RU2015114100A - Способы контролирования полимеризации олефинов с применением двухкомпонентного катализатора - Google Patents

Способы контролирования полимеризации олефинов с применением двухкомпонентного катализатора Download PDF

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RU2015114100A
RU2015114100A RU2015114100A RU2015114100A RU2015114100A RU 2015114100 A RU2015114100 A RU 2015114100A RU 2015114100 A RU2015114100 A RU 2015114100A RU 2015114100 A RU2015114100 A RU 2015114100A RU 2015114100 A RU2015114100 A RU 2015114100A
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Цин ЯН
Тони Р. КРЭЙН
Джерри Т. ЛЭНИЕР
Джефф С. ФОДОР
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ШЕВРОН ФИЛЛИПС КЕМИКАЛ КОМПАНИ ЭлПи
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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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
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    • 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
    • C08F2400/00—Characteristics for processes of polymerization
    • C08F2400/02—Control or adjustment of polymerization parameters
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    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
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    • 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
    • C08F4/65925—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 non-bridged
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
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    • 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

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

1. Способ полимеризации, включающий:(1) приведение двухкомпонентной каталитической системы в контакт с олефиновым мономером и факультативным олефиновым сомономером в системе реакторов полимеризации в условиях полимеризации с получением олефинового полимера,где олефиновый полимер содержит более высокомолекулярный компонент и более низкомолекулярный компонент,где двухкомпонентная каталитическая система содержит первый компонент на основе металлоценового катализатора и второй компонент на основе металлоценового катализатора, игде условия полимеризации включают температуру реакции и время пребывания двухкомпонентной каталитической системы; и(2) контролирование массового отношения более высокомолекулярного компонента к более низкомолекулярному компоненту путем регулирования температуры реакции, где массовое отношение более высокомолекулярного компонента к более низкомолекулярному компоненту возрастает при увеличении температуры реакции.2. Способ по п. 1, отличающийся тем, что температура реакции находится в любом из диапазонов температур реакции, описанных в настоящей заявке.3. Способ по любому из пп. 1 или 2, отличающийся тем, что температура реакции находится в диапазоне от примерно 60°C до примерно 110°C или от примерно 80°C до примерно 105°C.4. Способ по любому из пп. 1 или 2, отличающийся тем, что массовое отношение более высокомолекулярного компонента к более низкомолекулярному компоненту возрастает при увеличении времени пребывания (или времени взаимодействия) двухкомпонентной каталитической системы.5. Способ по любому из пп. 1 или 2, отличающийся тем, что время пребывания двухкомпонентной каталитической системы находится

Claims (15)

1. Способ полимеризации, включающий:
(1) приведение двухкомпонентной каталитической системы в контакт с олефиновым мономером и факультативным олефиновым сомономером в системе реакторов полимеризации в условиях полимеризации с получением олефинового полимера,
где олефиновый полимер содержит более высокомолекулярный компонент и более низкомолекулярный компонент,
где двухкомпонентная каталитическая система содержит первый компонент на основе металлоценового катализатора и второй компонент на основе металлоценового катализатора, и
где условия полимеризации включают температуру реакции и время пребывания двухкомпонентной каталитической системы; и
(2) контролирование массового отношения более высокомолекулярного компонента к более низкомолекулярному компоненту путем регулирования температуры реакции, где массовое отношение более высокомолекулярного компонента к более низкомолекулярному компоненту возрастает при увеличении температуры реакции.
2. Способ по п. 1, отличающийся тем, что температура реакции находится в любом из диапазонов температур реакции, описанных в настоящей заявке.
3. Способ по любому из пп. 1 или 2, отличающийся тем, что температура реакции находится в диапазоне от примерно 60°C до примерно 110°C или от примерно 80°C до примерно 105°C.
4. Способ по любому из пп. 1 или 2, отличающийся тем, что массовое отношение более высокомолекулярного компонента к более низкомолекулярному компоненту возрастает при увеличении времени пребывания (или времени взаимодействия) двухкомпонентной каталитической системы.
5. Способ по любому из пп. 1 или 2, отличающийся тем, что время пребывания двухкомпонентной каталитической системы находится в диапазоне от примерно 10 мин до примерно 2 ч или от примерно 15 мин до примерно 90 мин.
6. Способ по любому из пп. 1 или 2, отличающийся тем, что массовое отношение более высокомолекулярного компонента к более низкомолекулярному компоненту находится в диапазоне от примерно 1:100 до примерно 100:1, от примерно 1:10 до примерно 10:1 или от примерно 1:5 до примерно 5:1.
7. Способ по любому из пп. 1 или 2, отличающийся тем, что % твердых веществ в реакторе находится в диапазоне от примерно 30 до примерно 65 масс. %.
8. Способ по любому из пп. 1 или 2, отличающийся тем, что % твердых веществ в реакторе находится в диапазоне от примерно 30 до примерно 55 масс. %.
9. Способ по любому из пп. 1 или 2, отличающийся тем, что система реакторов полимеризации содержит суспензионный реактор, газофазный реактор, растворный реактор или их комбинацию.
10. Способ по любому из пп. 1 или 2, отличающийся тем, что система реакторов полимеризации содержит суспензионный реактор.
11. Способ по любому из пп. 1 или 2, отличающийся тем, что система реакторов полимеризации содержит один реактор.
12. Способ по любому из пп. 1 или 2, отличающийся тем, что система реакторов полимеризации содержит 2 реактора.
13. Способ по любому из пп. 1 или 2, отличающийся тем, что массовое отношение первого компонента на основе металлоценового катализатора ко второму компоненту на основе металлоценового катализатора находится в диапазоне от примерно 1:100 до примерно 100:1, от примерно 1:5 до примерно 5:1 или от примерно 1:2 до примерно 2:1.
14. Способ по любому из пп. 1 или 2, дополнительно включающий стадию регулирования массового отношения первого компонента на основе металлоценового катализатора ко второму компоненту на основе металлоценового катализатора.
15. Способ по любому из пп. 1 или 2, дополнительно включающий стадию определения (или измерения) массового отношения более высокомолекулярного компонента к более низкомолекулярному компоненту и регулирования температуры реакции и/или времени пребывания двухкомпонентной каталитической системы на основе разницы между измеренным массовым отношением и требуемым массовым отношением.
RU2015114100A 2012-09-24 2013-09-16 Способы контролирования полимеризации олефинов с применением двухкомпонентного катализатора RU2642434C2 (ru)

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US13/625,065 2012-09-24
US13/625,065 US8940842B2 (en) 2012-09-24 2012-09-24 Methods for controlling dual catalyst olefin polymerizations
PCT/US2013/059961 WO2014047010A1 (en) 2012-09-24 2013-09-16 Methods for controlling dual catalyst olefin polymerizations

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US8940842B2 (en) 2015-01-27
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