WO1997046567A1 - Novel group iv metal complexes - Google Patents
Novel group iv metal complexes Download PDFInfo
- Publication number
- WO1997046567A1 WO1997046567A1 PCT/GB1997/001519 GB9701519W WO9746567A1 WO 1997046567 A1 WO1997046567 A1 WO 1997046567A1 GB 9701519 W GB9701519 W GB 9701519W WO 9746567 A1 WO9746567 A1 WO 9746567A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- complex
- catalyst
- polymerisation
- composition according
- olefins
- Prior art date
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
- 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
-
- 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
Definitions
- the present invention i elates to novel cyclooctatetraendiyl complexes of Group IV metals and to then use as olefin polymerisation catalysts
- Tiaditional olet ⁇ n polvmensation catalysts have been based on transition metal salts of Gt oup I V to VI I metals in combination with base metal alkyls of S Group 1 to III metals
- Such catalysts known as Ziegler-Natta catalysts have been used to poiymense olefins m solution, slurry and gas phase processes
- Another catalyst system used toi polymensation of olefins is based on chromium oxide and is often referred to as Phillips-type catalyst system
- Catalysts based on metalloce e complexes have also been widely used for 0 the polymerisation oi olefins These complexes are used in catalyst systems comprising a b ⁇ s(c ⁇ cl ⁇ pe ⁇ tad ⁇ enyl) transition metal and a cocatalyst
- bis (Cp) systems may be supported on silica
- complexes having a single cyclopentadienvl ring ligand and a hetero atom bonded to the metal atom may also be used in conjunction with aluminoxanes
- Similari catalyst systems ai e taught in EP 418044 and WO 92/00333 but which have a non-cooi d ating anion as the activating cocatalyst
- the catalyst is pi epared as the pi oduct of a mono(cyclopentad ⁇ enyl) heteroatom metal complex and an ionic activatoi compound and such systems have been referred to as ionic mono(cyclopentad ⁇ enyl) catalysts
- Typical ionic activators for S such systems may be exemplified by boi ates oi boranes More recently EP 6726
- bridged complexes comprising the cyclooctatetraendiyl ligand may be prepared and have been found to be particularly suitable as components of catalyst systems useful for the polymerisation of olefins.
- a complex suitable for use in a catah st system for the polymerisation of olefins comprising a transition metal complex having formula I
- M is zirconium, hafnium oi titanium
- Y is an aniomc ligand foi example halide oi hydride or a hydrocarbyl group having from I to 20 carbon atoms and
- the cyclopentadienyl I ing may optionally be substituted for example by alkyl groups or by sustituents which form a condensed ring e g indenyl Examples of silyl substituents ai e dialkysilyl or trialkylsilyl
- the cyclooctateti aene nng is pi eferably substituted by trimethylsilyl groups, most preferably in the 1 , 4 - position i
- the anionic groups suitable for use as the y ligand include hydride, halogen, alkyl etc
- Preferred complexes according to the present invention are those wherein Z is a dimethylsilyl bridging group and Y is a halogen
- the preferred complexes are those wherein M is zirconium.
- a particularly preferred complex is
- the complexes according to the pi esent invention may be used in catalyst systems in the presence of suitable cocatalysts, for example organometallic compounds having a metal from Group I A, II A, IIB or IIIB of the Periodic Table
- suitable cocatalysts for example organometallic compounds having a metal from Group I A, II A, IIB or IIIB of the Periodic Table
- cocataiysts are known for their use in the polymerisation of olefins and include organoaluminium compounds such as trialkyl, alkyl hydride, alkyl halo and alkyl alkoxy aluminium compounds and alumoxanes, the latter being preferred
- a preferred co-catalyst is methyl aluminoxane (MAO) and commercial materials known as modified MAO (MMAO)
- cocatalysts are boron compounds for example boranes such as tris (pentafluorophenyl) boron or borates such as trialkylammonium tetraphenylborates or N,N-dialkyl anilinium tetraphenylborates
- boron compounds for example boranes such as tris (pentafluorophenyl) boron or borates such as trialkylammonium tetraphenylborates or N,N-dialkyl anilinium tetraphenylborates
- Such activating cocatalysts are particularly suitable with complexes having anionic Y ligands comprising alkyl ligands for example methyl ligands
- the co-catalyst may be mixed with the complex optionally on an inorganic support Alternatively, the co-catalyst may be added to the polymerisation medium along with the complex
- the co-catalyst e g MAO may also be prepared in-situ by pretreating the support with for example trimethyl aluminium or other alkyl aluminium
- the amount of co-catalyst mixed with complex may be such as to provide an atom ratio of M from the complex to the metal in the co-catalyst of 1 to 10,000 10,000 to 1 for aluminoxanes and 1 to 100 100 to 1 otherwise.
