EP0931099A1 - Method for producing olefin polymers with a higher melting point - Google Patents
Method for producing olefin polymers with a higher melting pointInfo
- Publication number
- EP0931099A1 EP0931099A1 EP98920472A EP98920472A EP0931099A1 EP 0931099 A1 EP0931099 A1 EP 0931099A1 EP 98920472 A EP98920472 A EP 98920472A EP 98920472 A EP98920472 A EP 98920472A EP 0931099 A1 EP0931099 A1 EP 0931099A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- methyl
- indenyl
- cιo
- aryl
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
Links
Classifications
-
- 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
- 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
- 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 an improved process for the preparation of polyolefins by polymerizing olefins at pressures in the range from 0.5 to 3000 bar and temperatures in the range from -60 to 300 ° C. in the presence of a metallocene support catalyst, and to the use of polymers of olefins thus obtainable for the production of fibers, films and moldings.
- Metallocene catalysts are increasingly being used in carrier-fixed form, for example for the polymerization of olefins, since this has process engineering advantages.
- catalysts which are obtainable from metallocene and aluminoxanes provide polymers, in particular propylene polymers, in a fixed form with a lower polymer melting point than the analogous soluble catalyst system (see EP-A 0 576 970 compared to EP-A 0 780 402) ).
- a reduced melting point means reduced crystallinity of the polymer and deteriorates mechanical properties, such as rigidity.
- the object of the present invention was therefore to find a polymerization process using a supported catalyst system, which polymers with an increased melting point, similar to those with the analog solution
- Catalyst systems are available, accessible, the other properties of the polymer, such as high molecular weight M w narrow molecular weight distribution M w / M n and low xylene-soluble fractions remain practically unchanged during the transition from the soluble to the supported catalyst.
- a process for the preparation of polyolefins by polymerizing olefins at pressures in the range from 0.5 to 3000 bar and temperatures in the range from -60 to 300 ° C in the presence of a supported metallocene catalyst characterized in that a supported metallocene catalyst containing active ingredients A) a metallocene complex
- a metallocenium ion-forming compound selected from the group consisting of Lewis acids and ionic compounds with non-coordinating anions
- any metallocene can serve as the metallocene component A) of the process according to the invention.
- the metallocene can be both bridged and unbridged and have the same or different ligands.
- Highly suitable metallocene components A are those which are described, for example, in DE-A 196 06 167, to which reference is expressly made here, with particular reference to the disclosure on page 3, line 28 to page 6, line 48 of the DE- A 196 06 167 is pointed out.
- Preferred metallocene components A) are those of the formula (I) below.
- M 1 is a metal from group IVb of the Periodic Table of the Elements
- R 1 and R 2 are the same or different and are a hydrogen atom, a C ⁇ -C ⁇ o-alkyl group, a C ⁇ -C ⁇ o-alkoxy group, a C 6 -C 0 aryl group, a C 6 -C ⁇ o-aryloxy group, a C 2 -C ⁇ o -Alkenyl group, an OH group, an NR 12 group, where R 12 is a C 1 -C 2 -alkyl group or C 6 -C 4 -aryl group, or a halogen atom,
- R 3 to R 8 and R 3 'to R 8 ' are the same or different and a hydrogen atom is a C ⁇ -C4o-hydrocarbon group, which can be linear, cyclic or branched, for example a C ⁇ -C ⁇ o-alkyl group, C 2 - C ⁇ o-alkenyl group, C 6 -C o-aryl group, a C 7 -C 4 o-arylalkyl group, a C 7 -C 4 o-alkylaryl group or a C 8 -C 40 -arylalkenyl group, or adjacent radicals R 4 to R 8 and / or R 4 'to R 8 ' form a ring system with the atoms connecting them, R 9 signifies a bridge, preferably Rio R ⁇ o R ⁇ o R ⁇ o R ⁇ o R ⁇ o
- R i ° and R U are the same or different and is a hydrogen atom, a halogen atom or a -C-C 4 o-carbon-containing group such as a C ⁇ -C o-alkyl, a C ⁇ -C ⁇ rj-fluoroalkyl, a C ⁇ -C ⁇ o- Alkoxy, a C 6 -C 4 aryl -, a C ⁇ -Cio-fluoroaryl-, a C- 6 -C ⁇ o-aryloxy-, a C -C ⁇ 0 alkenyl-, a C -C 4 o-aralkyl-, a C 7 -C 4 o "alkylaryl or a Cs-Cirj-arylalkenyl group or R 10 and R 11 each form one or more rings with the atoms connecting them and x is an integer from zero to 18,
- M 2 is silicon, germanium or tin, and rings A and B are the same or different, saturated, unsaturated or partially saturated.
