RU2002124131A - Способ получения композиции металлоорганических катализаторов и способ полимеризации с использованием данной композиции - Google Patents
Способ получения композиции металлоорганических катализаторов и способ полимеризации с использованием данной композицииInfo
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Claims (23)
1. Способ получения композиции катализатора, включающий контактное взаимодействие, по меньшей мере, одного металлоорганического соединения, по меньшей мере одного алюмоорганического соединения и, по меньшей мере, одного твердого вещества, в котором металлоорганическое соединение имеет следующую общую формулу:
(X1)(X2)(X3)(X4)M1,
где M1 представляет собой титан, цирконий или гафний;
(X1) независимо означает циклопентадиенил, инденил, фторенил, замещенный циклопентадиенил, замещенный инденил или замещенный фторенил;
каждая из заместительных групп в замещенных циклопентадиенилах, замещенных инденилах и замещенных фторенилах на (X1) представляет собой алифатическую группу, циклическую группу, комбинацию из алифатической и циклической группы, силиловую группу, алкилгалидную группу, галид, металлоорганическую группу, фосфорную группу, азотную группу, кремний, фосфор, бор, германий или водород;
по меньшей мере одна заместительная группа на (X1) может служить мостиком, связывающим (X1) и (X2);
(X3) и (X4) независимо означают галид, алифатическую группу, замещенную алифатическую группу, циклическую группу, замещенную циклическую группу, комбинацию из алифатической группы и циклической группы, комбинацию из замещенной алифатической группы и циклической группы, комбинацию из алифатической группы и замещенной циклической группы, комбинацию из замещенной алифатической группы и замещенной циклической группы, амидогруппу, замещенную амидогруппу, фосфидогруппу, замещенную фосфидогруппу, алкоксидную группу, замещенную алкоксидную группу, арилоксидную группу, замещенную арилоксидную группу, металлоорганическую группу или замещенную металлоорганическую группу;
(X2) означает циклопентадиенил, инденил, фторенил, замещенный циклопентадиенил, замещенный инденил, замещенный фторенил, галид, алифатическую группу, замещенную алифатическую группу, циклическую группу, замещенную циклическую группу, комбинацию из алифатической группы и циклической группы, комбинацию из замещенной алифатической группы и циклической группы, комбинацию из алифатической группы и замещенной циклической группы, комбинацию из замещенной алифатической группы и замещенной циклической группы, амидогруппу, замещенную амидогруппу, фосфидогруппу, замещенную фосфидогруппу, алкоксидную группу, замещенную алкоксидную группу, арилоксидную группу, замещенную арилоксидную группу, металлоорганическую группу или замещенную металлоорганических группу;
каждая из заместительных групп на (X2) представляет собой алифатическую группу, циклическую группу, комбинацию из алифатической группы и циклической группы, силильную группу, алкилгалидную группу, галид, металлоорганическую группу, фосфорную группу, азотную группу, кремний, фосфор, бор, германий или водород;
по меньшей мере одна заместительная группа на (X2) может служить мостиком, связывающим (X1) и (X2);
в котором алюмоорганическое соединение имеет следующую общую формулу:
Al(X5)n(X6)3-n,
(X5) означает углеводород, имеющий от 1 до 20 атомов углерода;
(X6) означает галид, гидрид или алкоксид;
n - число от 1 до 3 включительно;
в котором твердое вещество представляет собой тетрафторид титана, тетрафторид циркония или обработанное твердое оксидноое соединение;
обработанное твердое оксидное соединение включает твердое оксидное соединение с нанесенным на его поверхность тетрафторидом титана или тетрафторидом циркония;
твердое оксидное соединение включает кислород и по меньшей мере один элемент из групп IIA-VIIIA и IB-VIIB Периодической Таблицы Элементов, включая лантаниды и актиниды.