- the complex may suitably be supported on a suitable inorganic support material
- any suitable inorganic support may be used for example, inorganic oxides such as silica, alumina
- inorganic halides such as silica, alumina
- Suitable hahdes include Group IIA halides e g magnesium chloride
- a preferred inorganic support is silica
- the complex may be impregnated onto the support material under anhydrous conditions and under an inert atmosphere
- the impregnation can be conducted using an inert solvent, in which case the solvent may then be evaporated under reduced pi essui e
- the impregnated support may then be heated to remove any remaining solvent
- the complex and co-cataiyst may be dissolved in the inert solvent
- Suitable inert solvents include aromatic hydrocarbons such as toluene
- the solution of complex and co-catalyst may then be added to the inorganic support material
- Other suitable means of foi ming a supported polymerisation catalyst may also be used
- a catalyst composition suitable for the polymerisation of olefins comprising (A) a complex as disclosed above and (B) an activating cocatalyst
- the olefin polymerisation catalysts according to the present invention may be used to produce polymers using solution, slurry or gas phase polymerisation processes Methods and appai tus tor effecting such polymerisation reactions are well known
- the catalysts according to the present invention can be used in similar amounts and undei similai conditions to known olefin polymerisation catalysts
- the complexes according to the present invention may also be used in the presence of conventional polymerisation catalysts e g Ziegler catalysts or metailocenes
- Complexes according to the pi esent invention may be suitably prepared from l ,4-b ⁇ s(tr ⁇ methyls ⁇ lyl) cyclooctatetraene as shown in the accompanying Figure 1 which repi esents prepai ative l outes to complexes of Formula I
- Ethylene was polymerised at 30°C in isobutane
- a solution containing 1 l mg dissovled in 1 7 2 ml MAO ( I 55 in toluene) and 4 8 ml toluene was prepared 2ml of this solution (2mg catalyst, 4 03 lnicromol) were added to the slurry reactor and after first 5h another 2ml 18 7g poiyethyiene were obtained after 1 h
- the Mw was very high 1 1 50000, Mn 447000, PD 2 4
- Ethylene was polymei ised at 75°C using a similar catalyst solution this time using 3 injections of catalyst - 2 3ml (0 5 mg catalyst), 2 3 mis after 15 mins and 4 6 is after a funhei 30 mm 10 4g polyethylene was isolated after 1 5 hrs M ⁇ V 444000, Mn 165000, PD 2 7
- Ethylene was polymerised in the presence of 10 mg [COT" - SiMe2-Cp] ZrCl prepared in Example 2 and methyl aluminoxane ( 1 ml, 2M in toluene) diluted in toluene (30 ml) and ethylene (7 bar) The temperature (23°C) increased to 38°C during the reaction After 1 min 2 6g of polyethylene was obtained.
- Example 6 Polymerisation
- a 3 litre autoclave was heated, whilst stirring, at 90°C for 1 hour with a flow of 1 -2 litre/min nitrogen purging the reactor.
