WO1999007716A1 - Nouveaux complexes de metaux de transition - Google Patents

Nouveaux complexes de metaux de transition Download PDF

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Publication number
WO1999007716A1
WO1999007716A1 PCT/GB1998/002335 GB9802335W WO9907716A1 WO 1999007716 A1 WO1999007716 A1 WO 1999007716A1 GB 9802335 W GB9802335 W GB 9802335W WO 9907716 A1 WO9907716 A1 WO 9907716A1
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WO
WIPO (PCT)
Prior art keywords
transition metal
pentalene
catalyst composition
cyclopentadienyl
composition according
Prior art date
Application number
PCT/GB1998/002335
Other languages
English (en)
Inventor
Frederick Geoffrey Nethersole Cloke
Julian Stephen Parry
Original Assignee
Bp Chemicals Limited
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 Bp Chemicals Limited filed Critical Bp Chemicals Limited
Priority to EP98937653A priority Critical patent/EP1003755A1/fr
Priority to AU86377/98A priority patent/AU8637798A/en
Publication of WO1999007716A1 publication Critical patent/WO1999007716A1/fr

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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
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the present invention relates to novel transition metal complexes and in particular to novel transition metal complexes comprising pentalene ligands and to their use as catalyst components for the polymerisation of olefins.
  • metallocene based olefin polymerisation catalysts are now well established. Examples of such catalysts may be found in EP 129368, EP 206794 and EP 260130.
  • the catalyst compositions comprise a metallocene complex for example a bis(cyclopentadienyl) zirconium dichloride together with an activator for example methyl aluminoxane.
  • a metallocene complex for example a bis(cyclopentadienyl) zirconium dichloride together with an activator for example methyl aluminoxane.
  • transition metal complex having a constrained geometry configuration has been used for the polymerisation of olefins. Examples of these complexes may be found in EP 420436 and EP 416815.
  • Such contrained geometry complexes may also be used in the presence of aluminoxanes but may also be used together with boron activators.
  • transition metal complex suitable for use as a catalyst component is described in EP 672672.
  • the complexes described therein comprise cyclooctatetraene ligands and may also be used for the polymerisation of olefins.
  • transition metal complexes comprise at least one cyclopentadienyl ligand together with the transition metal
  • transition metal complexes comprise at least one cyclopentadienyl ligand together with the transition metal
  • a novel class of transition metal complex comprising a pentalene ligand which may be used as a catalyst component for the polymerisation of olefins.
  • M is a Group IVA transition metal (Cotton and Wilkinson 2 n ⁇ Edition)
  • X is an anionic ligand
  • L is a neutral donor eg THF, amine and L, X or Y may be connected to the pentalene ligand,
  • Preferred complexes are those wherein y is 1 , M is zirconium or titanium, X is halogen and Y is cyclopentadienyl.
  • Suitable X ligands include hydride, halogen, alkyl, aryl or oxygen or nitrogen containing ligands.
  • the cyclopentadienyl ligand Y when present may be substituted with alkyl. Alternatively two substituents may be joined together to form a ring eg indenyl.
  • the pentalene ligand When substituted the pentalene ligand is most suitably substituted in the 1,5- position for example with trimethylsilyl groups.
  • X, Y or L group When a X, Y or L group is connected to the pentalene ligand it may be bridged via the group (J 2 Z) n wherein Z is carbon, silicon, germanium or boron and J is hydrogen or hydrocarbyl and n is 1-8.
  • Preferred complexes are:
  • the complexes When used as components of catalyst compositions for the polymerisation of olefins the complexes are used in the presence of a suitable activator.
  • a catalyst composition suitable for the polymerisation of olefins comprising:
  • the preferred activator is an organoaluminium oxy compound for example an aluminoxane.
  • a most preferred activator is methyl aluminoxane.
  • boron activators may also be suitable for use in the catalyst compositions according to the present invention for example boron compounds.
  • Suitable boron activators include tris(pentafluorophenyl) boron or trialkylammonium tetrakis (pentafluorophenyl) borates or N,N-dialkylanilinium tetrakis (pentafluorophenyl) borates.
  • the molar ratio of transition metal to activator is in the range 1 :0.1 to 1 : 10,000 and most preferably in the range 1 : 1 to 1 :2,000.