- R 9 can also link two units of the formula I to one another.
- M x is zirconium or hafnium
- the indenyl or tetrahydroindenyl ligands of the metallocenes of the formula I are preferably in 2-, 2,4-, 4,7-, 2,6-, 2,4,6-, 2,5,6-, 2,4, 5,6- and 2, 4, 5, 6, 7 position, in particular in the 2, 4 position, substituted.
- Preferred substituents are a C 1 -C alkyl group such as methyl, ethyl or isopropyl or a C 6 -Cio aryl group such as phenyl, naphthyl or mesityl.
- the 2 position is preferably substituted by a C 1 -C 4 alkyl group, such as methyl or ethyl. If substituted in the 2,4-position, the following applies:
- R 5 and R 5 ' are preferably the same or different and one
- Highly suitable metallocenes of the general formula I are those which are described in DE application 197 094 02.3 on page 78, line 21 to page 100, line 22 and in DE application 197 135 46.3 on page 78, line 14 to page 103, Line 22 are disclosed, to which express reference is made here; the dimethylsilanediylbis- [1- (2-methyl-4- (4-tert. -butylphenyl) indenyl)] zirconium dichloride being particularly suitable.
- metallocenes of the formula I in which the substituents in the 4- and 5-position of the indenyl radicals (R 5 and R 6 and R 5 'and R 6 ') together with the atoms connecting them form a ring system, preferably one Six-ring.
- This condensed ring system can also be substituted by radicals with the meaning of R 3 -R 8 .
- Examples of such compounds I include dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride.
- An example of such compounds of the formula I is dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride.
- Examples of the metallocene component A of the process according to the invention are:
- Dimethylsilanediylbis indenyl) zirconium dichloride Dimethylsilanediylbis -naphthyl- indenyl) zirconium dichloride Dimethylsilanediylbis 2 -methyl -benzo- indenyl) zirconium dichloride Dimethylsilanediylbis-2 -methyl-indenyl) zirconyldichloro-1-methyldichloride
- Dimethylsilanediylbis 2 -methyl-4- (2-naphthyl) indenyl) zirconium dichloride Dimethylsilanediylbis 2 -methyl -4 -phenyl -indenyl) zirconium dichloride
- Dimethylsilanediylbis (2,4,6 -trimethyl -indenyl) zirconium dichloride Dimethylsilanediylbis (2,5,6 -trimethyl -indenyl) zirconiumdichloride Dimethylsilanediylbis (2,4,7 -trimethyl -indenyl) zirconiumdichloride Dimethylsilanediylbis (2 -mutyl- 5-is ) zirconium dichloride dimethylsilanediylbis (2 -methyl- 5- t -butyl-indenyl) zirconium dichloride
- the catalyst system according to the invention contains compounds B) forming metallocenium ions. These can be Lewis acids and / or ionic compounds with non-coordinated anions.
- the Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C 1 -C 2 carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl, such as phenyl, tolyl, benzyl groups, p-fluorophenyl, 3, 5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3, 4, 5-trifluorophenyl and 3, 5-di (trifluoromethyl) phenyl.
- organoboron or organoaluminum compound which contains C 1 -C 2 carbon-containing groups, such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluor
- Organoboron compounds are particularly preferred.
