RU2015143202A - Бис(2-инденил)металлоценовый комплекс - Google Patents
Бис(2-инденил)металлоценовый комплекс Download PDFInfo
- Publication number
- RU2015143202A RU2015143202A RU2015143202A RU2015143202A RU2015143202A RU 2015143202 A RU2015143202 A RU 2015143202A RU 2015143202 A RU2015143202 A RU 2015143202A RU 2015143202 A RU2015143202 A RU 2015143202A RU 2015143202 A RU2015143202 A RU 2015143202A
- Authority
- RU
- Russia
- Prior art keywords
- metallocene complex
- complex according
- butyl
- olefin
- indenyl
- Prior art date
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- -1 2-INDENYL Chemical class 0.000 title claims 4
- 239000002184 metal Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims 7
- 150000001336 alkenes Chemical class 0.000 claims 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 4
- 239000010936 titanium Substances 0.000 claims 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 3
- 230000015572 biosynthetic process Effects 0.000 claims 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 230000003993 interaction Effects 0.000 claims 3
- 239000003446 ligand Substances 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 3
- 229920000098 polyolefin Polymers 0.000 claims 3
- 239000002243 precursor Substances 0.000 claims 3
- 229910052719 titanium Inorganic materials 0.000 claims 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 2
- 229910052735 hafnium Chemical group 0.000 claims 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 2
- 150000002430 hydrocarbons Chemical group 0.000 claims 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- CCUYEVNCRQDQRF-UHFFFAOYSA-N 2-bromo-1h-indene Chemical compound C1=CC=C2CC(Br)=CC2=C1 CCUYEVNCRQDQRF-UHFFFAOYSA-N 0.000 claims 1
- 239000007818 Grignard reagent Substances 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 150000004795 grignard reagents Chemical class 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 229920000092 linear low density polyethylene Polymers 0.000 claims 1
- 239000004707 linear low-density polyethylene Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims 1
- YAJATQWDNWKSKE-UHFFFAOYSA-N sodium;trimethyl(trimethylsilyloxy)silane Chemical compound [Na].C[Si](C)(C)O[Si](C)(C)C YAJATQWDNWKSKE-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
Classifications
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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
- 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
- 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
-
- 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
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/09—Long chain branches
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/10—Short chain branches
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Claims (25)
1. Металлоценовый комплекс формулы (1)
где R1 и R2 являются одинаковыми или различными и независимо выбраны из группы, состоящей из замещенных и незамещенных линейных и разветвленных углеводородных групп, содержащих 1-30 атомов углерода;
М представляет собой титан, цирконий или гафний и
X1 и Х2 являются одинаковыми и выбраны из группы, состоящей из галогена и углеводородных групп, содержащих 1-20 атомов углерода.
2. Металлоценовый комплекс по п. 1, где R1 и R2 выбраны из метила, этила, н-пропила, н-бутила, н-пентила, н-гексила, фенила, 1-инденила, 2-инденила или R1 и R2 образуют кольцо вместе с атомом углерода, с которым они связаны, образуя 5- или 6-членное кольцо, которое может быть замещенным или незамещенным.
3. Металлоценовый комплекс по п. 1 или 2, где R1 и R2 являются одинаковыми.
4. Металлоценовый комплекс по п. 1 или 2, где R1 и R2 выбраны из н-пропила, н-бутила, н-пентила и н-гексила.
5. Металлоценовый комплекс по п. 1 или 2, где М представляет собой титан.
6. Металлоценовый комплекс по п. 1 или 2, где X1 и Х2 представляют собой Cl.
7. Композиция, содержащая металлоценовый комплекс по любому из пп. 1-6, в которой металлоценовый комплекс нанесен на носитель.
