WO2021001855A1 - Titre de l'invention : nouveau procédé de synthèse de ligands cyclopentadiényles pontés en c2 et catalyseurs ansa-métallocènes correspondants - Google Patents

Titre de l'invention : nouveau procédé de synthèse de ligands cyclopentadiényles pontés en c2 et catalyseurs ansa-métallocènes correspondants Download PDF

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WO2021001855A1
WO2021001855A1 PCT/IN2020/050581 IN2020050581W WO2021001855A1 WO 2021001855 A1 WO2021001855 A1 WO 2021001855A1 IN 2020050581 W IN2020050581 W IN 2020050581W WO 2021001855 A1 WO2021001855 A1 WO 2021001855A1
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substituted
unsubstituted
bridged
ethylene
ester
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PCT/IN2020/050581
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English (en)
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Soumen Sensarma
Sandip Kumar KUNDU
Sumanta PATSA
Koushik ADHIKARY
Joydeb MANNA
Ranajit Ghosh
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Haldia Petrochemicals Limited
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Priority to CN202080020396.XA priority Critical patent/CN113574060A/zh
Priority to EP20834639.5A priority patent/EP3994144A1/fr
Priority to JP2021561044A priority patent/JP2023520744A/ja
Priority to AU2020300124A priority patent/AU2020300124A1/en
Priority to KR1020217026143A priority patent/KR20220029541A/ko
Publication of WO2021001855A1 publication Critical patent/WO2021001855A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to the development of new process to synthesize C2 bridged metallocene catalyst for the polymerization of ethylene or copolymerization of ethylene or for propylene polymerization. More particularly, the present invention relates to a new, improved and efficient process for synthesizing C2 (ethylene) bridged cyclopentadienyl ligands and eventually forming the corresponding ansa-metallocene catalysts which find potential applications in various olefin polymerization reactions.
  • Metallocene based catalysts for olefin polymerization offers significant advantages over traditional Ziegler- Natta (Z-N) catalysts. Due to their single site characteristics it offers greater co-monomer incorporation (more than 20%) and thus providing products with better flexibility, better film clarity, and improvement in dart and impact properties as compared to the products made from traditional Z-N catalysts. Uniform co-monomer distribution in the polymer backbone leads to sharper and narrow melting point range often require for heat seal packaging applications.
  • Metallocene based catalyst in conjunction with suitable co-catalyst such as methylaluminoxane or MAO (hydrolysis product of TMA and water) or in presence of boron based co-catalyst can produce polymer with improved activity, homogeneous co-monomer distribution in the polymer backbone and better stereo-regulating control.
  • suitable co-catalyst such as methylaluminoxane or MAO (hydrolysis product of TMA and water) or in presence of boron based co-catalyst
  • lithium salts of the indenyl or fluorenyl moieties are reacted with 1,2 dibromoethane (or 2- bromoethane indenyl or fluorenyl) to produce respective ethylene-bridged metallocene precursor:
  • lithium salts of the indenyl or fluorenyl moieties are made to react with ethylene oxide to form 9-hydroxyethylfluorene type moiety which is next reacted with trifluoromethane sulfonic acid anhydride (or p-toluenesulfonyl chloride) to replace the hydroxyl group by OTf (or OTs) group, such that the said OTf (or OTs) derivative being finally reacted with indenyllithium to produce the ethylene-bridged metallocene precursor:
  • the inventors of the current invention have developed a new, improved, economical and efficient route for synthesizing the “final products” so as to overcome the above disadvantages of the prior reported processes; and in order to synthesize ethylene bridged (C2 bridged) ansa metallocene precursors and in turn produce industrially scalable C2 bridged ansa metallocene catalysts thereof with excellent quality and quantity.
  • An object of the invention is to overcome the disadvantages of the prior art.
  • Another object of the present invention is to provide a novel process for the preparation of ethylene bridged (C2 bridged) ansa metallocene precursors (ligands) with 70 to 90 % yield.