- Lewis acids examples include trifluoroborane, triphenylborane, tris (4-fluorophenyl) orane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tis (pentafluorophenyl) borane, tris (tolyl) borane, tris ( 3, 5 -dimethylphenyl) borane, tris (3, 5-dime- thylfluorophenyl) borane and / or tris (3,4,5-trifluorophenyl) borane. Tris (pentafluorophenyl) borane is particularly preferred.
- Well-suited ionic compounds which contain a non-coordinating anion are, for example, tetrakis (pentafluorophenyl) borates, tetraphenylborates, SbF 6 " , CF 3 SO 3 " or CIO 4 ".
- Lewis bases such as methylamine are generally used as the cationic counterion , Aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N , N-dimehylaniline, tri-ethylphosphine, tri-phenylphosphine, diphenylphosphine, tetrahydrothiophene and triphenylcarbenium are used.
- Tributylammonium tetra (phenyl) borate Trimethylammonium tetra (tolyl) borate
- Triphenylcarbenium tetrakis (pentafluorophenyl) borate Triphenylcarbenium tetrakis (pentafluorophenyl) borate
- Ferrocenium tetrakis (pentafluorophenyl) aluminate Ferrocenium tetrakis (pentafluorophenyl) aluminate.
- Triphenylcarbenium tetrakis (pentafluorophenyl) borate and / or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferred.
- Mixtures of at least one Lewis acid and at least one ionic compound can also be used.
- Borane or carborane compounds such as e.g.
- Tri (butyl) mmonium-1-carbadecec. Tri (butyl) mmonium-1-carbadecec.
- the carrier component of the catalyst system according to the invention can be any organic or inorganic, inert solid, in particular a porous carrier such as talc, inorganic oxides and finely divided polymer powders (e.g. polyolefins).
- Suitable inorganic oxides can be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements.
- oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the two elements and corresponding oxide mixtures.
- Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxidic supports are, for example, MgO, Zr0, Ti0 2 or B0 3 , to name just a few.
- the carrier materials used generally have a specific surface area in the range from 10 to 1000 m 2 / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size of 1 to 500 ⁇ m.
- Carriers with a specific surface area in the range from 50 to 500 m 2 / g, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 ⁇ m are preferred.
- Carriers with a specific surface area in the range of 200 are particularly preferred up to 400 m 2 / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 ⁇ m.
- the carrier material used naturally has a low moisture content or residual solvent content, dehydration or drying can be avoided before use. If this is not the case, as is the case when using silica gel as the carrier material, dehydration or drying is recommended.
- the thermal dehydration or drying of the carrier material can take place under vacuum and at the same time inert gas blanket (e.g. nitrogen).
- the drying temperature is in the range between 100 and 1000 ° C, preferably between 200 and 800 ° C. In this case, the pressure parameter is not critical.
- the drying process can take between 1 and 24 hours. Shorter or longer drying times are possible, provided that under the chosen conditions the equilibrium can be established with the hydroxyl groups on the support surface, which normally requires between 4 and 8 hours.
- Suitable inerting agents are, for example, silicon halides and silanes, such as silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane and organometallic compounds of aluminum, boron and magnesium, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triethyl borane and dibutyl magnesium.
- the chemical dehydration or inertization of the carrier material takes place, for example, by reacting a suspension of the carrier material in a suitable solvent with the inerting reagent in pure form or dissolved in a suitable solvent with exclusion of air and moisture.
- suitable solvents are, for example, aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, toluene or xylene.
- the inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 and 70 ° C. Higher and lower temperatures are possible.
- the duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours.
- the carrier material is isolated by filtration under inert conditions, one or more times with suitable ten inert solvents, as described above, washed and then dried with an inert gas stream or in vacuo.
- Organic carrier materials such as finely divided polyolefin powders (e.g. polyethylene, polypropylene or polystyrene) can also be used and should also be removed by appropriate cleaning and drying operations before the use of adhering moisture, solvent residues or other contaminants.
