RU2011105195A - Каталитические составы, содержащие полуметаллоцены, и продукты полимеризации, полученные с их применением - Google Patents

Каталитические составы, содержащие полуметаллоцены, и продукты полимеризации, полученные с их применением Download PDF

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RU2011105195A
RU2011105195A RU2011105195/04A RU2011105195A RU2011105195A RU 2011105195 A RU2011105195 A RU 2011105195A RU 2011105195/04 A RU2011105195/04 A RU 2011105195/04A RU 2011105195 A RU2011105195 A RU 2011105195A RU 2011105195 A RU2011105195 A RU 2011105195A
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group
composition according
catalyst composition
substituted
oxide
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RU2011105195/04A
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RU2504556C2 (ru
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Мак П. МАКДЭНИЕЛ (US)
Мак П. МАКДЭНИЕЛ
Мэттью Дж. ТОРН (US)
Мэттью Дж. ТОРН
Элизабет А. БЕНХЭМ (US)
Элизабет А. БЕНХЭМ
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Шеврон Филлипс Кемикал Компани Лп (Us)
Шеврон Филлипс Кемикал Компани Лп
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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

1. Каталитический состав, содержащий продукт контакта гибридного металлоценового соединения с активатором, причем гибридное металлоценовое соединение имеет формулу: ! ! где М представляет собой Zr, Hf или Ti; ! X1 и X2 независимо представляют собой галид или замещенную или незамещенную алифатическую, ароматическую или циклическую группу, или их комбинацию; ! X3 представляет собой замещенный или незамещенный циклопентадиенил, инденил или флуоренил, при этом каждый из заместителей X3 группы независимо представляет собой атом водорода или замещенную или незамещенную алифатическую, ароматическую или циклическую группу, или их комбинацию; ! X4 представляет собой ! -O-RA, -NH-RA, -PH-RA, -S-RA, или -CRB=NRC, где ! RA представляет собой арильную группу, замещенную алкенильным заместителем, каждый из заместителей RA группы, отличные от алкенильного заместителя, независимо представляет собой атом водорода или замещенную или незамещенную алкильную, алкенильную или алкоксигруппу; и ! RB и RC независимо представляют собой атом водорода или замещенную или незамещенную алифатическую, ароматическую или циклическую группу, или их комбинацию. ! 2. Каталитический состав по п.1, отличающийся тем, что X1 и X2 независимо представляют собой метальную группу, фенильную группу, бензильную группу или галид. ! 3. Каталитический состав по п.1, отличающийся тем, что каждый из заместителей X3 независимо представляет собой атом водорода, метильную группу, этильную группу, пропильную группу, н-бутильную группу, трет-бутильную группу или гексильную группу. ! 4. Каталитический состав по п.1, отличающийся тем, что алкенильный заместитель R представляет собой этенил, пропе

Claims (19)