2. Способ по п.1, в котором обработанное твердое оксидное соединение получают способом, включающим: 1) обжиг твердого оксидного соединения, получая обожженное твердое оксидное соединение; 2) растворение тетрафторида титана или тетрафторида циркония в любом апротонном полярном растворителе, получая раствор фторида металла; 3) контактирование раствора фторида металла с обожженным твердым оксидным соединением, получая смесь фторида металла/твердого оксидного соединения; 4) выпаривание апротонного полярного растворителя из смеси фторида металла/твердого оксидного соединения, получая обработанное твердое оксидное соединение.
3. Способ по п.2, включающий высушивание обработанного твердого оксидного соединения для удаления практически всего апротонного полярного растворителя.
4. Способ по п.1, в котором обработанное твердое оксидное соединение получают способом, включающим: 1) обжиг твердого оксидного соединения, получая обожженное твердое оксидное соединение; 2) смешивание в сухом состоянии обожженного твердого оксидного соединения с тетрафторидом титана, получая смесь тетрафторида титана/твердого оксидного соединения; 3) обжиг смеси тетрафторида титана/твердого оксидного соединения при температуре в пределах от 250°С до 500°С в течение от 1 минуты до 10 часов, получая обработанное твердое оксидное соединение.
5. Способ по п.1, в котором обработанное твердое оксидное соединение получают способом, включающим: 1) импрегнирование твердого оксидного соединения раствором, содержащим гексафторотитанат аммония (NH4)2TiF4 или гексафтороцирконат аммония (NH4)2ZrF4 и растворитель, получая твердое оксидное соединение, содержащее металлофторид аммония; 2) выпаривание растворителя из твердого оксидного соединения, содержащего металлофторид аммония; 3) обжиг содержащего металлофторид аммония твердого оксидного соединения при высокой температуре, достаточной для разложения гексафтортитаната аммония или гексафтороцирконата аммония до тетрафторида титана или тетрафторида циркония с выделением фторида аммония NH4F, при этом получают обработанное твердое оксидное соединение.
6. Способ получения композиции катализатора, включающий: 1) обжиг алюмосиликата при температуре в пределах от 300°С до 700°С в течение от 1 ч до 50 ч, получая обожженный алюмосиликат; 2) охлаждение обожженного алюмосиликата и добавление тетрафторида титана в количестве, достаточном для достижения от 0,1 до 5 ммоль тетрафторида титана на 1 г обожженного алюмосиликата, получая содержащий тетрафторид титана алюмосиликат; 3) обжиг содержащего тетрафторид титана алюмосиликата при температуре в пределах от 300°С до 500°С в течение от 1 ч до 5 ч, получая обработанное твердое оксидное соединение; 4) контактное взаимодействие между металлоорганическим соединением, алюмоорганическим соединением и обработанным твердым оксидным соединением, получая композицию катализатора.
7. Способ по п.6, состоящий в основном из стадий 1, 2, 3 и 4.
8. Способ по п.6, включающий: 1) обжиг алюмосиликата в безводном азоте при 500°С в течение примерно 3 часов, получая обожженный алюмосиликат; 2) охлаждение обожженного алюмосиликата и добавление тетрафторида титана в количестве, достаточном для достижения от 0,5 до 3 ммоль тетрафторида титана на 1 г обожженного алюмосиликата, получая содержащий тетрафторид титана алюмосиликат; 3) обжиг содержащего тетрафторид титана алюмосиликата при 500°С в течение примерно 1 часа, получая обработанное твердое оксидное соединение; 4) контактное взаимодействие между дихлоридом бис(н-бутилциклопентадиенил)диркония, триэтилалюминием и обработанным твердым оксидным соединением, получая композицию катализатора.
9. Способ по п.8, состоящий в основном из стадий 1, 2, 3 и 4.
10. Способ по п.1, в котором композиция катализатора имеет активность более 50 г полимера на 1 г твердого вещества в час в условиях полимеризации в суспензии, используя изобутан в качестве растворителя при температуре полимеризации 90°С и давлении этилена 3,89 МПа (550 psig).
