compound can be performed in a chlorinated solvent.
In a further embodiment, the process comprises contacting the cyclopentadiene with an alkyl εilyl chloride of the formula R~2 Si Hal2 wherein R~ is a hydrocarbyl having 1 to 20 carbon atoms and Hal is a halogen. A second equivalent of a substituted fluorene is added to produce a silicon bridged cyclopentadienyl-substituent fluorenyl ligand. The subsequent steps are similar to thθ9e above for producing a bridged substituted cyclopentadienyl-fluroenyl ligand coordinated to metals such as Zr, Hf and Ti.
In a further embodiment, the process comprises contacting the substituted cyclopentadiene with a fulvene producing agent such as acetone to produce a substituted fulvene. Subsequently, in a second step, the fulvene is reacted with a fluorene substituted in position 3 and/or 6, and preferably both 3 and 6 , to produce a carbon bridged substituted cyclopentadienyl-fluorenyl ligand that will produce the desired metallocene catalysts after reacting with MC14, in which M is Zr, Hf or Ti.
In a further aspect, the present invention provides an isotactic polyolefin having a monomer length of up to CIO and a pentad distribution comprising greate than 80% and preferably at least 87% mmmm as measured by 13C n r. The pentad distribution preferably comprises at least 90%, more preferably at least 95% mmmm as measured by 13C nmr. Preferably, the amount 2-1 and 1-3 monomer insertions in the polyolefin is less than 0.5%, more preferably, less than 0.2 and most preferably undetectable. In a further aspect, the present invention provides a syndiotactic polyolefin having a monomer length of up to ClO and a pentad distribution comprising at least 85% rrrr as measured by 13C nmr. Preferably, the pentad distribution comprises at least 90%, more preferably at least 94% rrrr as measured by 13C n r.
The invention will now be described in further detail, by way of example only, with reference to the attached drawings in which:
FIGURES 1 to 12 show illustrations of the structures of preferred catalyst components of the present invention; and
FIGURE 13 shows the results of differential scanning calorimetry analysis on isotactic polypropylene produced at 40°C using the catalyst shown in Figure 1.
Example 1
Preparation of isopropylidene [ (3-tertbutyl-5-mβthyl- cyclopen adienyl) - (3 , 6-di— ter but 1-f luorenyl ) 1 zirconium dichloride
A. Preparation of 3 , 6 , 6— trimethylf ulvene
Reaction
Methanol Me-Cp + Acetone ► 3, 6, 6-Me3-Ful
Pyrolidene
Procedure In a round bottom flask equipped with magnetic stirring bar and N2 inlet is placed 350 ml of methanol (at -78°C) containing freshly prepared methylcyclopentadiene under N2. To this solution is added a solution of 28.6 g (0.493 mol) of acetone in 50 ml of methanol dropwise. Subsequently 52.5 g (0.738 mol) of pyrolidene is added. The reaction mixture is stirred at ambient temperature for 24 hours. After neutralisation with acetic acid and separation of the organic phase the solvent is evaporated and the remaining yellow oil is subjected to distillation. A mixture of 3, 6, 6-Me3-Ful and 2, 6, 6-Me3-Ful is obtained in 65% yield.
B. Preparation of l-methyl-3-tert-butylcyclopentadiene
Reaction
Ether
3, 6,6-Me3-Ful + Me-Li > l-Me-3-t-Bu-Cp
0°C Procedure
50 g (0.417 mol) of 3 - 6, 6-Me3-t-Bu-Ful is placed in a 1 litre flask and dissolved in 500 ml of diethyl ether and cooled down to 0°C. To the solution is added dropwise 260.4 ml (0.417 mol) of methyllithiu in ether (1.6 mol). The reaction is completed after a few hours. After adding 75 ml of saturated solution of NH4C1 in water, the organic phase is separated and dried with MgS0 . The evaporation of the solvent leads to the isolation of a yellow oil. After distillation, 33.65 g (59.28%) of l-Me-3-t-Bu-Cp is obtained. C. Preparation of 1- 6, 6-trimethyl-3-tβrt-btttylfulvene
Reaction
Methanol l-Me-3-t-Bu-Cp + Acetone > 1, 6, 6-Me3-3-t-Bu-Ful
Pyrolidene Procedure
In a 1 1 flask is placed 30 g (0.220 mol) of l-Me-3-t-Bu-Cp and dissolved in 60 ml of methanol. The mixture is cooled down to -78°C. 5.11 g (0.088 mol) of acetone in 20 ml of methanol is added slowly. In the next step, 9.4 g (0.132 mol) of pyrolidene in 20 ml of methanol is added. After a week, the reaction is terminated by addition of 20 ml of acetic acid. After separation of the organic phase, drying, evaporation of solvents and distillation, 16.95 g of an orange oil is obtained (yield, 43.66%).
D. Preparation of 2 ,2- [ (3-tertbutyl-5-methyl— cyclopenta.dienyl) - (3 r 6-di-tβrtbv.tyl-fluorenyl) ] -propane
Reaction
THF 3, 6-d-t-Bu-Flu + Me-Li > (3, 6-d-t-Bu-Flu) -Li+
0°C
THF
(3,6-d-t-Bu-Flu)-Li+ + 1, 6, 6-Me3-3-t-Bu-Ful Me2C(3-t-Bu-
5-Me-Cp) (3, 6-d-t-Bu-Flu) Procedure