- the catalyst normally 0 25g
- the catalyst was kept in a nitrogen atmosphere within the catalyst injector and attached to the reactor in such a way to purge any air from the couplings
- the reactor was cooled to below 50°C and 300 g of predried sodium chloride added under nitrogen atmosphere
- the NaCl (1mm diameter) was dried at 1 50°C under vacuum for more than 4 hours.
- TMA (3ml, 2M in hexane) was added to the reactor under nitrogen at 50°C.
- the reactor was boxed in nitrogen at 1 atmosphere and the temperature then increased to 80°C for greater than 20 minutes
- the reactor was purged with nitrogen at 80°C and then left with 1 bar nitrogen.
- the reactor was adjusted to 3°C below that which was to be used in the polymerisation Hydrogen was added to the autoclave, if required, at this point Ethylene and hexene were then added
- the catalyst was injected in the reactor at this steady state condition
- the pressure of the reactor normally increases by 0 3 bar during the injection
- the reactor temperature was raised to the reaction temperature.
- the catalyst was tested for intervals between 30 minutes and 2 hours
- the invention is further illustrated by the preparation of a mulisite catalyst prepared by combining a complex according to the present invention with a conventional Ziegler catalyst Example 9
- ES70 silica was slurried in hexane and hexamethyldisilazane (0.8mM g Si02) added with stirring Dibutylmagnesium ( 1 5 mM/g Si02) was then added followed by t-butyl chloride (3mM/g Si02). Finally an equimolar mixture of titanium tetrachloride and titanium tetra-n-butoxide (0 1 + 0 15 mM/g Si02) were added before the slurry was dried under a flowing N2 stream.
- the mixture of the supported catalyst and the [COT" - SiMe2 Cp] ZrCl]/MAO solution was stirred for I hour at room temperature before the toluene was removed under vacuum, the nominal composition of the catalyst was 1.03% w/w TiO.28% w/w Zr with an Al/Zr ratio of 140/ 1
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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
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97925147A EP0906323A1 (en) | 1996-06-06 | 1997-06-05 | Novel group iv metal complexes |
AU30387/97A AU3038797A (en) | 1996-06-06 | 1997-06-05 | Novel group iv metal complexes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9612130.6 | 1996-06-06 | ||
GBGB9612130.6A GB9612130D0 (en) | 1996-06-06 | 1996-06-06 | Novel group IV metal complexes |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997046567A1 true WO1997046567A1 (en) | 1997-12-11 |
Family
ID=10795059
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1997/001519 WO1997046567A1 (en) | 1996-06-06 | 1997-06-05 | Novel group iv metal complexes |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0906323A1 (en) |
AU (1) | AU3038797A (en) |
GB (1) | GB9612130D0 (en) |
WO (1) | WO1997046567A1 (en) |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004094487A1 (en) | 2003-03-21 | 2004-11-04 | Dow Global Technologies, Inc. | Morphology controlled olefin polymerization process |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
US7456244B2 (en) | 2006-05-23 | 2008-11-25 | Dow Global Technologies | High-density polyethylene compositions and method of making the same |
WO2010071798A1 (en) | 2008-12-18 | 2010-06-24 | Univation Technologies, Llc | Method for seed bed treatment for a polymerization reaction |
WO2010088265A1 (en) | 2009-01-30 | 2010-08-05 | Dow Global Technologies Inc. | High-density polyethylene compositions, method of producing the same, closure devices made therefrom, and method of making such closure devices |
EP2218751A1 (en) | 2004-12-17 | 2010-08-18 | Dow Global Technologies Inc. | Rheology modified polyethylene compositions |
US7981517B2 (en) | 2007-08-28 | 2011-07-19 | Dow Global Technologies Inc. | Bituminous compositions and methods of making and using same |
US8445594B2 (en) | 2006-05-02 | 2013-05-21 | Dow Global Technologies Llc | High-density polyethylene compositions, method of making the same, articles made therefrom, and method of making such articles |
