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US6291609B1 Expired / Lapsed US ⏱️ 0.0 years remaining

High temperature olefin polymerization process

Assignee: ExxonMobil Chemical Patents Inc
•
Filing: 1999-03-03
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Granted: 2001-09-18
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Expires: 2019-03-03
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Abstract

Abstract The invention is directed to olefin polymerization processes using bridged hafnocene catalyst complexes comprising highly substituted noncoordinating anions that are surprisingly stable under high temperature olefin polymerization processes such that olefin copolymers having significant amount of incorporated comonomer can be prepared with high molecular weights. More specifically, the invention is a polymerization process for ethylene copolymers having a melt index of about 0.87 to about 0.930 comprising contacting, under homogeneous polymerization conditions at a reaction temperature at or above 140° C. to 225° C., ethylene and one or more comonomers capable of insertion polymerization with a bridged hafnocene catalyst complex derived from A) a biscyclopentadienyl hafnium organometallic compound having i) at least one unsubstituted cyclopentadienyl ligand or aromatic fused-ring substituted cyclopentadienyl ligand, ii) one aromatic fused-ring substituted cyclopentadienyl ligand, iii) and a covalent bridge connecting the two cyclopentadienyl ligands, said bridge comprising a single carbon or silicon atom; and B) an activating cocatalyst, precursor ionic compound comprising a halogenated tetraaryl-substituted Group 13 anion wherein each aryl substituent contains at least two cyclic aromatic rings.

Inventors

  • 👤 Donna J. Crowther
  • 👤 Bernard J. Folie
  • 👤 John F. Walzer, Jr.
  • 👤 Rinaldo S. Schiffino

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-08 08:16
CPC Classifications
C; C08; C08F; C08F10/00; C08F210/00; C08F210/16; C08F210/18; C08L; C08L23/00; C08L23/02; C08L23/10; C08L23/14; C08L23/142; C08L23/16; C08F210/04; C08F210/06; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08F4/65912; C08F4/6592; C08F4/65922; C08F4/65927; C08L2205/00; C08L2205/02; C08L2205/025; C08L2308/00; C08L2312/00; C08L2314/00; C08L2314/06; Y; Y10; Y10S; Y10S526/00; Y10S526/916; Y10S526/943