1.5 g (5.387 mmol) of 3, 6-d-t-Bu-Flu in 100 ml of dry tetrahydrofuran, is placed into a 250 ml flask, under N2 and the solution is pre-cooled to 0°C . The 3, 6-d-t-Bu-Flu may be synthesised according to Shoji Kajigaeshi et al . Bull. Chem. Soc. Jpn. 59,97-103(1986) or M Bruch et al . Liebigs Ann. Chem. 1976,74-88. Then, a solution of 3.4 ml (5.387 mmol) of methyllithium is added drop wise to the solution. The solution is red and is further continued at room temperature during 4 hours. After that, a solution of 0.9497 g (5.382 mmol) of 1, 6, 6-Me3-3-t-Bu-Ful in 10 ml of dry tetrahydrofuran is added dropwise to this solution. The reaction is further continued during 24 hours. After adding 40 ml of saturated solution of NH4C1 in water, the yellow organic phase is separated and dried with MgS04 anhydrous. The evaporation of the solvent leads to the isolation of 2.36 g (yield, 96.32%) of orange solid product.
E. Preparation of isopropylidene [ (3-tertb-utyl-5-methyl- cyclopentadienyl) - (3 , β-di-tertbutyl-fliiorenyl) ] zirconium dichloride (1)
Reaction
THF Me2C ( 3-t-Bu-5-Me-Cp ) ( 3 , 6-d-t-Bu-Flu) + 2 Me-Li
0°C
Me2C ( 3-t-Bu-5-Me-Cp ) -Li+ ( 3 , 6-d-Bu-Flu ) -Li+ ZrC14
Me2C (3-t-Bu-5-Me-Cp) -Li+ (3, 6-d-t-Bu-Flu) -Li+ ► n-C5
Me2C(3-t-Bu-5-Me-Cp) (3, 6-d-t-Bu-Flu) ZrC12 + 2 LiCl
Procedure
2 g (4.398 mmol) of ligand is dissolved in 100 ml of dry tetrahydrofuran under N2, and the solution is pre-cooled to 0°C. A solution of 5.5 ml (3.796 mmol) of methyllithium (1.6 mol/diethyl ether) is added dropwise to this solution. After
3 hours, the solvent is removed in vacuum, the red powder is washed with 2 x 100 ml of pentane. The red dianion ligand and 100 ml of pentane are placed into a 250 ml flask, under N2. 1.02 g (4.398 mmol) of zirconium tetrachloride is added to this suspension. The reaction mixture is red-brown and stirred overnight in a glove box. After filtration, the orange solution is removed in vacuo at 40°C and yielded 2.3 g (85.18%) of orange powder. Apparently, this metallocene is soluble in pentane. According the 1HNMR of the product it seems that a second isomer with a chemical structure of isopropylidene (2 (or 4) -methyl-3-tertbutylcyclopentadienyl- 3, 6-ditertbutylfluorenyl) ZrC12 (2) is formed as the second product which is less stereoregular .
Example 2
Preparation of isopropylidene [ (cyclopentadienyl) - (3 , 6-di- tertbutyl- luorenyl) ] zirconium dichloride The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2- [ (cyclopentadienyl) - (3, 6-di-tertbutyl- fluorenyl) ] -propane .
A. Preparation of 2 r2- [ (cyclopentadienyl) - (3 , 6-di- tertbutyl-fluorenyl) 3 -propane
Procedure
The preparation of this ligand is the same as described in Example 1, step D, except that the 1, 6, 6-trimethyl-3-tert- butylfulvene is replaced by 0,5720 g (5.387 mmol) of 6,6- dimethylfulvene .
Example 3
Preparation of isopropylidene [ (3-methyl- cyclopentadienyl) - (3 , 6-di-tertbutγl-fluorenyl) ] zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2-[(3- methyl-cyclopentadienyl) - (3, 6-di-tertbutyl-fluorenyl) ] - propane .
A. Preparation of 2 ,2- [ (3-methyl-cyclopentadienyl) - (3 , 6-di- tertbutyl-fluorenyl) ] -propane
Procedure The preparation of this ligand is the same as that of step D, but the 1, 6, 6-trimethyl-3-tert-butylfulvene is replaced by 0.6475 g (5.387 mmol) of 3, 6, 6-trimethylfulvene (the synthetic procedure is described in Example 1, step A) .
Example 4
Preparation of isopropylidene [ (3-tertbutyl- cyclopentadienyl) - (3 , 6-di-tertbutyl-fluorenyl) ] zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2, 2- [(3- tertbutyl-cyclopentadienyl) - (3, 6-di- tertbutyl-fluorenyl) ] -propane prepared as below.
A. Preparation of 2,2-[ (3-tertbutyl-cyclopentadienyl) - (3 , 6- di-tertbutyl-fluorenyl) 3 -propane
Procedure
The preparation of this ligand is the same that the step D, but the 1, 6r 6-trimethyl-3-tert-butylfulvene is replaced by C.8742 g (5.387 mmol) of 6, 6-dimethyl-3-tert-butylfulvene .
B. Preparation of , 6-dimethyl-3-tert-butylfulvene
Procedure
The synthetic procedure according to Example 1, step A, is followed, but the methylcyclopentadiene is replaced by the tert-butylcyclopentadiene . C. Preparation of tert-butylcyclopentadiene
Procedure
The synthetic procedure according to Example 1, step B, is followed, but the 3, 6, 6-trimethylfulvene is replaced by 6,6- dimethylfulven .
Example 5a
Preparation of isopropylidene[ Q-trimethylsilyl- cyclopentadienyl) - (3 , 6-di-tertbutyl-fluorenyl) 3 zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the diphenyl [ (3-trimethylsilyl-cyclopentadienyl) - (3, 6-di- tertbutyl-fluorenyl) Imethylene.
A. Preparation of 2,2-[ (3-trimethylsilyl- cyclopentadienyl) - (3 , 6-di-tertbutyl-fluorenyl) 3propane
Procedure
The preparation of this ligand is the same as described in Example 1, step D, except that the 1, , 6-trimethyl-3-tert- butylfulvene is replaced by 1.2407 g (5.387 mmol) of 6,6- dimethylfulvene .
B. Preparation of 2 ,2- [ (3-trimethyl3ilyl- cyclopentadienyl) - (3 , 6-di-tertbutyl-fluorenyl) 3propane Reaction
THF
