RU2019130039A - Каталитические системы, содержащие низковалентные титан-алюминиевые комплексы, и полимеры, полученные с применением таких систем - Google Patents

Каталитические системы, содержащие низковалентные титан-алюминиевые комплексы, и полимеры, полученные с применением таких систем Download PDF

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RU2019130039A
RU2019130039A RU2019130039A RU2019130039A RU2019130039A RU 2019130039 A RU2019130039 A RU 2019130039A RU 2019130039 A RU2019130039 A RU 2019130039A RU 2019130039 A RU2019130039 A RU 2019130039A RU 2019130039 A RU2019130039 A RU 2019130039A
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group
compound
titanium
independently
hydrocarbon radical
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RU2019130039A3 (ru
RU2759838C2 (ru
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Карлос А. КРУЗ
Джаред Л. БАРР
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Шеврон Филлипс Кемикал Компани Лп
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Claims (64)

1. Способ получения титан-алюминиевого комплекса, имеющий формулу:
Figure 00000001
(А), способ включает:
контактирование полуметаллоценового соединения титана, имеющего формулу:
Figure 00000002
(B)
с соединением алкилалюминия, имеющим формулу Al(RX)(RY)(RZ), с образованием смеси, содержащей титан-алюминиевый комплекс, имеющий формулу (A), где:
X1 и X2, независимо, представляют собой галоген;
R1, R2 и R3, независимо, представляют собой Н или галоген, С1-С36-углеводородный радикал, галогенированный С1-С36-углеводородный радикал, С1-С36-гидрокарбоксильную группу или С1-С36-гидрокарбилсилильную группу;
Cp представляет собой замещенную или незамещенную циклопентадиенильную, инденильную или флуоренильную группу; и
RX, RY и RZ, независимо, представляют собой C1-C10-алкильную группу.
2. Способ по п. 1, отличающийся тем, что соединение алкилалюминия содержит триметилалюминий, триэтилалюминий, триизобутилалюминий, три-н-октилалюминий или любую их комбинацию.
3. Способ по п. 1, отличающийся тем, что:
X1 и X2 представляют собой Cl;
R1, R2 и R3, независимо, представляют собой H или C1-C18-углеводородный радикал; и
Cp представляет собой незамещенную циклопентадиенильную или инденильную группу.
4. Способ по п. 1, отличающийся тем, что RX, RY и RZ, независимо, представляют собой C1-C8-алкильную группу.
5. Способ по п. 1, отличающийся тем, что смесь, содержащая титан-алюминиевый комплекс, образуется в течение периода времени от около 30 минут до около 36 часов.
6. Способ по п. 1, отличающийся тем, что смесь, содержащая титан-алюминиевый комплекс, содержит менее 10% мас. соединений Ti (IV).
7. Способ по п. 1, отличающийся тем, что
смесь дополнительно содержит соединения Ti (II) и/или дополнительные соединения Ti (III); и
смесь содержит менее 1% мас. соединений Ti (IV).
8. Способ по п. 1, отличающийся тем, молярное отношение соединения алкилалюминия к полуметаллоценовому соединению титана находится в диапазоне от около 1:1 до около 5:1.
9. Способ по п. 1, отличающийся тем, что молярное соотношение соединения алкилалюминия к полуметаллоценовому соединению титана находится в диапазоне от около 1,1:1 до около 2:1.
10. Титан-алюминиевый комплекс, имеющий формулу:
Figure 00000001
(A), где:
X1 и X2, независимо, представляют собой галоген;
R1, R2 и R3, независимо, представляют собой Н или галоген, С1-С36-углеводородный радикал, галогенированный С1-С36-углеводородный радикал, С1-С36-гидрокарбоксильную группу или С1-С36-гидрокарбилсилильную группу;
Cp представляет собой замещенную или незамещенную циклопентадиенильную, инденильную или флуоренильную группу; и
RY и RZ, независимо, представляют собой C1-C10-алкильную группу.
11. Комплекс по п. 10, отличающийся тем, что:
X1 и X2 представляют собой Cl;
R1, R2 и R3, независимо, представляют собой H или C1-C18-углеводородный радикал; и
Cp представляет собой незамещенную циклопентадиенильную или инденильную группу.
12. Комплекс по п. 10, отличающийся тем, что:
X1 и X2 представляют собой Cl;
R1, R2 и R3, независимо, представляют собой C1-C8-алкильную группу; и
RY и RZ, независимо, представляют собой C1-C8-алкильную группу.
13. Каталитическая композиция, содержащая комплекс титан-алюминий, активатор и необязательный сокатализатор, причем комплекс титан-алюминий имеет формулу:
Figure 00000001
(A), где:
X1 и X2, независимо, представляют собой галоген;
R1, R2 и R3, независимо, представляют собой Н или галоген, С1-С36-углеводородный радикал, галогенированный С1-С36-углеводородный радикал, С1-С36-гидрокарбоксильную группу или С1-С36-гидрокарбилсилильную группу;
Cp представляет собой замещенную или незамещенную циклопентадиенильную, инденильную или флуоренильную группу; и
RY и RZ, независимо, представляют собой C1-C10-алкильную группу.
14. Композиция по п. 13, отличающаяся тем, что активатор содержит алюмоксановое соединение, борорганическое соединение или органический борат, диссоциирующее на ионы соединение или любую их комбинацию.
15. Композиция по п. 13, отличающаяся тем, что активатор содержит активатор-носитель, причем активатор-носитель содержит твердый оксид, обработанный электроноакцепторным анионом.
16. Композиция по п. 13, отличающаяся тем, что
каталитическая композиция содержит алюмоорганический сокатализатор; и активатор содержит фторированный твердый оксид и/или сульфатированный твердый оксид.
17. Композиция по п. 13, отличающаяся тем, что каталитическую композицию получают способом, включающим:
(а) контактирование полуметаллоценового соединения титана, имеющего формулу:
Figure 00000002
(B)
с соединением алкилалюминия, имеющим формулу Al(RX)(RY)(RZ), в течение первого периода времени для образования первой смеси, причем первая смесь содержит титан-алюминиевый комплекс, имеющий формулу (A); и
(б) контактирование первой смеси с активатором и сокатализатором в течение второго периода времени для образования каталитической композиции; где:
X1 и X2, независимо, представляют собой галоген;
R1, R2 и R3, независимо, представляют собой Н или галоген, С1-С36-углеводородный радикал, галогенированный С1-С36-углеводородный радикал, С1-С36-гидрокарбоксильную группу или С1-С36-гидрокарбилсилильную группу;
Cp представляет собой замещенную или незамещенную циклопентадиенильную, инденильную или флуоренильную группу; и
RX, RY и RZ, независимо, представляют собой C1-C10-алкильную группу.
18. Способ полимеризации олефинов, включающий:
контактирование каталитической композиции по п. 13 с олефиновым мономером и необязательным олефиновым сомономером в реакторной системе полимеризации в условиях полимеризации для получения олефинового полимера.
19. Способ по п. 18, отличающийся тем, что
реакторная система полимеризации включает суспензионный реактор, газофазный реактор, растворный реактор или их комбинацию; и
олефиновый мономер содержит этилен, а олефиновый сомономер содержит 1-бутен, 1-гексен, 1-октен или их смесь.
20. Способ по п. 18, отличающийся тем, что
олефиновый полимер содержит гомополимер этилена или сополимер этилена/α-олефина;
активатор содержит активатор-носитель, алюмоксановое соединение, борорганическое соединение или органический борат, диссоциирующее на ионы соединение или любую их комбинацию; и
каталитическая композиция содержит алюмоорганический сокатализатор.
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