- polyolefin powders e.g. polyethylene, polypropylene or polystyrene
- the preparation of the supported catalyst is generally not critical.
- Well-suited variants are the following:
- At least one metallocene component A) is generally brought into contact with the compound B) forming metallocenium ions in an organic solvent, in order to obtain a dissolved or partially suspended product.
- This product is then generally added to the support material, preferably porous silicon dioxide (silica gel), if appropriate pretreated as described above, the solvent is removed and the supported catalyst is obtained as a free-flowing solid.
- the supported catalyst can then be prepolymerized, for example with C 2 - to C 1 -C 1 -enes.
- the metallocene supported catalyst is generally obtained by the following process steps
- an inorganic support material preferably porous silicon dioxide as described above
- an inerting agent as described above, preferably an aluminum tri-C ⁇ -C ⁇ o-alkyl, such as trimethylaluminium, triethylaluminium, triisobutylaluminum,
- an alkali metal, alkaline earth metal or main group -III- organometallic compound preferably aluminum tri- C ⁇ -C ⁇ o-alkyl, such as trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.
- olefins examples include 1-olefins having 2 to 40, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbornene, norbornadiene, ethyl norbornadiene and cyclic olefins such as norbornene, tetracyclododecene or methyl norbornene.
- 1-olefins having 2 to 40, preferably 2 to 10, carbon atoms, such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, Styrene, dienes such as 1, 3-butadiene, 1, 4-hexadiene, vinyl norbornene, norbornadiene
- Ethene or propene are preferably homopolymerized in the process according to the invention, or ethene with one or more 1-olefins with 3 to 20 C atoms, such as propene, and / or one or more dienes with 4 to 20 C atoms, such as 1, 4 -Butadiene, norbornadiene or ethylnorbornadiene, copolymerized.
- Examples of such copolymers are ethene / propene copolymers or ethene / propene / 1,4-hexadiene terpolymers.
- the polymerization is carried out at a temperature of -60 to 300 ° C, preferably 50 to 200 ° C.
- the pressure is 0.5 to 3000 bar, preferably 5 to 64 bar.
- the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
- the polyolefins according to the invention are distinguished, inter alia, by the fact that they have a high crystallinity, expressed, inter alia, by a high DSC melting point, and high rigidity. Based on current knowledge, this property profile can be traced back to a special microstructure of the polymer chains.
- Example 2 the metallocene used was rac-dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride.
- Example 2 the metallocene used was rac-dimethylsilanediylbis (2 -methyl -4 (1-naphthyl) indenyl) zirconium dichloride.
- the melting points of the corresponding polymers can be found in the table.
Abstract
Description
Claims
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19709402 | 1997-03-07 | ||
DE19709402 | 1997-03-07 | ||
DE19713546 | 1997-04-02 | ||
DE19713546A DE19713546A1 (en) | 1997-04-02 | 1997-04-02 | Free-flowing catalyst system for olefin polymerisation |
DE19757262 | 1997-12-23 | ||
DE1997157262 DE19757262A1 (en) | 1997-12-23 | 1997-12-23 | Production of polyolefin with a high melting point |
DE19757563 | 1997-12-23 | ||
DE19757563A DE19757563A1 (en) | 1997-03-07 | 1997-12-23 | Free-flowing catalyst system for olefin polymerisation |
PCT/EP1998/001231 WO1998040419A1 (en) | 1997-03-07 | 1998-03-05 | Method for producing olefin polymers with a higher melting point |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0931099A1 true EP0931099A1 (en) | 1999-07-28 |
Family
ID=27438564