Me2C(Cp) (3,6-d-t-Bu-Flu) + Me-Li >
Me2C(Li+Cp-) (3,6-d-t-Bu-Flu)
Me2C(Li+Cp-) (3,6-d-t-Bu-Flu) + Me3Si-Ci
Me2C(3-Me3Si-Cp) (3,6-d-t-Bu-Flu) + LiCl
Procedure
First, in a 1 1 flask, 10 g (0.026 mol) of 2,2- (cyclopentadienyl) (3, 6-di-tertbutyl-fluroenyl) propane is dissolved in 300 ml of tetrahydrofuran under N2. Then 16.25 ml (0.026 mol) of methyllithium is added dropwise to this solution at room temperature (the flask is pre-cooled with a water bath) . After a stirring period of one hour, 3.3 ml (0.026 mol) of chlorotrimethylsilane, is added to this solution. The reaction mixture is stirred for an additional 3 hours. Then the solvent is removed in vacuo. One litre of pentane is added to the solid orange residue. the reaction mixture is heated at 40°C for 10 minutes. The orange solution is filtered (to remove LiCl, 1.40 g of residue), concentrated to 100 ml, and cooled down to crystallise the product 2, 2- (3-trimethylsilyl-cyclopentadienyl) luorenyl) propane. The raw product has a beige colour. The crystallised product has a white colour, 65-70% yield. The product was stored under N2. Example 5b
Preparation of diphenylmethylidene [ (3-trimethyl3xlyl- cyclopentadiβnyl) - (3 , 6-di-tertbutyl-fluorenyl) 3 zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the diphenyl [ (3-trimethylsilyl-cyclopentadienyl) - (3, 6-di- tertbutyl-fluorenyl) ] methylene.
A. Preparation of 1, 1,1, 1-diphenyl[ (3-trimethylsilyl- cyclope tadienyl) - (3 , 6-di-tertbutyl-fluorenyl) 3methane
Procedure
The preparation of this ligand is the same as described in Example 1, step D, except that the 1, 6, 6-trimethyl-3-tert- butylfulvene is replaced by 1.2407 g (5.387 mmol) of 6,6- dimethylfulvene .
B. Preparation of diphenyl[ (3-t imethylsilyl- cyclopentadienyl) - (3 , 6-di-tertbutyl-fluorenyl) 1methane
Reaction
THF
Me2C(Cp) (3, 6-d-t-Bu-Flu) + Me-Li
Me2C(Lι+Cp-) (3, 6-d-t-Bu-Flu)
Me2C(Li+Cp-) (3,6-d-t-Bu-Flu) + Me3Si-Cl
Me2C(3-Me3Si-Cp) (3,6-d-t-Bu-Flu) + LiCl Procedure
First, in a 1 1 flask, 10 g (0.026 mol) of 2,2- ( cyclopentadienyl) (3, 6-di-tertbutyl-fluorenyl) propane is dissolved in 300 ml of tetrahydrofuran under N2. Then 16.25 ml (0.026 mol) of methyllithium is added dropwise to this solution at room temperature (the flask is pre-cooled with a water bath). After a stirring period of one hour, 3.3 ml (0.026 mol) of chlorotrimethylsilane, is added to this solution. The reaction mixture is stirred for an additional 3 hours. Then the solvent is removed in vacuo. One litre of pentane is added to the solid orange residue. the reaction mixture is heated at 40°C for 10 minutes. The orange solution is filtered (to remove LiCl, 1.40 g of residue), concentrated to 100 ml, and cooled down to crystallise the product 2,2- (3-trimethylsilyl-cyclopentadienyl) (3,6-di- tertbutyl fluorenyl) propane . The raw product has a beige colour. The crystallised product has a white colour/ 65-70% yield. The product was stored under N2.
Example 6
Preparation of isopropylidene [ (3 ,5-dimethγl- cyclopentadienyl) - (3 , 6-di-tertbutyl-fluorenyl) zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2- [ (3, 5-dimethyl-cyclopentadienyl) - (3, 6-di-tertbutyl- fluorenyl) ] -propane. A. Preparation of 2 , 2- [ (3 , 5 -dime th 1- cyclopentad enyl) - (3 , 6-di-tertbutyl-f luorenyl) ] -propane
Procedure
The preparation of this ligand is the same as in Example 1 step D, but the 1, 6, 6-trimethyl-3-tert-butylfulvene is replaced by 0.8742 g (5.387 mmol) of 1,3,6,6- tetramethylfulvene .
B . Preparation of 1 , 3 , 6 , 6-tetramethyl ulvene
The synthetic procedure according to Example 1 srep A, is followed but the methylcyclopentadiene is replaced by 1,3- dimethylcyclopentadiene .
C. Preparation of 1,3-dimethylcyclopentadiene
Reaction
Ether
3-Me-Cp=0 + CH3-Mg-Br >■ 1, 3-Me2-Cp-0-Mg-Be
0°C l,3-Me2-Cp-0-Mg-Br + H20 > 1,3-Me2-Cp + Mg-Br-OH
Procedure
195 ml (0.585 mole) of methyl magnesium bromide (solution 3.0 mole/diethyl ether) in 200 ml of dry diethyl ether, is placed into a 2 1 flask, under N2 and the solution is pre-cooled to 0°C. Then a solution of 47-15 g (0.4905 mole) of 3-methyl-2- cyclopentenone in 100 ml of diethyl ether is added dropwise to the solution for 3 hours at 0°C and for an hour at 10°C. This product is transferred into a 5 1 flask pre-cooled to 0°C and containing 1 1 of water. The solution is yellow. The yellow organic phase is separated and the solvent is removed in vacuo (500 mbars) at room temperature. The evaporation of the solvent leads to the isolation of a clear orange solution. After distillation 31.83 g (yield, 65.95%) of 1, 3-dimethylcyclopentadiene is obtained. The product is a colourless unstable liquid and used directly for the preparation of the 1, 3, 6, 6-trimethylfulvene.
Example 7
Preparation of diphenylmethylidene [ (cyclopentadienyl) -(3,6- di-tertbutyl-fluorenyl) 3 zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2, 2diphenyl[ (cyclopentadienyl) - (3, 6-di-tertbutyl- fluorenyl) ] ethylene.