  • the catalyst compositions according to the present invention may also be used in the supported form.
  • Typical supports include inorganic oxides for example silica, alumina.
  • Other supports include magnesium chloride or polyethylene.
  • the catalyst composition may be prepared by conventional means.
  • novel transition metal complexes according to the present invention may be prepared for example from cyclooctatetraene. Full experimental details of the preparation are given in the accompanying examples.
  • the present invention also provides a process for the production of polyolefins, in particular homopolymers of ethylene and copolymers of ethylene with minor amounts of at least one C3 to CIO, preferably C3 to C8 alpha-olefin.
  • the process comprises contacting the monomer or monomers, optionally in the presence of hydrogen, with the catalyst composition according to the invention at a temperature and pressure sufficient to initiate the polymerisation reaction.
  • the alpha olefin may be propylene, butene-1, hexene-1, 4-methyl pentene-1 and octene-1.
  • the olefin polymerisation catalyst compositions according to the present invention may be used to produce polymers using solution polymerisation, slurry polymerisation or gas phase polymerisation techniques. Methods and apparatus for effecting such polymerisation reactions are well known and described in, for example, Encyclopaedia of Polymer Science and Engineering published by John Wiley and Sons, 1987, Volume 7, pages 480 to 488 and 1988, Volume 12, pages 504 to 541.
  • the catalysts of the present invention are particularly suitable for use in the gas phase.
  • the catalyst according to the present invention can be used in similar amounts and under similar conditions to known olefin polymerisation catalysts.
  • the polymerisation may optionally be carried out in the presence of hydrogen.
  • Hydrogen or other suitable chain transfer agents may be used to control the molecular weight of the produced polyolefin.
  • Ethylene was polymerised in toluene at 10 bar and at room temperature in the presence of an aliquot (20 mg) of [Zr ⁇ C 8 H 4 (Si'Pr 3 -l,5) 2 ⁇ 2 ] prepared in
  • Example 2 and 1000 equivalents of methyl aluminoxane. The reaction proceeded exothermically (up to 50°C) and 2.5 gm polyethylene were produced after 1 hr.
  • Silica (lg, Crosfield ES70, calcined at 700°C under flowing N 2 ) was placed in a Schlenk tube. To this was added a solution of MAO (5.7ml of 1.5M MAO in toluene) and Pentalene(TMS) 2 cyclopentadienyl zirconium chloride (20mg) in toluene (10ml). The slurry was allowed to stand with occassional shaking for 90 minutes at room temperature. The catalyst was dried under vacuum at room temperature. Polymerisations
  • the reagents used in the polymerisations were Ethylene Grade 3.5 (Supplied by Air Products), 1-hexene (Supplied by Aldrich) distilled over sodium/nitrogen, trimethylaluminium (2M in hexanes, Supplied by Aldrich) and triisobutylauminium (1M in hexanes, Supplied by Aldrich).
  • a 3 litre reactor was heated under flowing nitrogen for 1 hour at 77°C before sodium chloride (300g, predried under vacuum, 160°C, >4 hours) was added.
  • Trimethyl aluminium (3ml, 2M in hexanes) was added to the reactor and allowed to scavenge the reactor of poisons for V ⁇ hour. After this period of time the alkyl aluminium was vented from the reactor using 4*4 bar nitrogen purges.
  • the gas phase was composed with 0.1 bar 1-hexene and 8 bar ethylene at 77°C prior to catalyst injection. After the catalyst (0.203g) prepared in Example 5 had been injected, under nitrogen the temperature was adjusted to 80°C. The ratio of hexene to ethylene during the polymerisation was keep constant by monitoring the gas phase composition by mass spectrometer and adjusting the flow rate of 1- hexene as required via a HPLC pump.
  • the polymerisation was allowed to continue for 1 hour before being terminated by purging the reactants from the reactor with nitrogen and reducing the temperature to ⁇ 30°C.
  • the polymer was washed with water to remove the sodium chloride, then with acidified methanol (50ml HC1/2.5L methanol) and finally with water/ethanol (4: 1 v/v).
  • the polymer was dried under vacuum, at 40°C, for 16 hours.
  • a 3 litre reactor was heated under flowing nitrogen for 1 hour at 78°C before sodium chloride (300g, predried under vacuum, 160°C, >4 hours) was added.
  • Trimethyl aluminium (3ml, 2M in hexanes) was added to the reactor and allowed to scavenge the reactor of poisons for 1 ' _ hours. After this period of time the alkyl aluminium was vented from the reactor using 4*4 bar nitrogen purges.