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98920472A Withdrawn EP0931099A1 (en) | 1997-03-07 | 1998-03-05 | Method for producing olefin polymers with a higher melting point |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0931099A1 (en) |
AU (1) | AU7332398A (en) |
CA (1) | CA2262493A1 (en) |
NO (1) | NO991113L (en) |
WO (1) | WO1998040419A1 (en) |
Families Citing this family (70)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19962910A1 (en) | 1999-12-23 | 2001-07-05 | Targor Gmbh | Chemical compound, process for its preparation and its use in catalyst systems for the production of polyolefins |
DE10028432A1 (en) | 2000-06-13 | 2001-12-20 | Basell Polyolefine Gmbh | High-activity olefin polymerization catalysts leaving little or no particulate residue in the polymer comprise calcined hydrotalcite carrier and organo-transition metal compound |
US6380330B1 (en) | 2000-06-30 | 2002-04-30 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6380331B1 (en) | 2000-06-30 | 2002-04-30 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6380122B1 (en) | 2000-06-30 | 2002-04-30 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6376627B1 (en) | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6380120B1 (en) | 2000-06-30 | 2002-04-30 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6376409B1 (en) | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6376411B1 (en) | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6376407B1 (en) | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6414095B1 (en) | 2000-06-30 | 2002-07-02 | Exxon Mobil Chemical Patents Inc. | Metallocene compositions |
CN1274701C (en) * | 2000-06-30 | 2006-09-13 | 埃克森美孚化学专利公司 | Metallocenes with bridged 4-phenyl-indenyl-ligand for olefin polymerization |
US6380123B1 (en) | 2000-06-30 | 2002-04-30 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US7122498B2 (en) | 2000-06-30 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Metallocenes and catalyst compositions derived therefrom |
US6380121B1 (en) | 2000-06-30 | 2002-04-30 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6376410B1 (en) | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6399723B1 (en) | 2000-06-30 | 2002-06-04 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6376408B1 (en) | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6376412B1 (en) | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6380124B1 (en) | 2000-06-30 | 2002-04-30 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6380334B1 (en) | 2000-06-30 | 2002-04-30 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6376413B1 (en) | 2000-06-30 | 2002-04-23 | Exxonmobil Chemical Patents Inc. | Metallocene compositions |
US6870016B1 (en) | 2000-06-30 | 2005-03-22 | Exxonmobil Chemical Patents Inc. | Polymerization process and polymer composition |
ATE321061T1 (en) | 2001-06-22 | 2006-04-15 | Basell Polyolefine Gmbh | METALLOCENES, USE IN CATALYSTS FOR OLEFIN POLYMERIZATION |
WO2003002583A2 (en) | 2001-06-29 | 2003-01-09 | Exxonmobil Chemical Patents Inc. | Metallocenes and catalyst compositions derived therefrom |
DE10145453A1 (en) | 2001-09-14 | 2003-06-05 | Basell Polyolefine Gmbh | Monocyclopentadienyl complexes with a condensed heterocycle |
KR100914423B1 (en) | 2001-09-14 | 2009-08-27 | 바젤 폴리올레핀 게엠베하 | Method for the polymerization of olefins |
DE10158656A1 (en) | 2001-11-30 | 2003-06-26 | Basell Polyolefine Gmbh | Organo transition metal compound, biscyclopentadienyl ligand system, catalyst system and process for making polyolefins |
US7157591B2 (en) | 2001-12-10 | 2007-01-02 | Exxonmobie Chemical Patents Inc. | Metallocenes and catalyst compositions derived therefrom |
WO2004018489A1 (en) | 2002-08-22 | 2004-03-04 | Basell Polyolefine Gmbh | Monocyclopentadienyl complexes |
