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RU2008110052A - Олефиновые блок-сополимеры, получаемые каталитически с использованием полимеризуемого челночного агента - Google Patents

Олефиновые блок-сополимеры, получаемые каталитически с использованием полимеризуемого челночного агента Download PDF

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RU2008110052A
RU2008110052A RU2008110052/04A RU2008110052A RU2008110052A RU 2008110052 A RU2008110052 A RU 2008110052A RU 2008110052/04 A RU2008110052/04 A RU 2008110052/04A RU 2008110052 A RU2008110052 A RU 2008110052A RU 2008110052 A RU2008110052 A RU 2008110052A
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polymerization
polymerizable
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Дэниел Дж. ЭРРАЙОЛА (US)
Дэниел Дж. ЭРРАЙОЛА
Эдмунд М. КАРНАХАН (US)
Эдмунд М. КАРНАХАН
Дэвид Д. ДИВОУР (US)
Дэвид Д. ДИВОУР
Филлип Д. ХАСТЭД (US)
Филлип Д. ХАСТЭД
Брайан А. ЯЖДЖЕВСКИ (US)
Брайан А. ЯЖДЖЕВСКИ
Роджер Л. КУЛМАН (US)
Роджер Л. КУЛМАН
Фрэнсис Дж. ТИММЕРС (US)
Фрэнсис Дж. ТИММЕРС
Тимоти Т. ВЕНЦЕЛ (US)
Тимоти Т. ВЕНЦЕЛ
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Дау Глобал Текнолоджиз Инк. (Us)
Дау Глобал Текнолоджиз Инк.
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    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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    • 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
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • 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
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    • 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+
    • C—CHEMISTRY; METALLURGY
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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
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    • C08F4/00—Polymerisation catalysts
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    • 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

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Abstract

1. Способ получения разветвленного полимера, включающий полимеризацию одного или нескольких аддитивно полимеризуемых мономеров и полимеризуемого челночного агента в присутствии по крайней мере одного катализатора аддитивной полимеризации, содержащего соединение или комплекс металла, и сокатализатора в условиях, характеризующихся образованием разветвленного полимера, причем полимеризуемый челночный агент содержит один или несколько полимеризуемых фрагментов. ! 2. Способ по п.1, где по крайней мере некоторые из разветвлений представляют собой длинноцепочечные разветвления, образованные при полимеризации двух или нескольких мономерных единиц. ! 3. Способ по п.1, где различные сегменты полимера получают при различных условиях проведения процесса. ! 4. Способ по п.1, где в процессе полимеризации используют два или несколько катализаторов полимеризации. ! 5. Способ по п.4, где два или несколько катализаторов полимеризации применяют в раздельных реакторах полимеризации, соединенных последовательно. ! 6. Способ по п.4, где полимеризацию проводят в одном реакторе. ! 7. Способ по п.1, где катализатор представляет собой комплекс металла, соответствующий формуле: ! , ! где R11 выбирают из алкила, циклоалкила, гетероалкила, циклогетероалкила, арила или их инертно замещенных производных, содержащих от 1 до 30 атомов, не считая атомов водорода, или их двухвалентного производного; ! Т1 обозначает двухвалентную мостиковую группу, содержащую от 1 до 41 атомов, отличных от атомов водорода, предпочтительно от 1 до 20 атомов, отличных от атомов водорода, и наиболее предпочтительно обозначает метиленовую или силановую группу, замещенную одно�

Claims (15)

