RU2018104667A - Газофазный способ полимеризации пропилена - Google Patents
Газофазный способ полимеризации пропилена Download PDFInfo
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- 238000000034 method Methods 0.000 title claims 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims 3
- 238000006116 polymerization reaction Methods 0.000 title 1
- -1 aluminum alkyl compound Chemical class 0.000 claims 7
- 150000001875 compounds Chemical class 0.000 claims 6
- 229910052736 halogen Inorganic materials 0.000 claims 5
- 229910052739 hydrogen Inorganic materials 0.000 claims 5
- 239000001257 hydrogen Substances 0.000 claims 5
- 150000002367 halogens Chemical class 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 3
- 150000001336 alkenes Chemical class 0.000 claims 3
- 125000005842 heteroatom Chemical group 0.000 claims 3
- 229920000098 polyolefin Polymers 0.000 claims 3
- 229910052710 silicon Inorganic materials 0.000 claims 3
- 239000011949 solid catalyst Substances 0.000 claims 3
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 150000003254 radicals Chemical class 0.000 claims 2
- 150000003377 silicon compounds Chemical class 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 150000002391 heterocyclic compounds Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
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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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
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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
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- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
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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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- C08F4/60—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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- C08F4/60—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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Claims (22)
1. Газофазный способ гомополимеризации и сополимеризации пропилена с прочими олефинами, осуществляемый в присутствии каталитической системы, включающей
(a) твердый компонент катализатора, содержащий Mg, Ti, галоген, донор электронов, выбранный из 1,3-диэфиров, и от 10 до 85% олефинового полимера исходя из общей массы твердого компонента катализатора;
(b) алкилалюминиевое соединение; и
(c) внешнее электронодонорное соединение, выбранное из соединений кремния, эфиров, сложных эфиров, аминов, гетероциклических соединений, кетонов, причем указанные компоненты (a) и (c) берутся в таких количествах, чтобы молярное соотношение Al/(ED) составляло от 2 до 200.
2. Газофазный способ по п.1, отличающийся тем, что твердый компонент катализатора имеет средний размер частиц, составляющий от 10 до 100 мкм.
3. Газофазный способ по п.1, отличающийся тем, что особенно предпочтительными и упомянутыми выше 1,3-диэфирами являются соединения формулы (I)
где RI и RII, равные или отличные друг от друга, представляют собой водород, линейные или разветвленные углеводородные группы C1- C18, которые способны образовывать одну или несколько циклических структур; группы RIII , равные или отличные друг от друга, представляют собой водород или углеводородные группы C1-С18; группы RIV, равные или отличные друг от друга, имеют то же значение RIII, за исключением того, что они не могут быть водородными; каждая из групп от RI до RIV может содержать гетероатомы, выбранные из галогенов, N, O, S и Si.
4. Способ по п.3, отличающийся тем, что 1,3-диэфиры выбираются из соединений формулы (III):
где RVI радикалы, равные или отличные друг от друга, представляют собой водород; галогены, предпочтительно Cl и F; линейные или разветвленные алкиловые радикалы Cl- C20; циклоалкил C3- C20, арил C6- C20, алкиларил C7-C20 и аралкильные радикалы C7-C20, необязательно содержащие один или несколько гетероатомов, выбранных из группы, состоящей из N, 0, S, P, Si и галогенов, в частности Cl и F в качестве заменителей углерода или атомов водорода, или их обоих; а радикалы RIII и RIV соответствуют определению в пункте 3 формулы изобретения.
5. Способ по п.1, отличающийся тем, что молярное соотношение 1,3-диэфир/Mg составляет от 0,030 до 0,150.
6. Способ по п.1, отличающийся тем, что молярное соотношение Mg/Ti составляет от 4 до 10.
7. Способ по п.1, отличающийся тем, что олефиновый полимер выбирается из (со) полимеров олефинов формулы CH2=CHR, в которой R представляет собой водород или углеводородный радикал с 1-12 атомами углерода.
8. Способ по п.7, отличающийся тем, что олефины выбираются из этилена, пропилена и их смесей.
9. Способ по п.7, отличающийся тем, что доля олефинового полимера составляет от 15 до 75 % исходя из общей массы твердого компонента катализатора (а).
10. Способ по п.1, отличающийся тем, что алкилалюминиевое соединение (b) выбирается среди соединений триалкилалюминия.
11. Способ по п.1, отличающийся тем, что алкилалюминиевое соединение используют в таком количестве, чтобы получить молярное соотношение Al/Ti, составляющее от 10 до 400.
12. Способ по п.1, отличающийся тем, что электронодонорное соединение выбирается из соединений кремния, имеющих, по меньшей мере, связь Si-O-C.
13. Способ по п.12, отличающийся тем, что соединения кремния имеют формулу Ra5Rb5Si(OR7)c , где a и b представляют собой целые числа от 0 до 2; c представляет собой целое число от 1 до 3; сумма (a+b+c) равна 4; R5, R6 и R7 представляют собой алкильные, циклоалкильные или арильные радикалы, содержащие от 1 до 18 атомов углерода, необязательно содержащие гетероатомы, выбранные из N, O, галогена и P.
14. Способ по п.1, осуществляемый в газофазном реакторе с псевдоожиженным слоем.
15. Способ по п.1, осуществляемый в газофазном реакторе с псевдоожиженным слоем при механическом перемешивании.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15179708 | 2015-08-04 | ||
| EP15179708.1 | 2015-08-04 | ||
| PCT/EP2016/068555 WO2017021454A1 (en) | 2015-08-04 | 2016-08-03 | Gas-phase process for the polymerization of propylene |
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| Publication Number | Publication Date |
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| RU2018104667A true RU2018104667A (ru) | 2019-08-07 |
| RU2018104667A3 RU2018104667A3 (ru) | 2019-12-13 |
| RU2721530C2 RU2721530C2 (ru) | 2020-05-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| RU2018104680A RU2717314C2 (ru) | 2015-08-04 | 2016-07-14 | Предварительно полимеризованные компоненты катализатора для полимеризации олефинов |
| RU2018104667A RU2721530C2 (ru) | 2015-08-04 | 2016-08-03 | Газофазный способ полимеризации пропилена |
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| RU2018104680A RU2717314C2 (ru) | 2015-08-04 | 2016-07-14 | Предварительно полимеризованные компоненты катализатора для полимеризации олефинов |
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| US (2) | US10435490B2 (ru) |
| EP (2) | EP3331926B1 (ru) |
| JP (2) | JP6841814B2 (ru) |
| KR (3) | KR102056017B1 (ru) |
| CN (2) | CN107873036B (ru) |
| BR (2) | BR112018002018B1 (ru) |
| CA (1) | CA2994495C (ru) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3331926B1 (en) * | 2015-08-04 | 2023-05-31 | Basell Poliolefine Italia S.r.l. | Prepolymerized catalyst components for the polymerization of olefins |
| US11401356B2 (en) * | 2017-07-19 | 2022-08-02 | China Petroleum & Chemical Corporation | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| US11866522B2 (en) | 2018-12-28 | 2024-01-09 | Braskem S.A. | Process for introducing catalyst in a polymerization process |
| JP7749024B2 (ja) * | 2021-04-06 | 2025-10-03 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | オレフィン重合用予備重合触媒成分 |
| US20240209125A1 (en) | 2021-04-16 | 2024-06-27 | Basell Poliolefine Italia S.R.L. | Prepolymerized catalyst components for the polymerization of olefins |
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