EP1567560B1 (en) | 2002-12-06 | 2011-01-19 | Basell Polyolefine GmbH | Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and process for preparing polyolefins |
CA2510061A1 (en) | 2002-12-20 | 2004-07-08 | Basell Polyolefin Gmbh | Copolymers of ethylene with .alpha.-olefins |
WO2004056481A1 (en) | 2002-12-20 | 2004-07-08 | Basell Polyolefine Gmbh | Monocyclopentadienyl complexes |
ATE364637T1 (en) | 2003-02-07 | 2007-07-15 | Basell Polyolefine Gmbh | POLYMERIZATION CATALYSTS, ORGANIC TRANSITION METAL COMPOUNDS, PROCESS FOR PRODUCING POLYOLEFINS |
ATE364641T1 (en) | 2003-04-03 | 2007-07-15 | Basell Polyolefine Gmbh | PRODUCTION OF HIGH MOLECULAR POLYOLEFINS IN THE PRESENCE OF AN ORGANIC TRANSITION METAL COMPOUND IN A GAS PHASE FLUIDIZED BED REACTOR |
JP2006528951A (en) | 2003-05-21 | 2006-12-28 | バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | Transition metal complexes with tridentate nitrogen-containing ligands |
US7589223B2 (en) | 2003-09-25 | 2009-09-15 | Basell Polyolefine Gmbh | Polymerization catalysts, preparation of polyolefins, organotransition metal compounds and ligands |
DE10352139A1 (en) | 2003-11-04 | 2005-06-09 | Basell Polyolefine Gmbh | Organometallic transition metal compound used for catalyst system for polymerization of olefin, is new |
DE10358082A1 (en) | 2003-12-10 | 2005-07-14 | Basell Polyolefine Gmbh | Organometallic transition metal compound used in catalyst system for preparation of polyolefins, uses biscyclopentadienyl ligand systems in its preparation |
WO2005058928A1 (en) | 2003-12-16 | 2005-06-30 | Basell Polyolefine Gmbh | Monocyclopentadienyl complexes |
US7629464B2 (en) | 2003-12-19 | 2009-12-08 | Basell Polyolefine Gmbh | Monocyclopentadienyl complexes |
DE102004020524A1 (en) | 2004-04-26 | 2005-11-10 | Basell Polyolefine Gmbh | Polyethylene for film, e.g. stretch film, used in carrier bags, contains ethylene homopolymers and/or copolymers of ethylene with 1-alkenes |
DE102004027332A1 (en) | 2004-06-04 | 2005-12-22 | Basell Polyolefine Gmbh | New organometallic transition metal compound useful as catalyst constituents of catalyst systems for the polymerization of ethylene |
DE102004032581A1 (en) | 2004-07-05 | 2006-02-09 | Basell Polyolefine Gmbh | Catalyst system for use in preparing isotactic polyolefin, comprises chiral coordination compound(s) of main group element, e.g. aluminum, silicon, or gallium, as central atom, and co-catalyst(s) |
DE102004039877A1 (en) | 2004-08-17 | 2006-02-23 | Basell Polyolefine Gmbh | Cyclopentadienyl complex of Group 6 for use in making a catalyst system for olefin polymerization has cyclopentadienyl system(s) being substituted by silyl group(s) that bears halogen substituent(s) |
DE102005014395A1 (en) | 2005-03-24 | 2006-09-28 | Basell Polyolefine Gmbh | Monocyclopentadienyl complex used in catalyst system for olefin polymerization, comprises component of specific formula having cyclopentadienyl ligands bearing bridged donor, i.e. bridged keto, thioketo, imino, and/or phosphino group |
DE102005019393A1 (en) | 2005-04-25 | 2006-10-26 | Basell Polyolefine Gmbh | Molding material, useful for the preparation of injection-molded body and screw valve, comprises ethylene monomer |
DE102005035477A1 (en) | 2005-07-26 | 2007-02-01 | Basell Polyolefine Gmbh | Preparation of olefin polymers, e.g. polyethylene, for producing pressure pipes for transport of gas and wastewater, by polymerization of alpha-olefin(s) with hybrid catalyst to produce higher and lower molecular weight polymer components |
DE102005057559A1 (en) | 2005-11-30 | 2007-05-31 | Basell Polyolefine Gmbh | New transition pyrazole metal compound useful for e.g. the oligomerization, polymerization or copolymerization of polyolefin, preferably ethylene |