11. Способ по п.10, в котором композиция катализатора имеет активность более 100 г полимера на 1 г твердого вещества в час в условиях полимеризации в суспензии, используя изобутан в качестве растворителя при температуре полимеризации 90°С и давлении этилена 3,89 МПа (550 psig).
12. Способ по п.1, в котором весовое отношение алюмоорганического соединения к твердому веществу в композиции катализатора составляет от 3:1 до 1:100.
13. Способ по п.12, в котором весовое отношение алюмоорганического соединения к твердому веществу в композиции катализатора составляет от 1:1 до 1:50.
14. Способ по п.1, в котором весовое соотношение твердого вещества и металлоорганического соединения в композиции катализатора составляет от 1000:1 до 10:1.
15. Способ по п.14, в котором весовое соотношение твердого вещества и металлоорганического соединения в композиции катализатора составляет от 250:1 до 20:1.
16. Способ по п.1, в котором композиция катализатора после контакта между металлоорганическим соединением, твердым веществом и алюмоорганическим соединением состоит в основном из металлоорганического соединения и твердого вещества.
17. Способ по п.1, в котором композиция катализатора после контакта между металлоорганическим соединением, твердым веществом и алюмоорганическим соединением состоит в основном из металлоорганического соединения, твердого вещества и алюмоорганического соединения.
18. Способ полимеризации, в котором контакт по меньшей мере одного мономера с композицией катализатора, полученной способом по п.1, осуществляют в условиях полимеризации для получения полимера.
19. Способ по п.18, в котором полимеризацию осуществляют в суспензии.
20. Способ по п.19, в котором контакт осуществляют в контурной зоне реактора.
21. Способ по п.20, в котором контакт осуществляют в присутствии растворителя, включающего по большей части изобутан.
22. Способ по п.18, в котором по меньшей мере один мономер представляет собой этилен.
23. Способ по п.18, в котором по меньшей мере один мономер включает этилен и алифатический 1-олефин с 3-20 атомами углерода в молекуле.
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-
2000
- 2000-02-11 US US09/502,277 patent/US6576583B1/en not_active Expired - Lifetime
-
2001
- 2001-02-12 AU AU2001236889A patent/AU2001236889A1/en not_active Abandoned
- 2001-02-12 CN CN01806473A patent/CN1426326A/zh active Pending
- 2001-02-12 WO PCT/US2001/004380 patent/WO2001058587A1/en active Application Filing
- 2001-02-12 RU RU2002124131/04A patent/RU2002124131A/ru unknown
- 2001-02-12 KR KR1020027010352A patent/KR100679766B1/ko not_active IP Right Cessation
- 2001-02-12 JP JP2001557686A patent/JP2003522226A/ja active Pending
- 2001-02-12 CA CA002399618A patent/CA2399618C/en not_active Expired - Fee Related
- 2001-02-12 EP EP01909102A patent/EP1259321A4/en not_active Withdrawn
- 2001-02-12 MX MXPA02007742A patent/MXPA02007742A/es unknown
- 2001-02-12 BR BR0108230-2A patent/BR0108230A/pt not_active Application Discontinuation
-
2003
- 2003-05-23 US US10/445,379 patent/US6838533B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US6838533B2 (en) | 2005-01-04 |
CA2399618A1 (en) | 2001-08-16 |
WO2001058587A1 (en) | 2001-08-16 |
US6576583B1 (en) | 2003-06-10 |
BR0108230A (pt) | 2003-03-05 |
AU2001236889A1 (en) | 2001-08-20 |
EP1259321A1 (en) | 2002-11-27 |
EP1259321A4 (en) | 2010-08-25 |
CA2399618C (en) | 2007-11-06 |
CN1426326A (zh) | 2003-06-25 |
US20040038807A1 (en) | 2004-02-26 |
KR100679766B1 (ko) | 2007-02-07 |
JP2003522226A (ja) | 2003-07-22 |
MXPA02007742A (es) | 2002-10-11 |
KR20030007416A (ko) | 2003-01-23 |
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