CN1138796C - 烯烃共聚合用的桥连茂金属 - Google Patents
烯烃共聚合用的桥连茂金属 Download PDFInfo
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- CN1138796C CN1138796C CNB998123811A CN99812381A CN1138796C CN 1138796 C CN1138796 C CN 1138796C CN B998123811 A CNB998123811 A CN B998123811A CN 99812381 A CN99812381 A CN 99812381A CN 1138796 C CN1138796 C CN 1138796C
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- cyclopentadienyl
- compound
- phenyl
- polymerization
- fluorenyl
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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
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- 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
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- 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
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- 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
-
- 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
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/10—Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
-
- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Ex# | μmol催化剂 | μmol活化剂 | 聚合物质量 | Wt%C3(IR) | Mw(LS) | Mw/Mn(DRI) |
9a | 0.13 | 0.79 | 12.41 | 32 | 629427 | 1.85 |
9b | 0.11 | 0.79 | 11.79 | 31 | 647659 | 1.7 |
9c | 0.12 | 0.79 | 10.33 | 32 | 575956 | 1.9 |
10a | 0.056 | 6.2 | 11.42 | 32 | 557884 | 1.95 |
10b | 0.094 | 1.5 | 11.28 | 32.5 | 589690 | 1.9 |
11a(Comp) | 0.70 | 3.8 | 2.92 | 32 | 573913 | 1.9 |
11b(Comp) | 0.893 | 3.8 | 0.7 | a | a | a |
12a | 0.183b | 0.79 | 12.60 | 31 | 510697 | 2.0 |
12b | 0.183b | 0.79 | 6.77 | 33.5 | 492952 | 2.0 |
12c(Comp) | c | 0.79 | 0.4 | a | a | a |
12d(Comp) | c | 0.79 | 0 | a | a | a |
预催化剂 | 所用预催化剂(μmol) | 共聚物产量(g) | Mol%辛烯 | Mw(DRI) | Mw/Mn(DRI) | Mw(LS) |
A | 2.1 | 12.18 | 6.4 | 195692 | 3.12 | 225188 |
A | 1.5 | 12.79 | 6.1 | 190771 | 2.30 | 210680 |
A | 2.2 | 13.82 | 6.4 | 207125 | 2.30 | 248319 |
A | 2.4 | 14.98 | 6.1 | 219112 | 2.43 | 254290 |
B | 5.0 | 12.40 | 7.3 | 150225 | 2.22 | 177924 |
B | 4.4 | 12.98 | 7.6 | 163758 | 2.22 | 194604 |
D | 5.8 | 12.49 | 9.5 | 140664 | 2.25 | 173690 |
D | 4.2 | 12.25 | 7.5 | 154822 | 2.20 | 189865 |
实施例14# | 催化剂 | 活化剂 | 催化剂进料(mg/hr) | 活化剂进料(mg/hr) | 烷基铝(mmol/l) | Rt(min) | 温度(℃) | 压力(巴) | 溶剂(kg/hr) | C2进料(kg/hr) | C8进料(kg/hr) |
a) | A | (F5C6)4B-(1) | 3.3 | 2.7 | 0.015 | 7.2 | 190 | 85.8 | 5.5 | 1.16 | 0.53 |
b) | A | (F7C10)4B-(2) | 5.2 | 5.8 | 0.015 | 7.0 | 196 | 85.8 | 5.7 | 1.17 | 0.54 |
实施例14# | C2转化率(%) | C8转化率(%) | 生产速率(kg/hr) | 催化剂效率(kgPE/mg Cat) | MI(dg/min) | MIR(I21/12) | 密度(kg/m3) | C8结合量(wt%) | Mw(kg/mol) | PDI(Mw/Mn) |
a) | 84 | 48 | 1.46 | 440 | 0.84 | 39 | 903 | 17 | 95 | 2.3 |
b) | 85 | 45 | 1.47 | 280 | 0.96 | 42 | 909 | 16 | 89 | 2.2 |
Claims (20)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10532998P | 1998-10-23 | 1998-10-23 | |
US60/105,329 | 1998-10-23 | ||
US13106799P | 1999-04-26 | 1999-04-26 | |
US60/131,067 | 1999-04-26 |
Publications (2)
Publication Number | Publication Date |
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CN1328580A CN1328580A (zh) | 2001-12-26 |
CN1138796C true CN1138796C (zh) | 2004-02-18 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB998123811A Expired - Lifetime CN1138796C (zh) | 1998-10-23 | 1999-10-22 | 烯烃共聚合用的桥连茂金属 |