A. Preparation of 1,1,1,1-diphenyl [ (cyclopentadienyl) -(3,6- di-tertbutyl-fluorenyl) ethane
Procedure
The preparation of this ligand is the same as described in Example 1, step D, except that the 1, 6, β-trimethyl-3-tert- butylfulvene is replaced by 1.2407 g (5.387 mmol) of 6,6- diphenylfulvene .
Example 8
Preparation of dphenylm thylidene [ (3-methyl- cyclopentadienyl) - (3 , 6-di-tertbutyl-fluorenyl) zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2- diphenyl [ (3-methyl-cyclopentadienyl) - (3, 6-di-tertbutyl- fluorenyl) ] propane.
A. Preparation of 1,1,1,1-diphenyl[ (3-methyl- σyσlopentadienyl) - (3 , 6-di-tertbutyl-fluorenyl) methane
Procedure
The preparation of this ligand is the same as described in Example 1, step D, except that the 1, 6, 6-trimethyl-3-tert- butylfulvene is replaced by 1.2407 g (5.387 mmol) of 3- methyl-6, 6-diphenylfulvene.
B . Preparation of 3 -me hy 1-6 , 6-diphenylf ulvene
Procedure
The preparation of this fulvene is the same as described in Example 1, step A, except that the acetone is replaced by 1.3162 g (5.387 mmol) of 6, 6-diphenylfulvene . Example 9
Preparation of diphenylmethylidene[ (3-tertbutyl- cyclopentadiβnyl) - (3 , 6-di-tertbutyl- luorenyl) 3 zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the diphenyl [ (3-terbutyl-cyclopentadienyl) - (3, 6-di-tertbutyl- fluorenyl) ] methylene .
A. Preparation of 1,1,1, 1-diphenyl [ (3-tertbutyl- cyclopenta.di.enyl) - (3 , 6-di-tertbutyl-fluorenyl) 3methane
Procedure
The preparation of this ligand is the same as described in Example 4, step A, except that the 6, 6-dimethyl-3-tert- butylfulvene is replaced by the 3-tertbutyl-6, 6- diphenylfulvene .
B. Preparation of 3-tertbutyl-6 , 6-diphenylfulvene
Procedure
The preparation of this fulvene is the same as described in Example 1, step A, except that the acetone is replaced by the benzophenone and the methylcyclopentadiene is replaced by the tert-butylcyclopentadiene (the synthetic procedure is described in Example 4, step C) . Example 10
Preparation of diphenylmethyl dene [ (3-trimethylsilyl- cyclopen adienyl) - (3 , 6-di-tertbutyl-fluorenyl) 3 zirconium dichloride
The synthetic procedure according to Example 1 is followed except that the ligand in step D is replaced by the 2,2- diphenylf (3-trimethylsilyl-cyclopentadienyl) - (3, 6-di- tertbutyl-fluorenyl) ] propane
A. Preparation of 1,1,1, 1-diphenyl [ (3-trimethylsilyl- cyclopentadienyl) - (3 , 6-di-tertbutyl- luorenyl) 3 ethane
Procedure
The preparation of this ligand is the same as described in Example 5, step B, except that the 2,2- [ (cyclopentadiene) (fluorenyl) ]propane is replaced by the 2,2- diphenyl[ (cyclopentadienyl) (fluorenyl) jpropane.
B. Preparation of 2 ,2-diphenyl[ (cyclopentadienyl) - (3 , 6-di- tertbutyl-fluorenyl) 3 ropane
Procedure
The preparation of this ligand is the same as described in Example 1, step D, except that the 1, 6, 6-trimethyl-3-tert- butylfulvene is replaced by the 6, 6-diphenylfulven .
Example 11 Polymerisation procedures
Each polymerisation was performed in a 4 litre bench reactor with pure propylene. Polymerisation was initiated by introducing metallocene (0.5 to 5 mg) precontacted with 1 ml of MAO (methylaluminoxane) (30% solution in toluene obtained from WITCO) three minutes prior to its introduction into the reactor.
Table la shows figures for production of syndiotactic polypropylene using as a catalyst component described in Example 2. Table lb shows corresponding figures for the metallocene described in Example 7.
Table la
Syndiotactic polypropylene made using isopropylidene bridge catalyst
Polymerisa .tion Mw i (kD) Mp°C Micro acticity emp (rrrr)
30°C 250 152 - 154 92 - 94%
40°C 200 150 90 - 92 %
60°C 170 145 88 - 90 %
80°C 140 142 86 - 88%
Table lb
Syndiotactic polypropylene made using diphenylmethylidenε bridge catalyst . Polymerisation Mw (kD) Mp°C Microtacticity temp (rrrr)
20°C 1000 152- 154 92-94%
40°C 800 150 90-92%
60°C 680 145 88-90%
80°C 350 142 86-88%
Table 2 shows the microtacticity of the polymer obtained using the catalyst according to Example 1 under polymerisation conditions as defined by the corresponding entries in Table 1. The results were obtained using "c NMR spectroscopy. It will be apparent that the polypropylene contained more than 95% of pentads in the purely isotactic form (mmmm) . The molecular weight (Mw) of the polypropylene was 530,000 and the melting point was 153°C. Melting point was determined by DSC analysis as shown in Figure 13. A sample was held at 25°C for 1 min, heated from 25°C to 220°C at 20°C/min and held for 5 mins at 220°C. The sample was then cooled from 220°C to 25°C at 20°C/min, held at 25°C for 3 mins and heated from 25°C to 220°C at 20°C/min.
Table 2
Pentad stereo-sequence distributions %
mmmm 95.7 mm r 1.70 rmmr 0.00 mmrr 1.70 mr m 0.00
+ r rr mrmr 0.00 rrrr 0.00 rrr 0.00 mrr 0.80