  • One aspect of the present invention provides a new, improved process for synthesizing C2 (ethylene) bridged cyclopentadienyl ligand having a general formula I:
  • R1 to R8 is same or different and in each occurrence is independently selected from H, substituted or unsubstituted C1 -C2 alkyl, substituted or unsubstituted C1-C10 alkenyl, substituted or unsubstituted C1-C10 alkynyl, substituted or unsubstituted C1-C12 heterocyclyl, substituted or unsubstituted C1-
  • step (c) adding another substituted or unsubstituted cyclopentadienyl (Cp 2 ) metal salt to the above aldehyde intermediate of step (b) in presence of a saturated cyclic secondary amine, preferably a saturated secondary N-heterocycle catalyst, forming a fulvene derivative; followed by
  • Another aspect of the present invention provides a new, improved process for synthesizing C2 (ethylene) bridged ansa metallocene catalyst comprising the steps of:
  • step (g) adding another substituted or unsubstituted cyclopentadienyl (Cp 2 ) metal salt to the above aldehyde intermediate of step (b), essentially in presence of a saturated cyclic secondary amine, preferably a saturated secondary N-heterocycle catalyst, forming fulvene intermediate;
  • Another aspect of the present invention provides an improved process for synthesizing C2 bridged ansa metallocene catalyst comprising steps of:
  • step (m) adding another substituted or unsubstituted cyclopentadienyl (Cp 2 ) metal salt to the above aldehyde intermediate of step (b) in presence of a saturated cyclic secondary amine, preferably, asaturated secondary N-heterocycle catalyst, forming a fulvene intermediate; followed by
  • ansa metallocene catalyst (n) directly adding a lithiating agent and MCU to the said fulvene intermediate, wherein M is a transition metal preferably selected from Ti, Hf and Zr, preferably Zr, forming an ansa metallocene catalyst.
  • M is a transition metal preferably selected from Ti, Hf and Zr, preferably Zr, forming an ansa metallocene catalyst.
  • R1 to R8 is same or different and in each occurrence is independently selected from H, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C10 alkenyl, substituted or unsubstituted C1-C10 alkynyl, substituted or unsubstituted C1-C12 heterocyclyl, substituted or unsubstituted C1-C12 cycloalkyl, substituted or unsubstituted C1-C12 aromatic ring system, silyl, alkylsilyl; wherein any two consecutive groups among R1 to R8 may be taken together to form a substituted or unsubstituted aromatic, partially saturated or saturated fused ring system with or without a heteroatom selected from N, O, S;
  • M represents a transition metal atom selected from one of the Groups 3 to 12 of the Periodic Table of Elements, preferably, Ti, Zr and Hf;
  • X is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, including that two X's may form a part of an aromatic or non-aromatic fused ring or a ring system;
  • R9 and R10 are same or different and at each occurrence are independently selected from H, Si, alkylsilyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 cycloalkyl, substituted or unsubstituted C1-C10 alkenyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C5-C18 heteroaryl.
  • Figure 1 illustrates 1H NMR data confirming formation of intermediate 2-(9H-Fluoren-9-yl)- propionic acid ethyl ester
  • Figure 2 illustrates 1H NMR data confirming formation of intermediate 2-(9H-Fluoren-9-yl)- propionaldehyde
  • Figure 3 illustrates 1H NMR data confirming formation of intermediate 9-(2-Cyclopenta-2,4- dienylidene-Fmethyl-ethyl)-9F[-fluorene;
  • Figure 4 illustrates 1H NMR data confirming formation of C2 bridged Cp ligand 9-(2- Cyclopenta-1 ,3-dienyl-Fmethyl-ethyl)-9F[-fluorene;
  • Figure 5 illustrates 1H NMR data confirming formation of desired ansa metallocene catalyst i.e. dichloro-[9-(2-cyclopenta-1,3-dien-Fyl-Fmethyl-ethyl)fluoren-9-yl] -methyl zirconium;
  • Figure 6 illustrates 1H NMR data confirming formation of intermediate 2-(9H-Fluoren-9-yl)- butyric acid ethyl ester
  • Figure 7 illustrates 1H NMR data confirming formation of intermediate 2-(9H-fluoren-9-yl)- butyraldehyde
  • Figure 8 illustrates 1H NMR data confirming formation of intermediate 9-(1-Cyclopenta-2,4- dienylidenemethyl-propyl)-9H-fluorene
  • Figure 9 illustrates 1H NMR data confirming formation of Cp ligand 9 -(1-Cyclopenta-2,4- dienylmethyl-propyl)-9H-fluorene;
  • Figure 10 illustrates 1H NMR data confirming formation of ansa metallocene catalyst i.e. dichloro-[9- [1-(cyclopenta-1, 3 -dien-1-ylmethyl)propyl]fluoren-9-yl] -methyl-zirconium
  • ansa metallocene refers to bridged metallocenes, wherein the cyclopentadienyl (Cp) rings are linked by a chemical bridge such as ethylene, propylene etc.