Country Status (15)
Country | Link |
---|---|
US (2) | US6528670B1 (zh) |
EP (1) | EP1196464B9 (zh) |
JP (1) | JP4689829B2 (zh) |
KR (1) | KR100568839B1 (zh) |
CN (1) | CN1138796C (zh) |
AT (1) | ATE284422T1 (zh) |
AU (1) | AU757241B2 (zh) |
BR (1) | BR9914717A (zh) |
CA (1) | CA2345628C (zh) |
DE (1) | DE69922548T2 (zh) |
ES (1) | ES2233109T3 (zh) |
HK (1) | HK1041705A1 (zh) |
MX (1) | MXPA01003978A (zh) |
RU (1) | RU2232766C2 (zh) |
WO (1) | WO2000024793A1 (zh) |
Families Citing this family (70)
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JP4610859B2 (ja) * | 2002-09-27 | 2011-01-12 | 三井化学株式会社 | オレフィン重合用の架橋メタロセン化合物およびそれを用いたオレフィンの重合方法 |
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DE3907964A1 (de) | 1989-03-11 | 1990-09-13 | Hoechst Ag | Verfahren zur herstellung eines syndiotaktischen polyolefins |
DE3916553A1 (de) * | 1989-05-20 | 1990-11-22 | Hoechst Ag | Syndio- isoblockpolymer und verfahren zu seiner herstellung |
DE69107006T2 (de) | 1990-10-17 | 1995-09-21 | Idemitsu Kosan Co | Verfahren zur Herstellung von Oligomeren auf Basis von Propylen. |
WO1992009640A1 (en) | 1990-11-30 | 1992-06-11 | Idemitsu Kosan Co., Ltd. | Process for producing olefinic polymer |
JP3193066B2 (ja) | 1991-05-02 | 2001-07-30 | 三菱化学株式会社 | プロピレンランダム共重合体の製造法 |
US5401817A (en) | 1991-05-09 | 1995-03-28 | Phillips Petroleum Company | Olefin polymerization using silyl-bridged metallocenes |
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US6313240B1 (en) | 1993-02-22 | 2001-11-06 | Tosoh Corporation | Process for producing ethylene/α-olefin copolymer |
KR100311244B1 (ko) | 1993-02-22 | 2001-12-15 | 가지와라 야스시 | 에틸렌/α-올레핀공중합체의제조방법 |
US5631202A (en) * | 1993-09-24 | 1997-05-20 | Montell Technology Company B.V. | Stereospecific metallocene catalysts with stereolocking α-CP substituents |
CA2172635A1 (en) * | 1993-09-30 | 1995-04-06 | Noriyuki Tani | Transition metal compound, olefin polymerization catalyst, and process for producing olefin polymer by using said catalyst |
JP3423378B2 (ja) | 1993-11-12 | 2003-07-07 | 三井化学株式会社 | 新規な遷移金属化合物および該遷移金属化合物からなるオレフィン重合用触媒成分、該オレフィン重合用触媒成分を含むオレフィン重合用触媒ならびにオレフィンの重合方法 |
US5502017A (en) | 1994-03-10 | 1996-03-26 | Northwestern University | Metallocene catalyst containing bulky organic group |
IT1273420B (it) * | 1994-04-06 | 1997-07-08 | Spherilene Srl | Composti metallocenici, procedimento per la preparazione e loro utilizzo in catalizzatori per la polimerizzazione delle olefine |
EP0707016B1 (en) | 1994-10-13 | 1997-09-24 | Japan Polyolefins Co., Ltd. | Catalyst component for producing polyolefin, catalyst for producing polyolefin comprising the catalyst component, and process for producing polyolefin in the presence of the catalyst |
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JP3850048B2 (ja) | 1994-12-08 | 2006-11-29 | 東ソー株式会社 | 有機遷移金属化合物およびそれを用いたポリオレフィンの製造方法 |
AT403376B (de) * | 1995-07-03 | 1998-01-26 | Danubia Petrochem Polymere | Metallocene mit silylsubstituierten brücken und deren einsatz für die olefinpolymerisation |
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-
1999
- 1999-10-22 US US09/426,099 patent/US6528670B1/en not_active Expired - Lifetime