WO2014105614A1 (en) | 2012-12-28 | 2014-07-03 | Univation Technologies, Llc | Methods of integrating aluminoxane production into catalyst production |
WO2014109832A1 (en) | 2013-01-14 | 2014-07-17 | Univation Technologies, Llc | Methods for preparing catalyst systems with increased productivity |
WO2016182920A1 (en) | 2015-05-08 | 2016-11-17 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063764A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063767A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063765A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018118155A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2019118073A1 (en) | 2017-12-13 | 2019-06-20 | Exxonmobil Chemical Patents Inc. | Deactivation methods for active components from gas phase polyolefin polymerization process |
WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
WO2019213227A1 (en) | 2018-05-02 | 2019-11-07 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
WO2019217173A1 (en) | 2018-05-02 | 2019-11-14 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
WO2020014138A1 (en) | 2018-07-09 | 2020-01-16 | Exxonmobil Chemical Patents Inc. | Polyethylene cast films and methods for making the same |
WO2020023207A1 (en) | 2018-07-26 | 2020-01-30 | Exxonmobil Chemical Patents Inc. | Multilayer foam films and methods for making the same |
WO2020102380A1 (en) | 2018-11-13 | 2020-05-22 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and films |
WO2020102385A1 (en) | 2018-11-13 | 2020-05-22 | Exxonmobil Chemical Patents Inc. | Polyethylene films |
WO2020109870A2 (en) | 2018-06-28 | 2020-06-04 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions, wires and cables, and methods for making the same |
WO2020163079A1 (en) | 2019-02-06 | 2020-08-13 | Exxonmobil Chemical Patents Inc. | Films and backsheets for hygiene articles |
WO2021126458A1 (en) | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved sealing performance and mechanical properties |
WO2021183337A1 (en) | 2020-03-12 | 2021-09-16 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved bending stiffness and high md tear resistance |
US11447620B2 (en) | 2007-05-02 | 2022-09-20 | Dow Global Technologies Llc | High-density polyethylene compositions, method of making the same, injection molded articles made therefrom, and method of making such articles |
WO2022232760A1 (en) | 2021-04-30 | 2022-11-03 | Exxonmobil Chemical Patents Inc. | Processes for transitioning between different polymerization catalysts in a polymerization reactor |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH06263768A (en) * | 1993-03-12 | 1994-09-20 | Idemitsu Kosan Co Ltd | Production of organometallic compound, polymerization catalyst and production of polymer using the catalyst system |
EP0672676A2 (en) * | 1994-03-15 | 1995-09-20 | BP Chemicals Limited | Polymerization catalysts |
-
1996
- 1996-06-06 GB GBGB9612130.6A patent/GB9612130D0/en active Pending
-
1997
- 1997-06-05 EP EP97925147A patent/EP0906323A1/en not_active Withdrawn
- 1997-06-05 WO PCT/GB1997/001519 patent/WO1997046567A1/en not_active Application Discontinuation
- 1997-06-05 AU AU30387/97A patent/AU3038797A/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06263768A (en) * | 1993-03-12 | 1994-09-20 | Idemitsu Kosan Co Ltd | Production of organometallic compound, polymerization catalyst and production of polymer using the catalyst system |
EP0672676A2 (en) * | 1994-03-15 | 1995-09-20 | BP Chemicals Limited | Polymerization catalysts |
Non-Patent Citations (4)
Title |
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F.G.N. CLOKE ET AL, JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, 1994, pages 1207 - 1208, XP002012291 * |
P. BERNO ET AL, JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS, 1991, pages 3085 - 3091, XP002012289 * |
P. BERNO ET AL, JOURNAL OF THE CHEMICAL SOCIETY DALTON TRANSACTIONS, 1991, pages 3093 - 3095, XP002012290 * |
PATENT ABSTRACTS OF JAPAN vol. 18, no. 668 (C - 1289) 16 December 1994 (1994-12-16) * |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004094487A1 (en) | 2003-03-21 | 2004-11-04 | Dow Global Technologies, Inc. | Morphology controlled olefin polymerization process |