Claims Analysis

Total Claims: 22
Claim 1
Independent Claim 121 words
A polymerization process for ethylene copolymers having a density of about 0.87 to about 0.93 comprising contacting, under homogeneous polymerization conditions at a reaction temperature at or above 140° C. to 220° C., ethylene and one or more comonomers capable of insertion polymerization with a hafnocene catalyst complex derived from: (A) a biscyclopentadienyl hafnium organometallic compound having: (i) one unsubstituted cyclopentadienyl ligand and one aromatic fused-ring substituted cyclopentadienyl ligand, or two aromatic fused-ring substituted cyclopentadienyl ligands; and (ii) a covalent bridge connecting the two cyclopentadienyl ligands, said bridge comprising a single carbon or silicon atom; and (B) an activating cocatalyst precursor ionic compound comprising a halogenated tetraaryl-substituted Group 13 anion wherein each aryl substituent contains at least two cyclic aromatic rings.
Claim 2
Dependent Claim 121 words
A polymerization process for ethylene copolymers having a density of about 0.87 to about 0.93 comprising contacting, under homogeneous polymerization conditions at a reaction temperature at or above 140° C. to 220° C., ethylene and one or more comonomers capable of insertion polymerization with a hafnocene catalyst complex derived from: (A) a biscyclopentadienyl hafnium organometallic compound having: (i) one unsubstituted cyclopentadienyl ligand and one aromatic fused-ring substituted cyclopentadienyl ligand, or two aromatic fused-ring substituted cyclopentadienyl ligands; and (ii) a covalent bridge connecting the two cyclopentadienyl ligands, said bridge comprising a single carbon or silicon atom; and (B) an activating cocatalyst precursor ionic compound comprising a halogenated tetraaryl-substituted Group 13 anion wherein each aryl substituent contains at least two cyclic aromatic rings.
Claim 3
Dependent Claim 18 words
The process of claim 1 wherein said hafnium compound has at least one substituted or unsubstituted fluorenyl ligand.
Claim 4
Dependent Claim 23 words
The process of claim 2 wherein said hafnium compound is covalently bridged between the biscyclopentadienyl ligands with a substituted or unsubstituted carbon atom.
Claim 5
Dependent Claim 17 words
The process of claim 3 wherein said carbon atom is substituted with at least one aryl group.
Claim 6
Dependent Claim 33 words
The process of claim 4 wherein said hafnium compound is selected from the group consisting of diphenyl methylene (cyclopentadienyl)(9-fluorenyl) hafnium dimethyl, diphenyl methylene (cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) hafnium dimethyl and diphenyl methylene (cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl) hafnium dimethyl.
Claim 7
Dependent Claim 21 words
The process of claim 2 wherein said hafnium compound is covalently bridged between the biscyclopentadienyl ligands with a substituted silicon atom.
Claim 8
Dependent Claim 37 words
The process of claim 6 wherein said substituted silicon is substituted with hydrocarbyl substituent groups having from one to twenty carbon atoms or wherein said substituents are covalently connected such as to form a cyclic substituent group.
Claim 9
Dependent Claim 24 words
The process of claim 1 wherein the aryl groups of said halogenated tetraaryl Group 13 anion comprise at least one fused polycyclic aromatic ring.
Claim 10
Dependent Claim 20 words
The process of claim 8 wherein the at least one fused polycyclic aromatic ring contains at least three fluorine substituents.
Claim 11
Dependent Claim 14 words
The process of claim 9 wherein said halogenated tetraaryl Group 13 anion is [tetrakis(perfluoronaphthyl)borate].
Claim 12
Dependent Claim 31 words
The process of claim 1 wherein the aryl groups of said halogenated tetraaryl Group 13 anion comprise at least one aromatic ring pendant in the 4 position to a phenyl ligand.
Claim 13
Dependent Claim 14 words
The process of claim 11 wherein said halogenated tetraaryl Group 13 anion is [tetrakis(perfluoro-4-biphenyl)borate].
Claim 14
Dependent Claim 24 words
The process of claim 8 wherein said cocatalyst precursor ionic compound comprises a cationic complex selected from anilinium, ammonium, carbenium and silylium cationic complexes.
Claim 15
Dependent Claim 24 words
The process of claim 10 wherein said cocatalyst precursor ionic compound comprises a cationic complex selected from anilinium, ammonium, carbenium and silylium cationic complexes.
Claim 16
Dependent Claim 24 words
The process of claim 11 wherein said cocatalyst precursor ionic compound comprises a cationic complex selected from anilinium, ammonium, carbenium and silylium cationic complexes.
Claim 17
Dependent Claim 24 words
The process of claim 12 wherein said cocatalyst precursor ionic compound comprises a cationic complex selected from anilinium, ammonium, carbenium and silylium cationic complexes.
Claim 18
Dependent Claim 18 words
The process of claim 1 wherein said homogeneous polymerization conditions are adiabatically conducted in a continuous polymerization process.
Claim 19
Dependent Claim 19 words
The process of claim 17 wherein the reaction temperature is in a range of 160° C. to 200° C.
Claim 20
Dependent Claim 24 words
The process of claim 18 wherein said homogeneous polymerization conditions are conducted in a continuous process at a pressure of at least 500 bar.
Claim 21
Dependent Claim 26 words
The process of claim 17 wherein said one or more comonomers capable of insertion polymerization are selected from the group consisting of 1-butene, 1-hexene, and 1-octene.
Claim 22
Dependent Claim 26 words
The process of claim 19 wherein said one or more comonomers capable of insertion polymerization are selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 2004-09-17 2005-03-19 2005-09-18 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 2008-09-17 2009-03-19 2009-09-18 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2012-09-17 2013-03-19 2013-09-18 $7700.00 Window Closed / Lapsed

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