8. Способ получения металлоценового комплекса по любому из пп. 1-6, включающий следующие стадии:
a. превращение 2-броминдена в соответствующий реагент Гриньяра 2-инден-MgBr;
b. взаимодействие 2-иден-MgBr с три-н-бутилхлоридом, которое дает
(2-С9Н7)Mg(н-бутил)3;
c. взаимодействие (2-С9Н7)Mg(н-бутил)3 с Br2C=CR1R2 в условиях Pd катализа с образованием предшественников лигандов,
d. образование анионов предшественников лигандов с натрийгексаметилдисилоксаном;
e. взаимодействие аниона предшественника лиганда с (Me2N)2MCl2, где M представляет собой титан (Ti), цирконий (Zr) или гафний (Hf), и затем с триметилсилилхлоридом, которое приводит к образованию металлоценового комплекса по любому из пп. 1-6.
9. Способ получения олефиновых полимеров полимеризацией одного или нескольких олефинов в присутствии металлоценового комплекса по любому из пп. 1-6 или в присутствии композиции по п. 7 и сокатализатора.
10. Способ по п. 9, в котором по меньшей мере один олефин представляет собой этилен.
11. Способ по п. 9 или 10, в котором используют смесь этилена с по меньшей мере одним другим олефином.
12. Способ по п. 11, где другой олефин выбирают из 1-бутена, 1-гексена или 1-октена.
13. Способ по п. 9 или 10, в котором участвует алюминийорганический сокатализатор.
14. Полиолефин, предпочтительно полиэтилен, более предпочтительно линейный полиэтилен низкой плотности, получаемый способом по любому из пп. 9-13.
15. Полиолефин по п. 14, в котором количество разветвлений на 1000 атомов углерода, определенное с использованием 13С ЯМР, составляет по меньшей мере 18.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13001242.0 | 2013-03-12 | ||
| EP13001242 | 2013-03-12 | ||
| US201461927084P | 2014-01-14 | 2014-01-14 | |
| US61/927,084 | 2014-01-14 | ||
| PCT/EP2014/054578 WO2014139949A1 (en) | 2013-03-12 | 2014-03-10 | Bis(2-indenyl) metallocene complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| RU2015143202A true RU2015143202A (ru) | 2017-04-17 |
Family
ID=47877720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| RU2015143202A RU2015143202A (ru) | 2013-03-12 | 2014-03-10 | Бис(2-инденил)металлоценовый комплекс |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US9156929B2 (ru) |
| EP (1) | EP2970348A1 (ru) |
| JP (1) | JP2016516019A (ru) |
| CN (1) | CN105073764A (ru) |
| BR (1) | BR112015019437A2 (ru) |
| RU (1) | RU2015143202A (ru) |
| WO (1) | WO2014139949A1 (ru) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104379680B (zh) * | 2012-08-03 | 2017-11-28 | 埃克森美孚化学专利公司 | 具有长链支化的乙烯基封端的聚烯烃 |
| US9382349B2 (en) * | 2012-08-03 | 2016-07-05 | Exxonmobil Chemical Patents Inc. | Polyalphaolefins prepared using modified Salan catalyst compounds |
| EP2880096B1 (en) * | 2012-08-03 | 2018-01-03 | ExxonMobil Chemical Patents Inc. | Process for preparing polyalphaolefins using modified salan catalyst compounds and polyalphaolefins prepared therewith |
| KR102667176B1 (ko) | 2015-05-27 | 2024-05-20 | 사빅 글로벌 테크놀러지스 비.브이. | 메탈로센 착체 및 조촉매를 포함하는 촉매 |
| EP3400230B1 (en) | 2016-01-05 | 2019-09-11 | SABIC Global Technologies B.V. | Catalyst comprising a metallocene complex and a co-catalyst |
| US11155659B2 (en) * | 2017-04-04 | 2021-10-26 | Sabic Global Technologies B.V. | Dimethyl-silyl-bridged-1-substituted-2-indenyl metallocene complexes for olefin polymerization |