1. Способ получения разветвленного полимера, включающий полимеризацию одного или нескольких аддитивно полимеризуемых мономеров и полимеризуемого челночного агента в присутствии по крайней мере одного катализатора аддитивной полимеризации, содержащего соединение или комплекс металла, и сокатализатора в условиях, характеризующихся образованием разветвленного полимера, причем полимеризуемый челночный агент содержит один или несколько полимеризуемых фрагментов.
2. Способ по п.1, где по крайней мере некоторые из разветвлений представляют собой длинноцепочечные разветвления, образованные при полимеризации двух или нескольких мономерных единиц.
3. Способ по п.1, где различные сегменты полимера получают при различных условиях проведения процесса.
4. Способ по п.1, где в процессе полимеризации используют два или несколько катализаторов полимеризации.
5. Способ по п.4, где два или несколько катализаторов полимеризации применяют в раздельных реакторах полимеризации, соединенных последовательно.
6. Способ по п.4, где полимеризацию проводят в одном реакторе.
7. Способ по п.1, где катализатор представляет собой комплекс металла, соответствующий формуле:
Figure 00000001
,
где R11 выбирают из алкила, циклоалкила, гетероалкила, циклогетероалкила, арила или их инертно замещенных производных, содержащих от 1 до 30 атомов, не считая атомов водорода, или их двухвалентного производного;
Т1 обозначает двухвалентную мостиковую группу, содержащую от 1 до 41 атомов, отличных от атомов водорода, предпочтительно от 1 до 20 атомов, отличных от атомов водорода, и наиболее предпочтительно обозначает метиленовую или силановую группу, замещенную одной или двумя С1-20 углеводородными группами; и
R12 обозначает С5-20 гетероарильную группу, которая содержит функциональную группу, являющуюся основанием Льюиса, в частности, пиридин-2-ильную или замещенную пиридин-2-ильную группу, или ее двухвалентное производное;
М1 обозначает металл Группы 4, предпочтительно гафний;
Х1 обозначает анионную, нейтральную или дианионную лигандную группу;
х' означает число от 0 до 5, указывающее количество подобных групп Х1; и
связи, необязательные связи и электроно-донорные взаимодействия обозначены линиями, пунктирными линиями и стрелками, соответственно, или
комплекс металла, который соответствуют формуле:
Figure 00000002
,
где М2 обозначает металл Групп 4-10 Периодической таблицы элементов;
Т2 обозначает азот-, кислород- или фосфорсодержащую группу;
Х2 обозначает атом галогена, углеводородную группу или (углеводородный радикал)окси группу;
t равно один или два;
х" обозначает число, выбранное таким образом, чтобы обеспечить баланс зарядов; и
T2 и N соединены друг с другом мостиковым лигандом.
8. Способ получения многократно разветвленного псевдоблок-сополимера, включающий:
полимеризацию в реакторе полимеризации одного или нескольких олефиновых мономеров в присутствии катализатора полимеризации олефина и полимеризующегося челночного агента с образованием по крайней мере некоторого количества первичного полимера, содержащего функциональную группу челночного агента;
перегрузку продукта реакции из первого реактора или первой зоны во второй реактор полимеризации или вторую зону полимеризации, работающую при условиях полимеризации, которые отличны от условий полимеризации в первом реакторе полимеризации или первой зоне полимеризации;
перенос по крайней мере части первичного полимера, содержащего функциональную группу челночного агента, к активному участку катализатора во втором реакторе полимеризации или второй зоне полимеризации; и
проведение полимеризации во втором реакторе полимеризации или второй зоне полимеризации с образованием второго полимерного сегмента, связанного с частью или со всеми сегментами первичного полимера и имеющего полимерные свойства, отличные от полимерных свойств сегмента первичного полимера.
9. Способ получения многократно разветвленного псевдоблок-сополимера, включающего:
полимеризацию одного или нескольких олефиновых мономеров в присутствии катализатора полимеризации олефинов и полимеризуемого челночного агента (PSA) с образованием по крайней мере некоторого количества первичного полимера, содержащего на концах цепи челночный агент и содержащего аддитивно полимеризуемые функциональные группы;
продолжение полимеризации в том же самом или другом реакторе полимеризации, необязательно в присутствии одного или нескольких дополнительных катализаторов полимеризации, сокатализаторов, мономеров или челночных агентов с получением второго полимерного сегмента, связанного с частью или со всеми сегментами первичного полимера посредством аддитивно полимеризуемой функциональной группы PSA.
10. Разветвленный псевдоблок-сополимер, полученный или получаемый согласно способу по п.1.
11. Многократно разветвленный псевдоблок-сополимер по п.10.
12. Многократно разветвленный псевдоблок-сополимер по п.11, имеющий гребенчатую молекулярную структуру.
13. Многократно разветвленный псевдоблок-сополимер по п.11, имеющий дендримерный тип молекулярной структуры.
14. Разветвленный или многократно разветвленный псевдоблок-сополимер по пп.10, 11, 12 или 13, содержащий в полимеризованной форме этилен и сополимеризуемый мономер, пропилен и по крайней мере один сополимеризуемый мономер, содержащий от 4 до 20 атомов углерода, или 4-метил-1-пентен и по крайней мере один другой сополимеризуемый мономер, содержащий от 4 до 20 атомов углерода.
15. Смесь полимеров, содержащая: (1) органический или неорганический полимер, предпочтительно гомополимер этилена, сополимер этилена и способного к сополимеризации мономера или гомополимер пропилена; и (2) разветвленный псевдоблок-сополимер по любому из пп.10-13 или разветвленный сополимер, полученный способом по любому из пп.1-9.
RU2008110052/04A 2005-09-15 2006-09-14 Олефиновые блок-сополимеры, получаемые каталитически с использованием полимеризуемого челночного агента RU2008110052A (ru)

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