DE102007017903A1 (en) | 2007-04-13 | 2008-10-16 | Basell Polyolefine Gmbh | Polyethylene and catalyst composition and process for its preparation |
US8207281B2 (en) | 2007-12-18 | 2012-06-26 | Basell Polyolefine Gmbh | Process for preparing transition metal compounds for olefins polymerization |
ATE522550T1 (en) | 2007-12-19 | 2011-09-15 | Basell Polyolefine Gmbh | ETHYLENE TERPOLYMERS |
EP2225283B1 (en) | 2007-12-24 | 2013-08-14 | Basell Polyolefine GmbH | Multistage process for the polymerization of olefins |
EP2236577A3 (en) | 2008-02-18 | 2011-05-04 | Basell Polyolefine GmbH | Polyethylene article |
US8957158B2 (en) | 2008-09-25 | 2015-02-17 | Basell Polyolefine Gmbh | Impact resistant LLDPE composition and films made thereof |
US8846188B2 (en) | 2008-09-25 | 2014-09-30 | Basell Poliolefine GmbH | Impact resistant LLDPE composition and films made thereof |
CN102227452B (en) | 2008-12-01 | 2015-02-04 | 巴塞尔聚烯烃股份有限公司 | Process for polymerization of ethylene, and ethylene polymers having broad molecular weight distribution and long-chain branching |
US8664140B2 (en) | 2008-12-17 | 2014-03-04 | Basell Polyolefine Gmbh | Catalyst system for olefin polymerization, its production and use |
US9828699B2 (en) | 2009-09-21 | 2017-11-28 | Basell Poliolefine Italia S.R.L. | Polymer filament |
WO2011061087A1 (en) | 2009-11-17 | 2011-05-26 | Basell Poliolefine Italia S.R.L. | Soft polyolefin compositions with improved processability |
CN106947166A (en) | 2009-11-24 | 2017-07-14 | 巴塞尔聚烯烃意大利有限责任公司 | Polyolefin composition with improvement sealability |
EP2576642B1 (en) | 2010-05-28 | 2017-08-16 | Basell Polyolefine GmbH | Process for preparing a supported catalyst system for olefin polymerization, the catalyst system and its use |
US8916648B2 (en) | 2010-10-15 | 2014-12-23 | Basell Poliolefine Italia S.R.L. | Polymer filament |
EP2655445B1 (en) | 2010-12-22 | 2014-11-26 | Basell Polyolefine GmbH | Process for controlling the relative activity of active centers of catalyst systems comprising at least one late transition metal catalyst component and at least one ziegler catalyst component |
EP2607391A1 (en) | 2011-12-21 | 2013-06-26 | Basell Polyolefine GmbH | Process for controlling the polymer composition of an ethylene copolymer obtained by a catalyst system comprising a transition metal catalyst component and a Ziegler catalyst component |
JP6434660B2 (en) | 2015-05-26 | 2018-12-05 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | Polyolefin gasket for closure |
EP4153669A1 (en) | 2020-05-22 | 2023-03-29 | Basell Poliolefine Italia S.r.l. | Highly filled and flexible polyolefin composition |
US20240043672A1 (en) | 2020-12-15 | 2024-02-08 | Basell Poliolefine Italia S.R.L. | Polyolefin composition with high transparency |
WO2023104697A1 (en) | 2021-12-10 | 2023-06-15 | Basell Poliolefine Italia S.R.L. | Polyolefin filament |
WO2023104696A1 (en) | 2021-12-10 | 2023-06-15 | Basell Poliolefine Italia S.R.L. | Polyolefin filament |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991009882A1 (en) * | 1990-01-02 | 1991-07-11 | Exxon Chemical Patents Inc. | Supported ionic metallocene catalysts for olefin polymerization |
JP2882241B2 (en) * | 1993-06-07 | 1999-04-12 | 東ソー株式会社 | Olefin polymerization catalyst and olefin polymerization method |
US5498582A (en) * | 1993-12-06 | 1996-03-12 | Mobil Oil Corporation | Supported metallocene catalysts for the production of polyolefins |
US5939347A (en) * | 1995-01-25 | 1999-08-17 | W.R. Grace & Co. -Conn. | Supported catalytic activator |
DE69611554T2 (en) * | 1995-02-20 | 2001-07-05 | Tosoh Corp | Catalyst for the polymerization of olefins and process for the preparation of olefin polymers |