  • C2 bridged ansa metallocene refers to metallocenes wherein the cyclopentadienyl (Cp) rings are linked by essentially an ethylene bridge.
  • improved process refers to a process for the preparation of C2 bridged ansa metallocene precursors and catalysts thereof without formation of any unwanted by-product like spiro-cyclopropane.
  • higher/ superior yield refers to synthesizing C2 bridged ansa metallocene precursors and catalysts thereof with 70 to 85 % yield.
  • THF tetrahydrofuran
  • the term“MAO” is used in the specification is methylaluminoxane.
  • the present invention relates to a new, improved, economical process for the preparation of ethylene (C2) bridged ansa metallocene precursors (A) and catalysts (B) thereof, represented by the general formula (I):
  • R1 to R8 is same or different and in each occurrence is independently selected from H, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C10 alkenyl, substituted or unsubstituted C1-C10 alkynyl, substituted or unsubstituted C1-C12 heterocyclyl, substituted or unsubstituted C1-C12 cycloalkyl, substituted or unsubstituted
  • C1-C12 aromatic ring system silyl, alkylsilyl; wherein any two consecutive groups among R1 to R8 may be taken together to form a substituted or unsubstituted aromatic, partially saturated or saturated fused ring system with or without a heteroatom selected from N, O, S;
  • M represents a transition metal atom selected from one of the Groups 3 to 12 of the
  • Periodic Table of Elements preferably, Ti, Zr and Hf;
  • X is independently selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, including that two X's may form a part of an aromatic or non-aromatic fused ring or a ring system;
  • R9 and R10 are same or different and at each occurrence are independently selected from H, Si, alkylsilyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 cycloalkyl, substituted or unsubstituted C1-C10 alkenyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C5-C18 heteroaryl.
  • An embodiment of the present invention provides a new, improved, economical and easily scalable process for the preparation of C2 bridged ansa metallocene precursor / Cp ligand with 70-90 % yield.
  • each step of the currently developed process for synthesizing C2 bridged ansa metallocene precursor / Cp ligand and the reaction conditions involved have been narrated in details below:
  • a base selected from butyl lithium (BuLi) or potassium tert-butoxide, in an amount of 1-1.2 eqv is added to stirred solutions of a substituted or unsubstituted cyclopentadienyl (Cp 1 ) (leqv.) in a solvent such as THF, at a temperature of about -78°C to 0°C under stirring at RT (room temperature) for lh.
  • a halo-ester selected from bromo-ester or chloro-ester is dissolved in a solvent such as THF and added to the said reaction mixture drop wise at -78°C to 0°C or.
  • reaction mixture is stirred for around 16-18 hrs at room temperature (RT).
  • RT room temperature
  • reaction mixture is quenched with ammonium chloride (NH 4 C1) solution and extracted with ethyl acetate.
  • the organic layer is washed with brine, dried over sodium sulphate and evaporated.
  • the resulting crude is purified by column chromatography (0- 10% ethyl acetate/hexane) in order to achieve the desired ester intermediate (X) with 75-85% yield.
  • reducing agents selected from diisobutylaluminium hydride (DIBALH)in an amount of 1-1.2 eqv, 25% in toluene is added to stirred solutions of esters (1 eqv) in solvents like DCM or toluene at -78°C and stirred for lh at -78°C. Reactions are quenched with methanol (MeOH) and extracted with DCM . The organic layer is washed with water and brine. The organic layer is next dried over sodium sulphate and evaporated to get the desired aldehyde with 80-90% yield. This aldehyde intermediate (Y) thus formed is used in the next step (c) without further purification.
  • Cp 2 another prior substituted or unsubstituted cyclopentadiene (Cp 2 ) (1-3 eqv.) is added to the stirred solution of the aldehyde (1 eqv) in methanol (MeOH) at 0-5°C and stirred for 5 minute at this temperature with a saturated cyclic secondary amine, preferably a saturated secondary N-heterocycle as catalyst selected from Pyrrolidine, Piperidine, Morpholine (0.02 to 0.05 eqv) is added to the reaction mixture at 0-5°C. The reaction mixture is allowed to warm to RT and stirred for another 3-12 hrs.