  • the gas phase was composed with 0.1 bar 1 -hexene and 8 bar ethylene at 78°C prior to catalyst injection. After the catalyst (0.23g) prepared in Example 6 had been injected, under nitrogen the temperature was adjusted to 80°C. The ratio of hexene to ethylene during the polymerisation was keep constant by monitoring the gas phase composition by mass spectrometer and adjusting the flow rate of 1- hexene as required via a HPLC pump.
  • the polymerisation was allowed to continue for 1 hour before being terminated by purging the reactants from the reactor with nitrogen and reducing the temperature to ⁇ 30°C.
  • the polymer was washed with water to remove the sodium chloride, then with acidified methanol (50ml HC1/2 5L methanol) and finally with water/ethanol (4: 1 v/v).
  • the polymer was dried under vacuum, at 40°C, for 16 hours.
  • a 3 litre reactor was heated under flowing nitrogen for 1 hour at 78°C before sodium chloride (300g, predried under vacuum, 160°C, >4 hours) was added.
  • Trimethyl aluminium (4ml, 2M in hexanes) was added to the reactor and allowed to scavenge the reactor of poisons for lhour. After this period of time the alkyl aluminium was Vented from the reactor using 4*4 bar nitrogen purges.
  • the reactor was cooled to below 30°C and trimethyl aluminium (2ml of 2M in hexanes) was added to the reactor.
  • the reactor was heated to 78°C and the gas phase composed 0.1 bar 1 -hexene and 8 bar ethylene at 78°C prior to catalyst injection.
  • the catalyst (0.173g) prepared in Example 6 had been injected, under nitrogen the temperature was adjusted to 80°C.
  • the ratio of hexene to ethylene during the polymerisation was keep constant by monitoring the gas phase composition by mass spectrometer and adjusting the flow rate of 1 -hexene as required via a HPLC pump.
  • the polymerisation was allowed to continue for 1 hour before being terminated by purging the reactants from the reactor with nitrogen and reducing the temperature to ⁇ 30°C.
  • the polymer was washed with water to remove the sodium chloride, then with acidified methanol (50ml HC1/2.5L methanol) and finally with water/ethanol (4: 1 v/v).
  • the polymer was dried under vacuum, at 40°C, for 16 hours.
  • a 3 litre reactor was heated under flowing nitrogen for 1 hour at 78°C before sodium chloride (300g, predried under vacuum, 160°C, >4 hours) was added.
  • Trimethyl aluminium (4ml, 2M in hexanes) was added to the reactor and allowed to scavenge the reactor of poisons for lhour. After this period of time the alkyl aluminium was vented from the reactor using 4*4 bar nitrogen purges.
  • the reactor was cooled to below 30°C and triisobutyl aluminium (2ml of 1M in hexanes) was added to the reactor.
  • the reactor was heated to 78°C and the gas phase composed 0.1 bar 1 -hexene and 8 bar ethylene at 78°C prior to catalyst injection.
  • the catalyst 0.220g prepared in Example 6 had been injected, under nitrogen the temperature was adjusted to 80°C.
  • the ratio of hexene to ethylene during the polymerisation was keep constant by monitoring the gas phase composition by mass spectrometer and adjusting the flow rate of 1 -hexene as required via a HPLC pump.
  • the polymerisation was allowed to continue for 1 hour before being terminated by purging the reactants from the reactor with nitrogen and reducing the temperature to ⁇ 30°C.
  • the polymer was washed with water to remove the sodium chloride, then with acidified methanol (50ml HC1/2.5L methanol) and finally with water/ethanol (4: 1 v/v).
  • the polymer was dried under vacuum, at 40°C, for 16 hours.
  • the weight of polymer was 7.3g
  • Examples 11-17 were carried out in a 1 litre capacity autoclave using isobutane as the reaction medium.
  • the reactor was heated to 85°C and thoroughly purged with nitrogen (2l/min) for 90 min. The temperature was then reduced to 50°C and the reactor charged with the chosen alkylaluminium scavenger and isobutane (500ml). The mixture was stirred (200rpm) at 75°C for a minimum of 120 min, the temperature was varied to the subsequent polymerisation temperature (T) and 10 bar overpressure of ethylene was then added.
  • the metal complex (see belov ) and MAO were mixed together and then added to the reactor. Ethylene was added to maintain constant reactor pressure for the duration of the run.
  • the metal complexes were (cyclopentadienyl) (1,5 -d i(trimethylsilyl) pentalene) zirconium chloride or the titanium analogue or (pentamethyl cyclopentadienyl) zirconium (l,5-di(trimethylsilyl) pentalene) zirconium chloride.