- 1999-10-22 RU RU2001113445/04A patent/RU2232766C2/ru not_active IP Right Cessation
- 1999-10-22 KR KR1020017004930A patent/KR100568839B1/ko not_active IP Right Cessation
- 1999-10-22 CN CNB998123811A patent/CN1138796C/zh not_active Expired - Lifetime
- 1999-10-22 BR BR9914717-3A patent/BR9914717A/pt not_active IP Right Cessation
- 1999-10-22 MX MXPA01003978A patent/MXPA01003978A/es not_active IP Right Cessation
- 1999-10-22 AU AU13212/00A patent/AU757241B2/en not_active Ceased
- 1999-10-22 JP JP2000578362A patent/JP4689829B2/ja not_active Expired - Lifetime
- 1999-10-22 CA CA2345628A patent/CA2345628C/en not_active Expired - Fee Related
- 1999-10-22 EP EP99974265A patent/EP1196464B9/en not_active Expired - Lifetime
- 1999-10-22 DE DE69922548T patent/DE69922548T2/de not_active Expired - Lifetime
- 1999-10-22 WO PCT/US1999/024944 patent/WO2000024793A1/en active IP Right Grant
- 1999-10-22 ES ES99974265T patent/ES2233109T3/es not_active Expired - Lifetime
- 1999-10-22 AT AT99974265T patent/ATE284422T1/de not_active IP Right Cessation
-
2002
- 2002-03-07 US US10/092,660 patent/US6506857B2/en not_active Expired - Lifetime
- 2002-05-03 HK HK02103341.8A patent/HK1041705A1/zh unknown
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ES2233109T3 (es) | 2005-06-01 |
MXPA01003978A (es) | 2003-06-06 |
AU1321200A (en) | 2000-05-15 |
CA2345628C (en) | 2010-02-16 |
WO2000024793A1 (en) | 2000-05-04 |
WO2000024793A8 (en) | 2001-10-11 |
HK1041705A1 (zh) | 2002-07-19 |
EP1196464A1 (en) | 2002-04-17 |
US6506857B2 (en) | 2003-01-14 |
EP1196464B1 (en) | 2004-12-08 |
JP4689829B2 (ja) | 2011-05-25 |
BR9914717A (pt) | 2001-07-10 |
CN1328580A (zh) | 2001-12-26 |
AU757241B2 (en) | 2003-02-06 |
CA2345628A1 (en) | 2000-05-04 |
ATE284422T1 (de) | 2004-12-15 |
KR100568839B1 (ko) | 2006-04-10 |
RU2232766C2 (ru) | 2004-07-20 |
US6528670B1 (en) | 2003-03-04 |
JP2002528463A (ja) | 2002-09-03 |
DE69922548D1 (de) | 2005-01-13 |
DE69922548T2 (de) | 2006-01-05 |
KR20010099705A (ko) | 2001-11-09 |
EP1196464B9 (en) | 2005-03-23 |
US20020137959A1 (en) | 2002-09-26 |
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Correction item: Priority Correct: 1999.10.23 US 60/105,329|1994.04.26 US 60/131,067 False: 1998.10.23 US 60/105,329 Number: 7 Page: 400 Volume: 20 |
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CI03 | Correction of invention patent |
Correction item: Priority Correct: 1999.10.23 US 60/105,329|1994.04.26 US 60/131,067 False: 1998.10.23 US 60/105,329 Number: 7 Page: The title page Volume: 20 |
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Free format text: CORRECT: PRIORITY; FROM: 1998.10.23 US 60/105,329 TO: 1998.10.23 US 60/105,329 1999.4.26 US 60/131,067 |
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Correction item: Priority Correct: 1990.10.23 US 60/105,329|1999.04.26 US 60/131,067 False: 1998.10.23 US 60/105,329 Number: 7 Volume: 20 |
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CI03 | Correction of invention patent |
Correction item: Priority Correct: 1990.10.23 US 60/105,329|1999.04.26 US 60/131,067 False: 1998.10.23 US 60/105,329 Number: 7 Page: The title page Volume: 20 |
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