| CN110650965B (zh) | 2017-04-04 | 2022-10-04 | Sabic环球技术有限责任公司 | 用于烯烃聚合的二烃基-甲硅烷基-桥连-1,3二取代-2-茚基茂金属络合物 |
| US11472895B2 (en) | 2018-08-30 | 2022-10-18 | Sabic Global Technologies B.V. | Substituted bis-2-indenyl metallocene compounds |
| EP4031592B1 (en) | 2019-09-20 | 2025-04-30 | SABIC Global Technologies B.V. | Compounds for use in catalyst compositions for the production of polyolefins |
| CN115485311B (zh) * | 2020-02-24 | 2024-12-06 | 埃克森美孚化学专利公司 | 用于生产乙烯叉基封端的聚α-烯烃的柄型-双(茚-2-基)催化剂 |
| WO2025172436A1 (en) | 2024-02-14 | 2025-08-21 | Sabic Global Technologies B.V. | Metallocene complexes with vinylene bridge for alpha-olefin polymerization |
| LU506875B1 (en) | 2024-04-10 | 2025-10-10 | Saudi Arabian Oil Company Saudi Aramco | Metallocene complexes with vinylene bridge for alpha-olefin polymerization |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2952697A (en) * | 1958-10-07 | 1960-09-13 | Ethyl Corp | Cyclopentadienyl metal compounds |
| US4003712A (en) | 1970-07-29 | 1977-01-18 | Union Carbide Corporation | Fluidized bed reactor |
| DE3743321A1 (de) * | 1987-12-21 | 1989-06-29 | Hoechst Ag | 1-olefinpolymerwachs und verfahren zu seiner herstellung |
| DE3922546A1 (de) * | 1989-07-08 | 1991-01-17 | Hoechst Ag | Verfahren zur herstellung von cycloolefinpolymeren |
| ES2087339T3 (es) * | 1991-05-27 | 1996-07-16 | Hoechst Ag | Procedimiento para la preparacion de poliolefinas con amplia distribucion de masas moleculares. |
| DE4121368A1 (de) * | 1991-06-28 | 1993-01-07 | Hoechst Ag | Katalysator und verfahren zur herstellung von hochmolekularen polyolefinen |
| JP3379172B2 (ja) | 1993-11-11 | 2003-02-17 | 東ソー株式会社 | エチレン・α−オレフィン共重合体 |
| JPH08259619A (ja) * | 1995-03-20 | 1996-10-08 | Tokuyama Corp | ポリオレフィンの製造方法および触媒 |
| DK0830395T3 (da) | 1995-05-09 | 2001-08-06 | Fina Research | Fremgangsmåde til fremstilling og anvendelse af en støttet katalysator af metalagtigt aluminiumoxan |
| EP0786466B1 (en) | 1996-01-25 | 2003-04-16 | Tosoh Corporation | Olefin polymerisation process which comprises a transition metal catalyst. |
| EP0969019A1 (en) | 1998-07-02 | 2000-01-05 | Fina Research S.A. | Polyolefin production |
| DE60020694T2 (de) * | 2000-08-07 | 2006-05-04 | Total Petrochemicals Research Feluy, Seneffe | Polyolefinherstellung |
| US20050137364A1 (en) | 2003-12-23 | 2005-06-23 | Univation Technologies, Llc | Condensing mode operation of gas-phase polymerization reactor |
| CN1637023A (zh) * | 2004-12-09 | 2005-07-13 | 中山大学 | 乙烯聚合单核及多核苊二亚胺镍催化剂及其制备方法 |
-
2014
- 2014-03-10 CN CN201480013483.7A patent/CN105073764A/zh active Pending
- 2014-03-10 EP EP14710230.5A patent/EP2970348A1/en not_active Withdrawn
- 2014-03-10 RU RU2015143202A patent/RU2015143202A/ru not_active Application Discontinuation
- 2014-03-10 WO PCT/EP2014/054578 patent/WO2014139949A1/en not_active Ceased
- 2014-03-10 BR BR112015019437A patent/BR112015019437A2/pt not_active IP Right Cessation
- 2014-03-10 JP JP2015562070A patent/JP2016516019A/ja active Pending
- 2014-03-12 US US14/205,530 patent/US9156929B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| BR112015019437A2 (pt) | 2017-07-18 |
| US20140275455A1 (en) | 2014-09-18 |
| EP2970348A1 (en) | 2016-01-20 |
| CN105073764A (zh) | 2015-11-18 |
| US9156929B2 (en) | 2015-10-13 |
| WO2014139949A1 (en) | 2014-09-18 |
| JP2016516019A (ja) | 2016-06-02 |
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