Claims

CLAIMS :
1. A metallocene catalyst component for use in preparing polyolefins having a monomer length of up to CIO, which component has the general formula:
R CpR-RaR,) (C- R, ' R2 ' ) MQ2 (I)
wherein Cp is a substituted or unsubstituted cyclopentadienyl ring,- C.J is a substituted fluorenyl ring; R" is -a structural bridge imparting stereorigidity to the component; R^ is optionally a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is of the formula YR#3 in which Y is chosen from group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$3, in which Z is chosen from group IVA, and each R$ is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, Rλ' and R-, ' are each independently substituent groups on the fluorenyl ring, one of which is a group of the formula AR' * ' j, in which A is chosen from Group IVA, and each R' ' ' is independently hydrogen or a hydrocarbyl having 1 to 20 carbon atoms and the other is hydrogen or a second group of the formula AR1'^; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen.
2. A catalyst component according to claim 1, wherein R.J and R-J are at positions 3 and 6 on the fluorenyl ring.
3. A catalyst component according to claim 1 or claim 2, wherein A is carbon or silicon.
. A catalyst component according to claim, 3 , wherein AR' * ' j is hydrocarbyl having from 1 to 20 carbon atoms.
5. A catalyst component according to claim , wherein AR' • « a is C(CH3)3.
6. A catalyst component according to claim 2, wherein AR' ' '3 is Si(CH3)3.
7. A catalyst component according to any one of the preceding claims, wherein R- and R- ' are the same.
8. A catalyst component according to any one of the preceding claims, wherein R" is alkylidene having 1 to 20 carbon atoms, a dialkyl germanium or silicon or siloxane, alkyl phosphine or amine.
9. A catalyst component according to claim 8, wherein R" is isopropylidene, dimethylsilanediyl or diphenylmethylidene .
10. A catalyst component according to any one of the preceding claims, wherein M is zirconium or titanium.
11. A catalyst component according to any one of the preceding claims, wherein Q is halogen.
12. A catalyst component according to any one of the preceding claims, wherein R-, is C(CH3)3, c(CH,)aPh, CPh3 or Si(CH3)a.
13. A catalyst component according to claim 12, wherein Rx is C(CH3)3.
14. A catalyst component according to any one of the preceding claims, wherein Y is carbon.
15. A catalyst component according to any one of the preceding claims, wherein Z is carbon.
16. A catalyst component according to any preceding claim, wherein R, is CH,.
1 . A catalyst component according to any one of the preceding claims, wherein R3 is CH3.
18. A metallocene catalyst component for use in preparing isotactic polyolefins, which component comprises iεopropylidene-3-t-butyl-5-methyl-cyclopentadienyl 3,6 di t- butyl fluorenyl ZrCl2.
19. A metallocene catalyst component for use in preparing polyolefins having a monomer length of up to CIO, which comprises (i) a catalyst component according to any one of the preceding claims; and (ii) a regioisomer thereof in which -j is proximal to the bridge and positioned vicinal to the distal substituent.
20. A metallocene catalyst component for use in preparing polyolefins, which comprises isopropylidene- (3-t- butyl-5- methyl cyclopentadienyl- , 6 di t-butyl fluorenyl) ZrCl2 and isopropylidene- (3 -t-butyl-2-methyl cyclopentadienyl-3 , 6 di t- butyl fluorenyl) ZrCl2.
21. A catalyst system for use in preparing polyolefins, which comprises (a) a catalyst component according to any one of the preceding claims; and (b) an aluminium- or boron- containing co-catalyst capable of activating the catalyst component .
22. A catalyst system according to claim 17, which further comprises an inert support .
23. Use of a catalyst component according to any one of claims 1 to 11, and a cocatalyst which activates the catalyst component, for the preparation of a syndiotactic polyolefin having a monomer length of up to CIO.