1. Каталитический состав, содержащий продукт контакта гибридного металлоценового соединения с активатором, причем гибридное металлоценовое соединение имеет формулу:
Figure 00000001
где М представляет собой Zr, Hf или Ti;
X1 и X2 независимо представляют собой галид или замещенную или незамещенную алифатическую, ароматическую или циклическую группу, или их комбинацию;
X3 представляет собой замещенный или незамещенный циклопентадиенил, инденил или флуоренил, при этом каждый из заместителей X3 группы независимо представляет собой атом водорода или замещенную или незамещенную алифатическую, ароматическую или циклическую группу, или их комбинацию;
X4 представляет собой
-O-RA, -NH-RA, -PH-RA, -S-RA, или -CRB=NRC, где
RA представляет собой арильную группу, замещенную алкенильным заместителем, каждый из заместителей RA группы, отличные от алкенильного заместителя, независимо представляет собой атом водорода или замещенную или незамещенную алкильную, алкенильную или алкоксигруппу; и
RB и RC независимо представляют собой атом водорода или замещенную или незамещенную алифатическую, ароматическую или циклическую группу, или их комбинацию.
2. Каталитический состав по п.1, отличающийся тем, что X1 и X2 независимо представляют собой метальную группу, фенильную группу, бензильную группу или галид.
3. Каталитический состав по п.1, отличающийся тем, что каждый из заместителей X3 независимо представляет собой атом водорода, метильную группу, этильную группу, пропильную группу, н-бутильную группу, трет-бутильную группу или гексильную группу.
4. Каталитический состав по п.1, отличающийся тем, что алкенильный заместитель R представляет собой этенил, пропенил или бутенил.
5. Каталитический состав по п.1, отличающийся тем, что каждый из заместителей RA, помимо алкенильного заместителя, независимо представляет собой атом водорода, метальную группу, этильную группу, пропильную группу, н-бутильную группу, трет-бутильную группу, метоксигруппу, этоксигруппу, пропоксигруппу или бутоксигруппу.
6. Каталитический состав по п.1, отличающийся тем, что Х4 представляет собой
-O-RA.
7. Каталитический состав по п.1, отличающийся тем, что RB и RC независимо представляют собой атом водорода, метильную группу, этильную группу, пропильную группу, н-бутильную группу, трет-бутильную группу, фенильную группу, бензильную группу, толильную группу или ксилильную группу.
8. Каталитический состав по п.1, отличающийся тем, что активатор представляет собой подложку-активатор, содержащую твердофазный оксид, обработанный электрон-акцепторным анионом, причем
твердофазный оксид представляет собой оксид кремния, оксид алюминия, оксид кремния и алюминия, фосфат алюминия, гетерополивольфраматы, оксид титана, оксид циркония, оксид магния, оксид бора, оксид цинка, любой смешанный оксид из указанных оксидов или их любую смесь; и
электрон-акцепторный анион представляет собой фторид, хлорид, бромид, фосфат, трифлат, бисульфат, сульфат или их любую комбинацию.
9. Каталитический состав по п.8, отличающийся тем, что подложка-активатор дополнительно содержит металл или ион металла, при этом металл или ион металла представляет собой цинк, никель, ванадий, серебро, медь, галлий, олово, вольфрам, молибден, или их любую комбинацию.
10. Каталитический состав по п.1, отличающийся тем, что активатор представляет собой подложку-активатор, содержащую глинистый минерал, столбчатую глину, чешуйчатую глину, чешуйчатую глину внедренную в другую оксидную матрицу, слоистый силикатный минерал, неслоистый силикатный минерал, слоистый алюмосиликатный минерал, неслоистый алюмосиликатный минерал, или их любую комбинацию.
11. Каталитический состав по п.1, дополнительно содержащий алюминийорганическое соединение, соответствующее формуле:
Al(X5)m(X6)3-m;
где X5 представляет собой гидрокарбил;
X6 представляет собой алкоксид или арилоксид, галид или гидрид; и
m составляет от 1 до 3 включительно.
12. Каталитический состав по п.11, отличающийся тем, что алюминийорганическое соединение представляет собой триметилалюминий, триэтилалюминий, три-н-пропилалюминий, этоксид диэтилалюминия, три-н-бутилалюминий, гидрид диизобутилалюминия, триизобутилалюминий, хлорид диэтилалюминия, или их любую комбинацию.
13. Каталитический состав по п.1, отличающийся тем, что активатор представляет собой подложку-активатор, алюмоксановое соединение, борорганическое или бораторганическое соединение, ионизирующее ионное соединение, или их любую комбинацию.
14. Каталитический состав по любому из пп.1-13, отличающийся тем, что гибридное металлоценовое соединение представляет собой:
Figure 00000002
;
Figure 00000003
; или
инденил(X4)Zr(CH2фeнил)2; где X4 представляет собой
Figure 00000004
;
Figure 00000005
или
Figure 00000006
.
15. Способ олефиновой полимеризации, включающий взаимодействие каталитического состава по любому из пп.1-14, с олефиновым мономером и возможно олефиновым сомономером в условиях полимеризации, с получением полимера или сополимера.
16. Способ по п.15, отличающийся тем, что каталитический состав и олефиновый мономер подвергают контакту в газофазном реакторе, петлевом суспензионном реакторе или в реакторе с механическим перемешиванием.
17. Способ по п.15, отличающийся тем, что олефиновый мономер включает этилен, пропилен или стирол.
18. Способ по п.15, отличающийся тем, что олефиновый сомономер представляет собой 1-бутен, 2-бутен, 3-метил-1-бутен, изобутилен, 1-пентен, 2-пентен, 3-метил-1-пентен, 4-метил-1-пентен, 1-гексен, 2-гексен, 3-этил-1-гексен, 1-гептен, 2-гептен, 3-гептен, 1-октен или стирол.
19. Соединение, соответствующее формуле: инденил(Х4)Zr(СН2фенил)2; где X4 представляет собой
Figure 00000004
;
Figure 00000005
или
Figure 00000006
.
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