  • a saturated cyclic secondary amine preferably a saturated secondary N-heterocycle as catalyst selected from Pyrrolidine, Piperidine, Morpholine (0.02 to 0.05 eqv) is added to the reaction mixture at 0-5°C.
  • the reaction mixture is allowed to warm to RT and stirred for another 3-12 hrs.
  • LAH lithum aluminium hydride
  • cyclopentadienyl (Cp) moieties as used in the present invention is selected from cyclopentadiene, fluorene, indene.
  • Another embodiment of the present invention provides a process for preparing a C2 bridged ansa metallocene catalyst comprising the steps of:
  • the formed metallocene complex is then further analyzed by NMR and other elemental analytical.
  • Another specific embodiment of the present invention thus provides a process for preparing a C2 bridged ansa metallocene catalyst comprising the steps of:
  • Another embodiment of the present invention provides a process for preparing a C2 bridged ansa metallocene catalyst comprising the steps of:
  • Another specific embodiment of the present invention thus provides a process for preparing a C2 bridged ansa metallocene catalyst comprising the steps of:
  • step (iv) passing the said suspension of step (iv) through celite and washing the remaining solid fraction with toluene ; followed by
  • Example 1 illustrates the process for preparing Dichloro-[9-[1-(cyclopenta-1,3-dien-1- ylmethyl)propyl]fluoren-9-yl] -methyl-zirconium ansa metallocene catalyst.
  • the accompanying figure 1 shows 1 H NMR (CDC1 3 ) study results: 7.74 (d, 2H), 7.49 (d, 1H), 7.37-7.25 (m, 5H) 4.53 (s, 1H), 4.31 (d, 2H), 3.28 (m, 1H), 1.34-1.30 (t, 3H), 0.63 (d, 3H), confirming formation of pure compound 2-(9H-Fluoren-9-yl)-propionic acid ethyl ester.
  • Example 2 illustrates the process for utilizing the said ansa metallocene catalyst of example 1 i.e. Dichloro-[9- [1 -( cyclopenta- 1, 3 -dien-1-ylmethyl)propyl]fluoren-9-yl] -methyl-zirconium in polymerization of ethylene.
  • a dried 600 mL stainless steel parr reactor equipped with a mechanical stirrer, thermometer probe are backfilled with nitrogen for 30 min.
  • Dried hexane is introduced to the reaction flask, followed by 1 mL of MAO, and nitrogen is bubbled through the solvent for 10 min under stirring at 400 rpm.
  • the nitrogen is then replaced by ethylene gas, which is left bubbling through the solvent and released it through vent.
  • the desired amount of MAO (5 mL) and 6 mg of ansa metallocene catalyst of example 1 i.e.
  • Example 3 illustrates the process for utilizing the said ansa metallocene catalyst of example 1 i.e. Dichloro-[9- [1-(cyclopenta-1, 3 -dien-1-ylmethyl)propyl]fluoren-9-yl] -methyl-zirconium in copolymerization of ethylene/l-hexene.
  • a dried 600 ml stainless steel parr reactor equipped with a mechanical stirrer, thermometer probe are backfilled with nitrogen for 30 min.
  • Dried hexane is introduced to the reaction flask, followed by 1 ml of MAO, and nitrogen is bubbled through the solvent for 10 min under stirring at 400 rpm.
  • the nitrogen is then replaced by ethylene gas, which is left bubbling through the solvent and released it through vent.
  • Dichloro-[9-[1-(cyclopenta-1,3-dien-1- ylmethyl)propyl]fluoren-9-yl]-methyl-zirconium in toluene are introduced into the reaction flask; and then placed at 70°C temperature. When the requisite temperature is reached, then 2.5 ml of 1-hexene and subsequently ethylene are fed with the pressure adjusted at the constant ethylene pressure of 5 bars. Polymerization reaction is allowed to proceed for 15 min and then quenched with 10 ml of methanol. The reactor is vented, and the polymers are collected and precipitated into acidified methanol (5% HC1). Polymers are washed with methanol and water and dried in a vacuum oven at 60 °C for overnight to get 1.2 gm of polymer.
  • Example 4 illustrates the process for preparing Dichloro-[9-[1-(cyclopenta-1,3-dien-1- ylmethyl)propyl]fluoren-9-yl] -methyl-zirconium ansa metallocene catalyst.
  • reaction mixture is allowed to warm to 25 °C and stirred for another 2h, excess pyrrolidine is quenched with acetic acid.