24. Use according to claim 23, wherein Cp is unsubstituted.
25. Use of a catalyst component according to any one of claims 1 to 13, and a cocatalyst which activates the catalyst component, for the preparation of a syndiotactic/isotactic block polyolefin having a monomer length of up to CIO, wherein Rx is a substituent on the cyclopentadienyl ring.
26. Use of a catalyst component according to any one of claims 1 to 17, and a cocatalyst which activates the catalyst component, for the preparation of an isotactic polyolefin having a monomer length of up to CIO, wherein R^ and R-, are both substituents on the cyclopentadienyl ring.
27. Use of a catalyst component according to claim 19 or claim 20, and a cocatalyst which activates the catalyst component, for the preparation of isotactic polyolefins having a monomer length of up to CIO and having a multimodal molecular weight distribution.
28. A process for preparing polyolefins having a monomer length of up to CIO, which comprises contacting a catalyst system according to claim 21 or claim 22 with at least one olefin in a reaction zone under polymerisation conditions.
29. A process according to claim 28, wherein the olefin is propylene.
30. A process according to claim 28, wherein two or more olefins are present in the reaction zone to produce a polyolefin copolymer.
31. An isotactic polyolefin having a monomer length of up to CIO and a pentad distribution comprising at least 87% mmmm as measured by 13C nmr.
32. A polyolefin according to claim 31, wherein the pentad distribution comprises at least 95% mmmm as measured by 13C nmr.
33. A polyolefin according to claim 31 or claim 32, wherein the amount of 2-1 and 1-3 monomer insertions in the polyolefin is undetectable .
34. A syndiotactic polyolefin having a monomer length of up to CIO and a pentad distribution comprising greater than 80% rrrr as measured by 13C nmr.
35. A syndiotactic polyolefin according to claim 34, wherein the pentad distribution comprises at least 85% rrrr as measured by 13 C nmr.
36. A polyolefin according to any one of claims 31 to 35, which comprises a polypropylene.
PCT/EP1999/001094 1999-02-19 1999-02-19 Polyolefin production WO2000049029A1 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
PCT/EP1999/001094 WO2000049029A1 (en) 1999-02-19 1999-02-19 Polyolefin production
AU31411/99A AU3141199A (en) 1999-02-19 1999-02-19 Polyolefin production
JP51283599A JP4864176B2 (en) 1999-02-19 1999-02-19 Polyolefin production
RU2001124801/04A RU2244721C2 (en) 1999-02-19 2000-02-18 Polyolefin production
EP00906358A EP1169356B1 (en) 1999-02-19 2000-02-18 Polyolefin production
AU28062/00A AU2806200A (en) 1999-02-19 2000-02-18 Polyolefin production
PCT/EP2000/001378 WO2000049056A1 (en) 1999-02-19 2000-02-18 Polyolefin production
ES00906358T ES2223460T3 (en) 1999-02-19 2000-02-18 POLYOLEFIN PRODUCTION.
BRPI0008312-7A BR0008312B1 (en) 1999-02-19 2000-02-18 process for preparing polyolefins.
US09/506,943 US6515086B1 (en) 1999-02-19 2000-02-18 Polyolefin production
AT00906358T ATE271071T1 (en) 1999-02-19 2000-02-18 POLYOLEFIN PRODUCTION
KR1020017010519A KR100663788B1 (en) 1999-02-19 2000-02-18 Polyolefin production
DE60012166T DE60012166T2 (en) 1999-02-19 2000-02-18 polyolefin
CA2371835A CA2371835C (en) 1999-02-19 2000-02-18 Stereorigid, bridged metallocene catalysts for polyolefin production
CNB008059535A CN1152056C (en) 1999-02-19 2000-02-18 Polyolefin production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP1999/001094 WO2000049029A1 (en) 1999-02-19 1999-02-19 Polyolefin production

Publications (1)

Publication Number Publication Date
WO2000049029A1 true WO2000049029A1 (en) 2000-08-24

Family

ID=8167219

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/EP1999/001094 WO2000049029A1 (en) 1999-02-19 1999-02-19 Polyolefin production
PCT/EP2000/001378 WO2000049056A1 (en) 1999-02-19 2000-02-18 Polyolefin production

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/001378 WO2000049056A1 (en) 1999-02-19 2000-02-18 Polyolefin production

Country Status (11)