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  • 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)

Abstract

L'invention concerne de nouveaux complexes de métaux de transition comprenant des ligands pentalène. Ces complexes conviennent à la polymérisation d'oléfines en présence d'activateurs adéquats. Des exemples caractéristiques de ces complexes sont: (I) ou (II).
PCT/GB1998/002335 1997-08-07 1998-08-04 Nouveaux complexes de metaux de transition WO1999007716A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98937653A EP1003755A1 (fr) 1997-08-07 1998-08-04 Nouveaux complexes de metaux de transition
AU86377/98A AU8637798A (en) 1997-08-07 1998-08-04 Novel transition metal complexes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9716653.2 1997-08-07
GBGB9716653.2A GB9716653D0 (en) 1997-08-07 1997-08-07 Novel transition metal complexes

Publications (1)

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WO1999007716A1 true WO1999007716A1 (fr) 1999-02-18

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EP (1) EP1003755A1 (fr)
AU (1) AU8637798A (fr)
GB (1) GB9716653D0 (fr)
WO (1) WO1999007716A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110774A2 (fr) * 2007-03-09 2008-09-18 Isis Innovation Limited Pentalènes
WO2017060689A1 (fr) * 2015-10-06 2017-04-13 Scg Chemicals Co., Ltd. Catalyseur comprenant des ligands de type perméthylpentalène
CN108137636A (zh) * 2015-10-06 2018-06-08 Scg化学有限公司 复合物及其在烯烃聚合中的应用
US11053269B2 (en) 2016-05-12 2021-07-06 Scg Chemicals Co., Ltd. Unsymmetrical metallocene catalysts and uses thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0673946A2 (fr) * 1994-03-22 1995-09-27 PCD-Polymere Gesellschaft m.b.H. Metallocènes et leur application dans le polymérisation d'oléfines
EP0749985A2 (fr) * 1995-06-19 1996-12-27 Hoechst Aktiengesellschaft Composés de métallocène stéréo rigides
DE19642432A1 (de) * 1996-10-15 1998-04-16 Hoechst Ag Stereorigide Metallocenverbindung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0673946A2 (fr) * 1994-03-22 1995-09-27 PCD-Polymere Gesellschaft m.b.H. Metallocènes et leur application dans le polymérisation d'oléfines
EP0749985A2 (fr) * 1995-06-19 1996-12-27 Hoechst Aktiengesellschaft Composés de métallocène stéréo rigides
DE19642432A1 (de) * 1996-10-15 1998-04-16 Hoechst Ag Stereorigide Metallocenverbindung

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 128, no. 20, 18 May 1998, Columbus, Ohio, US; abstract no. 244149, GABOR, BARBARA ET AL: "Bis(.eta.3-allyl)(.eta.8-pentalene)zirconium: preparation, structure and structural dynamics" XP002084994 *
INORG. CHIM. ACTA (1998), 270(1,2), 555-558 CODEN: ICHAA3;ISSN: 0020-1693, 1998 *
JONAS, KLAUS ET AL: "Mononuclear pentalene and methylpentalene complexes of titanium, zirconium, and hafnium", ANGEW. CHEM., INT. ED. ENGL. (1997), 36(16), 1714-1718 CODEN: ACIEAY;ISSN: 0570-0833, 1997, XP002085019 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008110774A2 (fr) * 2007-03-09 2008-09-18 Isis Innovation Limited Pentalènes
WO2008110774A3 (fr) * 2007-03-09 2009-03-05 Isis Innovation Pentalènes
US8716456B2 (en) 2007-03-09 2014-05-06 Isis Innovation Limited Pentalenes
WO2017060689A1 (fr) * 2015-10-06 2017-04-13 Scg Chemicals Co., Ltd. Catalyseur comprenant des ligands de type perméthylpentalène
CN108137740A (zh) * 2015-10-06 2018-06-08 Scg化学有限公司 包含全甲基并环戊二烯配体的催化剂
CN108137636A (zh) * 2015-10-06 2018-06-08 Scg化学有限公司 复合物及其在烯烃聚合中的应用
JP2018535945A (ja) * 2015-10-06 2018-12-06 エスシージー ケミカルズ カンパニー，リミテッド 錯体およびオレフィン重合のためのその使用
US10888854B2 (en) 2015-10-06 2021-01-12 Oxford University Innovation Limited Catalyst comprising permethylpentalene ligands
US11053269B2 (en) 2016-05-12 2021-07-06 Scg Chemicals Co., Ltd. Unsymmetrical metallocene catalysts and uses thereof

Also Published As

Publication number Publication date
EP1003755A1 (fr) 2000-05-31
AU8637798A (en) 1999-03-01
GB9716653D0 (en) 1997-10-15

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