  • Methanol is concentrated, diluted with ethyl acetate (70 ml) and washed with water (2x50 ml) and brine (2x50 ml).
  • the organic layer is separated, dried over sodium sulphate and concentrated under reduced pressure to get the crude material.
  • the resulting crude material is purified by flash column chromatography (hexane) to get the desired fulvene intermediate 9-(1 -Cyclopenta-2, 4-dicnylidcncmcthyl -propyl )-9H-Fluorene as light yellow liquid with 86% yield.
  • the accompanying figure 8 shows 1 H NMR (CDC1 3 ) study results: 7.75 (q, 2H), 7.61 (d, 1H), 7.55 (d, 1H), 7.40 (t,1H), 7.32 (t,1H), 7.24 (t, 1H), 6.53 (d,2H), 6.41 (d,1H), 6.21 (d,1H), 6.10 (d, 1H), 4.19 (s, 1H), 3.49-3.42 (m, 1H), 1.44-1.25 (m, 2H), 0.82 (t, 3H), confirming formation of the fulvene intermediate 9-(1-Cyclopenta-2,4-dienylidenemethyl-propyl)-9H-fluorene.
  • Example 5 illustrates the process for utilizing the said ansa metallocene catalyst of example 4 i.e. dichloro-[9- [1-(cyclopenta-1, 3 -dien-1-ylmethyl)propyl]fluoren-9-yl] -methyl-zirconium in polymerization of ethylene.
  • a dried 600 ml stainless steel parr reactor equipped with a mechanical stirrer, thermometer probe are backfilled with nitrogen for 30 min.
  • Dried hexane is introduced to the reaction flask, followed by 1 ml of MAO, and nitrogen is bubbled through the solvent for 10 min under stirring at 400 rpm.
  • the nitrogen is then replaced by ethylene gas, which is left bubbling through the solvent and released it through vent.
  • Example 6 provides a comparative data of the present invention in view of the closest reported prior art.

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Abstract

La présente invention concerne un nouveau procédé amélioré et efficace permettant la synthèse d'un ligand cyclopentadiényle ponté en C2 (éthylène) représenté par la formule I : et éventuellement la formation du catalyseur ansa-métallocène correspondant à partir de celui-ci ; qui trouvent des applications potentielles dans diverses réactions de polymérisation/co-polymérisation d'oléfines.
PCT/IN2020/050581 2019-07-04 2020-07-03 Titre de l'invention : nouveau procédé de synthèse de ligands cyclopentadiényles pontés en c2 et catalyseurs ansa-métallocènes correspondants WO2021001855A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN202080020396.XA CN113574060A (zh) 2019-07-04 2020-07-03 合成c2桥连环戊二烯基配体和相应柄型茂金属催化剂的新方法
EP20834639.5A EP3994144A1 (fr) 2019-07-04 2020-07-03 Nouveau procédé de synthèse de ligands cyclopentadiényles pontés en c2 et catalyseurs ansa-métallocènes correspondants
JP2021561044A JP2023520744A (ja) 2019-07-04 2020-07-03 Ｃ２架橋シクロペンタジエニル配位子を合成するための新しいプロセス及び対応するａｎｓａ－メタロセン触媒
AU2020300124A AU2020300124A1 (en) 2019-07-04 2020-07-03 Title of the invention:a new process for synthesizing C2 bridged cyclopentadienyl ligands and corresponding ansa-metallocene catalysts
KR1020217026143A KR20220029541A (ko) 2019-07-04 2020-07-03 C2 가교된 사이클로펜타다이에닐 리간드 및 상응하는 안사-메탈로센 촉매의 새로운 합성 공정

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995032979A1 (fr) * 1994-06-01 1995-12-07 University Of Iowa Research Foundation Nouvelle synthese de catalyseurs constituee d'alliages organometalliques en anse
IN305684B (fr) * 2011-10-06 2019-01-15

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995032979A1 (fr) * 1994-06-01 1995-12-07 University Of Iowa Research Foundation Nouvelle synthese de catalyseurs constituee d'alliages organometalliques en anse
IN305684B (fr) * 2011-10-06 2019-01-15

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KR20220029541A (ko) 2022-03-08
JP2023520744A (ja) 2023-05-19
AU2020300124A1 (en) 2021-08-26
EP3994144A1 (fr) 2022-05-11

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