Country Link
JP (1) JP4864176B2 (en)
KR (1) KR100663788B1 (en)
CN (1) CN1152056C (en)
AT (1) ATE271071T1 (en)
AU (2) AU3141199A (en)
BR (1) BR0008312B1 (en)
CA (1) CA2371835C (en)
DE (1) DE60012166T2 (en)
ES (1) ES2223460T3 (en)
RU (1) RU2244721C2 (en)
WO (2) WO2000049029A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001027124A1 (en) * 1999-10-08 2001-04-19 Mitsui Chemicals, Inc. Metallocene compound, process for producing metallocene compound, olefin polymerization catalyst, process for producing polyolefin, and polyolefin
US6469188B1 (en) 1999-01-20 2002-10-22 California Institute Of Technology Catalyst system for the polymerization of alkenes to polyolefins
US6800707B2 (en) 2000-08-07 2004-10-05 Fina Technology, Inc. Polyolefin production
EP1493759A1 (en) * 2003-07-04 2005-01-05 Total Petrochemicals Research Feluy Polymerisation process
EP1493778A1 (en) * 2003-07-04 2005-01-05 Total Petrochemicals Research Feluy Polyolefin production
EP1496070A1 (en) * 2003-07-09 2005-01-12 Total Petrochemicals Research Feluy A polyolefin having internal double bonds and a method for making the same
WO2005005498A1 (en) * 2003-07-04 2005-01-20 Total Petrochemicals Research Feluy Propylene-styrene copolymerisation process
EP1734059A1 (en) * 2005-06-13 2006-12-20 Total Petrochemicals Research Feluy Carbon-bridged cyclopentadienyl-fluorenyl ligands
EP1891120A1 (en) * 2005-06-13 2008-02-27 Total Petrochemicals Research Feluy Ethylene and alpha-olefins polymerisation catalyst system based on fluorenyl ligand
EP1988104A1 (en) * 2003-03-28 2008-11-05 Mitsui Chemicals, Inc. Propylene copolymer, polypropylene composition, use thereof, transition metal compounds, and catalysts for olefin polymerization
WO2009045301A2 (en) * 2007-09-28 2009-04-09 Youlu Yu Polymerization catalysts for producing polymers with low melt elasticity
US7879960B2 (en) 2004-08-30 2011-02-01 Mitsui Chemicals, Inc. Process for producing propylene polymer

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5000070B2 (en) * 2001-03-15 2012-08-15 三井化学株式会社 Auto parts made of polypropylene resin composition
KR20080022116A (en) * 2005-05-25 2008-03-10 미쓰이 가가쿠 가부시키가이샤 Transition metal compound, olefin polymerization catalyst, and process for producing olefin polymer
US8017705B2 (en) 2006-11-17 2011-09-13 Mitsui Chemicals, Inc. Process for production of syndiotactic propylene polymer
WO2008088022A1 (en) 2007-01-18 2008-07-24 Prime Polymer Co., Ltd. Propylene homopolymer for stress-resistant molded object, composition containing the polymer, and stress-resistant molded object obtained from the same
CN105330771B (en) * 2014-12-03 2018-12-14 亚培烯科技（杭州）有限公司 A kind of metallocene linear-low density polyethylene catalyst and its preparation method and application
CN115677879A (en) * 2021-07-31 2023-02-03 华为技术有限公司 Catalyst for preparing cycloolefin copolymer, preparation method of cycloolefin copolymer, cycloolefin copolymer and application of cycloolefin copolymer

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0419677A1 (en) * 1989-04-18 1991-04-03 MITSUI TOATSU CHEMICALS, Inc. Syndiotactic polypropylene resin composition
EP0487278A2 (en) * 1990-11-20 1992-05-27 Mitsubishi Chemical Corporation Functionalized olefin polymers
EP0577581A2 (en) * 1992-06-22 1994-01-05 Fina Technology, Inc. Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
EP0748824A1 (en) * 1995-06-02 1996-12-18 Chisso Corporation High stereoregular polypropylenes
EP0780396A1 (en) * 1995-12-18 1997-06-25 Hoechst Aktiengesellschaft Process for depleting by-products in reaction mixtures
EP0824112A1 (en) * 1996-08-13 1998-02-18 Hoechst Aktiengesellschaft Supported chemical compound
EP0881236A1 (en) * 1997-05-26 1998-12-02 Fina Research S.A. Metallocene catalyst component for use in producing isotactic polyolefins

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0419677A1 (en) * 1989-04-18 1991-04-03 MITSUI TOATSU CHEMICALS, Inc. Syndiotactic polypropylene resin composition
EP0487278A2 (en) * 1990-11-20 1992-05-27 Mitsubishi Chemical Corporation Functionalized olefin polymers
EP0577581A2 (en) * 1992-06-22 1994-01-05 Fina Technology, Inc. Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
EP0748824A1 (en) * 1995-06-02 1996-12-18 Chisso Corporation High stereoregular polypropylenes
EP0780396A1 (en) * 1995-12-18 1997-06-25 Hoechst Aktiengesellschaft Process for depleting by-products in reaction mixtures
EP0824112A1 (en) * 1996-08-13 1998-02-18 Hoechst Aktiengesellschaft Supported chemical compound
EP0881236A1 (en) * 1997-05-26 1998-12-02 Fina Research S.A. Metallocene catalyst component for use in producing isotactic polyolefins