DE19606167A1 (en) * | 1996-02-20 | 1997-08-21 | Basf Ag | Supported catalyst systems |
-
1998
- 1998-03-05 EP EP98920472A patent/EP0931099A1/en not_active Withdrawn
- 1998-03-05 CA CA 2262493 patent/CA2262493A1/en not_active Abandoned
- 1998-03-05 AU AU73323/98A patent/AU7332398A/en not_active Abandoned
- 1998-03-05 WO PCT/EP1998/001231 patent/WO1998040419A1/en not_active Application Discontinuation
-
1999
- 1999-03-08 NO NO991113A patent/NO991113L/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9840419A1 * |
Also Published As
Publication number | Publication date |
---|---|
AU7332398A (en) | 1998-09-29 |
CA2262493A1 (en) | 1998-09-17 |
NO991113D0 (en) | 1999-03-08 |
NO991113L (en) | 1999-05-07 |
WO1998040419A1 (en) | 1998-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0931099A1 (en) | Method for producing olefin polymers with a higher melting point | |
EP1054911B1 (en) | Catalyst system, method for the production thereof and its use for the polymerization of olefins | |
EP0859800B1 (en) | Supported catalyst system, process for its production and its use in polymerising olefines | |
EP0942938B1 (en) | Supported catalyst system, method for the production and use thereof in olefin polymerization | |
EP1396495B1 (en) | Metallocenes with a single halogenide attached to the metal | |
WO1999033881A1 (en) | Supported catalyst system for the polymerisation of olefins | |
WO2000044799A1 (en) | Organometal compound, catalyst system containing said organometal compound and its use | |
EP1771484A1 (en) | Method for producing ultrahigh molecular weight polymers while using unbridged metallocene catalysts | |
EP0687682A1 (en) | Transition metal compounds | |
EP1082353B1 (en) | Catalyst system and the use of said catalyst system for polymerising propylene | |
EP1000073B1 (en) | Method for producing metallocenes | |
EP1003757B1 (en) | Method for producing metallocenes | |
EP0811640A1 (en) | Supported catalyst system, process for its preparation and its use in the polymerization of olefins | |
EP1054914B1 (en) | Zwitterionic, neutral transition metal compound | |
DE19922020A1 (en) | Transition metal compound, catalyst system, process for its preparation and its use for the polymerization of olefins | |
EP0780402B1 (en) | Supported catalyst system, process for production of the same and the use thereof for the polymerization of olefins | |
WO2000020466A1 (en) | Catalyst system | |
DE19823172A1 (en) | Metallocene catalyst system used in (co)polyolefin production | |
DE19757262A1 (en) | Production of polyolefin with a high melting point | |
DE19713549A1 (en) | Supported catalyst system for olefin polymerisation | |
DE19713550A1 (en) | Supported catalyst system for olefin polymerisation | |
WO2001014429A1 (en) | Supported catalyst systems, method for the production thereof and method for producing poly-1 alkenes with bimodal or multimodal molecular weight distribution | |
DE19900585A1 (en) | Purification of metallocene compounds for use as olefin polymerization catalysts involves replacing halide by other negative ligands, e.g. phenolate, and recrystallizing the more soluble metallocene obtained |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19990521 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE ES FI FR GB IT NL |
|
17Q | First examination report despatched |
Effective date: 20000419 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: BASELL POLYOLEFINE GMBH |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: BASELL POLYOLEFINE GMBH |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: BASELL POLYOLEFINE GMBH |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: BASELL POLYOLEFINE GMBH |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20060607 |