EP2218751A1 (en) | 2004-12-17 | 2010-08-18 | Dow Global Technologies Inc. | Rheology modified polyethylene compositions |
EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
US8445594B2 (en) | 2006-05-02 | 2013-05-21 | Dow Global Technologies Llc | High-density polyethylene compositions, method of making the same, articles made therefrom, and method of making such articles |
US7560524B2 (en) | 2006-05-23 | 2009-07-14 | Dow Global Technologies, Inc. | High-density polyethylene compositions and method of making the same |
US7456244B2 (en) | 2006-05-23 | 2008-11-25 | Dow Global Technologies | High-density polyethylene compositions and method of making the same |
US11447620B2 (en) | 2007-05-02 | 2022-09-20 | Dow Global Technologies Llc | High-density polyethylene compositions, method of making the same, injection molded articles made therefrom, and method of making such articles |
US7981517B2 (en) | 2007-08-28 | 2011-07-19 | Dow Global Technologies Inc. | Bituminous compositions and methods of making and using same |
WO2010071798A1 (en) | 2008-12-18 | 2010-06-24 | Univation Technologies, Llc | Method for seed bed treatment for a polymerization reaction |
WO2010088265A1 (en) | 2009-01-30 | 2010-08-05 | Dow Global Technologies Inc. | High-density polyethylene compositions, method of producing the same, closure devices made therefrom, and method of making such closure devices |
US9056970B2 (en) | 2009-01-30 | 2015-06-16 | Dow Global Technologies Llc | High-density polyethylene compositions, method of producing the same, closure devices made therefrom, and method of making such closure devices |
WO2014105614A1 (en) | 2012-12-28 | 2014-07-03 | Univation Technologies, Llc | Methods of integrating aluminoxane production into catalyst production |
WO2014109832A1 (en) | 2013-01-14 | 2014-07-17 | Univation Technologies, Llc | Methods for preparing catalyst systems with increased productivity |
WO2016182920A1 (en) | 2015-05-08 | 2016-11-17 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063767A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063765A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018063764A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2018118155A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Chemical Patents Inc. | Polymerization process |
WO2019118073A1 (en) | 2017-12-13 | 2019-06-20 | Exxonmobil Chemical Patents Inc. | Deactivation methods for active components from gas phase polyolefin polymerization process |
WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
WO2019213227A1 (en) | 2018-05-02 | 2019-11-07 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
WO2019217173A1 (en) | 2018-05-02 | 2019-11-14 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
WO2020109870A2 (en) | 2018-06-28 | 2020-06-04 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions, wires and cables, and methods for making the same |
WO2020014138A1 (en) | 2018-07-09 | 2020-01-16 | Exxonmobil Chemical Patents Inc. | Polyethylene cast films and methods for making the same |
WO2020023207A1 (en) | 2018-07-26 | 2020-01-30 | Exxonmobil Chemical Patents Inc. | Multilayer foam films and methods for making the same |
WO2020102380A1 (en) | 2018-11-13 | 2020-05-22 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and films |
WO2020102385A1 (en) | 2018-11-13 | 2020-05-22 | Exxonmobil Chemical Patents Inc. | Polyethylene films |
WO2020163079A1 (en) | 2019-02-06 | 2020-08-13 | Exxonmobil Chemical Patents Inc. | Films and backsheets for hygiene articles |
WO2021126458A1 (en) | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved sealing performance and mechanical properties |
WO2021183337A1 (en) | 2020-03-12 | 2021-09-16 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved bending stiffness and high md tear resistance |
WO2022232760A1 (en) | 2021-04-30 | 2022-11-03 | Exxonmobil Chemical Patents Inc. | Processes for transitioning between different polymerization catalysts in a polymerization reactor |
Also Published As
Publication number | Publication date |
---|---|
GB9612130D0 (en) | 1996-08-14 |
EP0906323A1 (en) | 1999-04-07 |
AU3038797A (en) | 1998-01-05 |
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