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6469188B1 (en) 1999-01-20 2002-10-22 California Institute Of Technology Catalyst system for the polymerization of alkenes to polyolefins
US6693153B2 (en) * 1999-01-20 2004-02-17 California Institute Of Technology Catalyst system for the polymerization of alkenes to polyolefins
WO2001027124A1 (en) * 1999-10-08 2001-04-19 Mitsui Chemicals, Inc. Metallocene compound, process for producing metallocene compound, olefin polymerization catalyst, process for producing polyolefin, and polyolefin
US6800707B2 (en) 2000-08-07 2004-10-05 Fina Technology, Inc. Polyolefin production
EP1988104A1 (en) * 2003-03-28 2008-11-05 Mitsui Chemicals, Inc. Propylene copolymer, polypropylene composition, use thereof, transition metal compounds, and catalysts for olefin polymerization
WO2005005492A1 (en) * 2003-07-04 2005-01-20 Total Petrochemicals Research Feluy Random olefin copolymers
EP1493759A1 (en) * 2003-07-04 2005-01-05 Total Petrochemicals Research Feluy Polymerisation process
WO2005005498A1 (en) * 2003-07-04 2005-01-20 Total Petrochemicals Research Feluy Propylene-styrene copolymerisation process
WO2005005535A1 (en) * 2003-07-04 2005-01-20 Total Petrochemicals Research Feluy Polypropylene blends having a narrow molecular weight distribution
EP1493778A1 (en) * 2003-07-04 2005-01-05 Total Petrochemicals Research Feluy Polyolefin production
KR101127652B1 (en) * 2003-07-04 2012-03-23 토탈 페트로케미칼스 리서치 펠루이 Polypropylene blends having a narrow molecular weight distribution
WO2005005502A1 (en) * 2003-07-09 2005-01-20 Total Petrochemicals Research Feluy A method for making polyolefins having internal double bonds
EP1496070A1 (en) * 2003-07-09 2005-01-12 Total Petrochemicals Research Feluy A polyolefin having internal double bonds and a method for making the same
US7879960B2 (en) 2004-08-30 2011-02-01 Mitsui Chemicals, Inc. Process for producing propylene polymer
WO2006134098A1 (en) * 2005-06-13 2006-12-21 Total Petrochemicals Research Feluy Carbon-bridged cyclopentadienyl-fluorenyl ligands
EA014645B1 (en) * 2005-06-13 2010-12-30 Тотал Петрокемикалс Рисерч Фелюй Carbon-bridged cyclopentadienyl-fluorenyl ligands
EP1891120A1 (en) * 2005-06-13 2008-02-27 Total Petrochemicals Research Feluy Ethylene and alpha-olefins polymerisation catalyst system based on fluorenyl ligand
CN101193921B (en) * 2005-06-13 2011-08-31 托塔尔石油化学产品研究弗吕公司 Carbon-bridged cyclopentadienyl-fluorenyl ligands
EP1734059A1 (en) * 2005-06-13 2006-12-20 Total Petrochemicals Research Feluy Carbon-bridged cyclopentadienyl-fluorenyl ligands
WO2009045301A2 (en) * 2007-09-28 2009-04-09 Youlu Yu Polymerization catalysts for producing polymers with low melt elasticity
WO2009045301A3 (en) * 2007-09-28 2009-11-19 Youlu Yu Polymerization catalysts for producing polymers with low melt elasticity

Also Published As

Publication number Publication date
JP2002510358A (en) 2002-04-02
ES2223460T3 (en) 2005-03-01
CN1346373A (en) 2002-04-24
BR0008312A (en) 2002-01-22
RU2244721C2 (en) 2005-01-20
CA2371835A1 (en) 2000-08-24
KR20020002471A (en) 2002-01-09
ATE271071T1 (en) 2004-07-15
WO2000049056A1 (en) 2000-08-24
CN1152056C (en) 2004-06-02
DE60012166D1 (en) 2004-08-19
BR0008312B1 (en) 2011-06-14
AU2806200A (en) 2000-09-04
KR100663788B1 (en) 2007-01-03
CA2371835C (en) 2010-07-27
DE60012166T2 (en) 2005-09-08
AU3141199A (en) 2000-09-04
JP4864176B2 (en) 2012-02-01

Similar Documents

Publication Publication Date Title
US6515086B1 (en) Polyolefin production
EP1283223B1 (en) Use of a mixture of two metallocene regioisomers as catalyst component for preparing bimodal isotactic polyolefins
EP0423101B2 (en) Catalyst for producing hemiisotactic polypropylene
US5416228A (en) Process and catalyst for producing isotactic polyolefins
CA2371835C (en) Stereorigid, bridged metallocene catalysts for polyolefin production
KR100626258B1 (en) Metallocene Catalysts Containing an Indenyl Moiety Substituted at the 4-, 5-, 6- or 7-Position by a Siloxy or Germyloxy Group
US20040087746A1 (en) Polyolefin production
JPH09136930A (en) Production of syndiotactic/isotactic block polyolefin
EP1095081B1 (en) Polyolefin production
US6800707B2 (en) Polyolefin production
EP1169356B1 (en) Polyolefin production
JP2000191715A (en) Polyolefin production
US6630550B1 (en) Olefin polymerization catalyst
EP2069372B1 (en) Preparation of diphenyl-bridged substituted cyclopentadienyl-fluorenyl ligands
WO2004046207A2 (en) Polyolefin production
EP2204375A1 (en) Preparation of mono-aryl-substituted methylene-bridged substituted cyclopentadienyl-fluorenyl ligands and zirconium complexes derived thereof

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 09506943

Country of ref document: US

AK Designated states

Kind code of ref document: A1

Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IN IS JP KE KG KP KR KZ LK LR LT LU LV MD MG MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase