RU2018141057A - Получение полиолефиновых продуктов - Google Patents
Получение полиолефиновых продуктов Download PDFInfo
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- RU2018141057A RU2018141057A RU2018141057A RU2018141057A RU2018141057A RU 2018141057 A RU2018141057 A RU 2018141057A RU 2018141057 A RU2018141057 A RU 2018141057A RU 2018141057 A RU2018141057 A RU 2018141057A RU 2018141057 A RU2018141057 A RU 2018141057A
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- catalyst
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- 229920000098 polyolefin Polymers 0.000 title claims 8
- 239000003054 catalyst Substances 0.000 claims 83
- 229920000642 polymer Polymers 0.000 claims 32
- 238000000034 method Methods 0.000 claims 23
- 229910052739 hydrogen Inorganic materials 0.000 claims 14
- 239000001257 hydrogen Substances 0.000 claims 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 13
- 239000005977 Ethylene Substances 0.000 claims 13
- -1 polyethylene copolymer Polymers 0.000 claims 13
- 239000000203 mixture Substances 0.000 claims 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 11
- 230000003197 catalytic effect Effects 0.000 claims 8
- 239000004698 Polyethylene Substances 0.000 claims 7
- 125000005842 heteroatom Chemical group 0.000 claims 7
- 229920000573 polyethylene Polymers 0.000 claims 7
- SVBLJDGZIHTZBY-UHFFFAOYSA-N C(CC)C1(C=CC=C1)[Hf]C1(C=CC=C1)CCC Chemical compound C(CC)C1(C=CC=C1)[Hf]C1(C=CC=C1)CCC SVBLJDGZIHTZBY-UHFFFAOYSA-N 0.000 claims 6
- PQWIFOZEPZWISQ-UHFFFAOYSA-N C1=CC=C2C(CC)C([Zr]C=3C(C4=CC=CC=C4C=3)CC)=CC2=C1 Chemical compound C1=CC=C2C(CC)C([Zr]C=3C(C4=CC=CC=C4C=3)CC)=CC2=C1 PQWIFOZEPZWISQ-UHFFFAOYSA-N 0.000 claims 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 6
- 239000000758 substrate Substances 0.000 claims 6
- 229910052726 zirconium Inorganic materials 0.000 claims 6
- 150000002430 hydrocarbons Chemical group 0.000 claims 5
- 239000003446 ligand Substances 0.000 claims 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 4
- 229920006158 high molecular weight polymer Polymers 0.000 claims 4
- 239000004215 Carbon black (E152) Substances 0.000 claims 3
- 125000000217 alkyl group Chemical group 0.000 claims 3
- 229910052736 halogen Inorganic materials 0.000 claims 3
- 150000002367 halogens Chemical class 0.000 claims 3
- 229930195733 hydrocarbon Natural products 0.000 claims 3
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 238000005259 measurement Methods 0.000 claims 3
- 238000010094 polymer processing Methods 0.000 claims 3
- 239000000725 suspension Substances 0.000 claims 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 2
- 239000000155 melt Substances 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 239000002685 polymerization catalyst Substances 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 claims 2
- 150000003624 transition metals Chemical class 0.000 claims 2
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 238000000071 blow moulding Methods 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 238000010276 construction Methods 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 230000000704 physical effect Effects 0.000 claims 1
- 229920003023 plastic Polymers 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 238000001175 rotational moulding Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08F4/62—Refractory metals or compounds thereof
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- C08F4/65925—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 non-bridged
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- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
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Claims (88)
1. Способ получения специфического для изделия полиолефина, включающий
выбор каталитической смеси, по меньшей мере частично на основе карты коэффициента полидисперсности (PDI), при этом карту полидисперсности получают посредством:
получения множества полимеров для по меньшей мере двух катализаторов, где каждый полимер получают при различном соотношении водорода к этилену, при этом один из по меньшей мере двух катализаторов обеспечивает получение более высокомолекулярного полимера, а другой из по меньшей мере двух катализаторов обеспечивает получение более низкомолекулярного полимера;
измерения молекулярной массы каждого полимера;
определения зависимости между молекулярной массой полимеров, полученных на каждом из по меньшей мере двух катализаторов, и соотношением водорода к этилену; и
построения группы кривых bPDI для полимеров, которые будут получены с применением множества соотношений смеси по меньшей мере двух катализаторов для каждого из множества соотношений водорода к этилену; и
выбора соотношения для каталитической смеси по меньшей мере двух катализаторов, которое обеспечивает получение полимера с bPDI, соответствующим процессу переработки полимера; и
получение специфического для изделия полиолефина с применением каталитической смеси.
2. Способ по п. 1, отличающийся тем, что взаимосвязь между молекулярной массой и соотношением водорода к этилену определяют по линейному приближению согласно уравнению
1/Mw = отсекаемый отрезок + тангенс угла наклона ⋅ (Н2/С2).
3. Способ по п. 2, включающий
расчет b-соотношения как соотношения отсекаемого отрезка первого катализатора к отсекаемому отрезку второго катализатора;
расчет m-соотношения как соотношения тангенса угла наклона первого катализатора к тангенсу угла наклона второго катализатора;
где
b-соотношение / m-соотношение для каталитической смеси составляет менее примерно 2;
b-соотношение для каталитической смеси составляет более примерно 5;
m-соотношение для каталитической смеси составляет более примерно 5;
полидисперсность низкомолекулярного полимера (1PDI) больше примерно 3,0; и
полидисперсность высокомолекулярного полимера (hPDI) больше примерно 3,0.
4. Способ по п. 1, включающий построение кривой bPDI с помощью зависимости bPDI=[Flmw+Fhmw*(hmw/lmw)]*[Flmw*lPDI+Fhmw*hPDI*(lmw/hmw)], где:Flmw представляет собой массовую долю низкомолекулярного полимерного компонента;
Fhmw представляет собой массовую долю высокомолекулярного полимерного компонента;
Flmw и Fhmw рассчитывают по количеству полимера, полученного на первом катализаторе при каждом соотношении водорода к этилену, и по количеству полимера, полученного на втором катализаторе при каждом соотношении водорода к этилену;
lmw представляет собой средневесовую молекулярную массу низкомолекулярного полимерного компонента;
hmw представляет собой средневесовую молекулярную массу высокомолекулярного полимерного компонента;
lmw и hmw рассчитывают по зависимости молекулярной массы от соотношения водорода к этилену;
lPDI представляет собой полидисперсность низкомолекулярного полимерного компонента;
hPDI представляет собой полидисперсность высокомолекулярного полимерного компонента; и
lPDI и hPDI измеряют для каждого полимера.
5. Способ по п. 1, отличающийся тем, что процесс переработки полимера включает выдувное формование, литьевое формование, получение выдувной пленки или ротационное формование.
6. Способ по п. 1, включающий добавление раствора, содержащего катализатор, к суспензии, содержащей другой катализатор.
7. Способ по п. 1, включающий получение продукта из полимера полиолефина.
8. Способ по п. 1, включающий непрерывное смешивание суспензии каталитического компонента с раствором каталитического компонента с получением системы катализатора на общей подложке.
9. Способ по п. 1, включающий
измерение образца полимера полиолефина для получения первоначального свойства продукта; и
изменение технологического параметра для получения второго свойства продукта, по меньшей мере частично на основании первоначального свойства продукта.
10. Способ по п. 9, отличающийся тем, что измерение образца полимера полиолефина включает измерение внедрения сомономера как функции от молекулярной массы.
11. Способ по п. 9, отличающийся тем, что измерение образца включает определение физического свойства пластикового образца.
12. Способ по п. 9, отличающийся тем, что измерение образца включает определение индекса потока, индекса расплава, соотношения двух индексов расплава, плотности, молекулярно-массового распределения, содержания сомономера или любых их комбинаций.
13. Способ по п. 9, отличающийся тем, что изменение технологического параметра включает регулирование молярного содержания каталитического компонента, который смешивают с суспензией каталитического компонента.
14. Способ по п. 9, отличающийся тем, что изменение технологического параметра включает регулирование температуры реактора.
15. Способ по п. 9, отличающийся тем, что изменение технологического параметра включает регулирование парциального давления этилена.
16. Способ по п. 1, включающий регулирование соотношения сомономера к этилену в реакторе полимеризации для регулирования распределения состава, молекулярно-массового распределения, индекса расплава (b) или соотношения двух индексов расплава, или любой их комбинации, полимера полиолефина.
17. Способ по п. 1, включающий регулирование соотношения водорода к этилену в реакторе полимеризации для регулирования распределения состава, молекулярно-массового распределения, индекса расплава (h) или соотношения двух индексов расплава, или любой их комбинации, полимера полиолефина.
18. Катализатор полимеризации для получения сополимера полиэтилена, содержащий
подложку катализатора;
смесь по меньшей мере двух катализаторов, выбранных посредством:
получения множества полимеров для по меньшей мере двух катализаторов, где каждый полимер получают при различном соотношении водорода к этилену, при этом один из по меньшей мере двух катализаторов обеспечивает получение полимера с более высокой средневесовой молекулярной массой (hmw), а другой из по меньшей мере двух катализаторов обеспечивает получение полимера с более низкой средневесовой молекулярной массой (lmw), где соотношение hmw к lmw составляет более примерно 5,0 при средневесовой молекулярной массе от примерно 30000 до примерно 150000;
измерения молекулярной массы каждого полимера;
определения зависимости между молекулярной массой полимеров, полученных на каждом из по меньшей мере двух катализаторов, и соотношением водорода к этилену;
построения группы кривых bPDI для полимеров, которые будут получены с применением множества соотношений смеси по меньшей мере двух катализаторов для каждого из множества соотношений водорода к этилену; и
выбора соотношения для каталитической смеси по меньшей мере двух катализаторов, которое обеспечивает получение полимера с bPDI, соответствующим процессу переработки полимера.
19. Катализатор по п. 18, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представляет собой бис(н-пропилциклопентадиенил)гафний (СН3)2, бис(н-пропилциклопентадиенил)гафний F2, бис(н-пропилциклопентадиенил)гафний Cl2 или любые их комбинации.
20. Катализатор по п. 18, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представляет собой бис(н-бутил, метилциклопентадиенил)цирконий (СН3)2, бис(н-бутил, метилциклопентадиенил)цирконий Cl2, бис(н-бутил, метилциклопентадиенил)цирконий F2 или любые их комбинации.
21. Катализатор по п. 18, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представляет собой бис(1-этилинденил)цирконий (СН3)2, бис(1-этилинденил)цирконий F2, бис(1-этилинденил)цирконий Cl2 или любые их комбинации.
22. Катализатор по п. 18, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представлен формулой
23. Катализатор по п. 18, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представляет собой любой один или любую комбинацию соединений, представленных следующими формулами
где R1 и R2, каждый независимо, представляют собой метил, хлор, фтор или углеводородную группу.
24. Катализатор полимеризации для получения сополимера полиэтилена, содержащий
подложку катализатора;
первый катализатор, которым пропитана подложка катализатора, при этом первый катализатор обеспечивает получение полимеров, имеющих тангенс угла наклона на кривой зависимости Н2/С2 от 1/Mw от примерно 1,0×10-6 до примерно 1,5×10-6, и где при соотношении С6/С2 от примерно 0,008 до примерно 0,012, первый катализатор обеспечивает получение полимера, имеющего MI примерно 1,0 град./10 мин., плотность примерно 0,92 г/см3 и отношение индекса расплава (MIR) менее примерно 25; и
второй катализатор, которым пропитана подложка катализатора с первым катализатором, при этом второй катализатор обеспечивает получение полимеров, имеющих тангенс угла наклона на кривой зависимости Н2/С2 от 1/Mw от примерно 3,0×10-6 до примерно 4×10-6, и где при соотношении С6/С2 от примерно 0,03 до примерно 0,04, второй катализатор обеспечивает получение полимера, имеющего MI примерно 1,0 град./10 мин., плотность примерно 0,92 г/см3 и отношение индекса расплава (MIR) менее примерно 25.
25. Катализатор по п. 24, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представляет собой бис(н-пропилциклопентадиенил)гафний (СН3)2, бис(н-пропилциклопентадиенил)гафний F2, бис(н-пропилциклопентадиенил)гафний Cl2 или любые их комбинации.
26. Катализатор по п. 24, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представляет собой бис(н-бутил, метилциклопентадиенил)цирконий (СН3)2, бис(н-бутил, метилциклопентадиенил)цирконий Cl2, бис(н-бутил, метилциклопентадиенил)цирконий F2 или любые их комбинации.
27. Катализатор по п. 24, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представляет собой бис(1-этилинденил)цирконий (СН3)2, бис(1-этилинденил)цирконий F2, бис(1-этилинденил)цирконий Cl2 или любые их комбинации.
28. Катализатор по п. 24, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представлен формулой
29. Катализатор по п. 24, отличающийся тем, что катализатор, которым пропитана подложка катализатора, представляет собой любой один или любую комбинацию соединений, представленных следующими формулами
где R1 и R2, каждый независимо, представляют собой метил, хлор, фтор или углеводородную группу.
30. Катализатор по п. 24, отличающийся тем, что подложка пропитана хромовым катализатором.
31. Катализатор по п. 24, отличающийся тем, что подложка пропитана обычным катализатором на основе переходного металла.
32. Катализатор по п. 24, отличающийся тем, что подложка катализатора содержит диоксид кремния.
33. Катализатор по п. 24, отличающийся тем, что подложка катализатора содержит алюминоксан.
34. Катализатор по п. 24, отличающийся тем, что катализатор, которым пропитана подложка, имеет формулу
CpACpBMXn or CpA(А)CpBMXn,
где М представляет собой атом группы 4, 5 или 6; каждый CpA и CpB связан с М и независимо выбран из группы, состоящей из циклопентадиенильных лигандов, замещенных циклопентадиенильных лигандов, лигандов, изолобальных циклопентадиенилу, и замещенных лигандов, изолобальных циклопентадиенилу; (А) представляет собой двухвалентную мостиковую группу, связанную с CpA и CpB, выбранную из группы, состоящей из двухвалентных С1-С20 углеводородных радикалов и C1-С20 углеводородных радикалов, содержащих гетероатом, где углеводородные радикалы, содержащие гетероатом, содержат от одного до трех гетероатомов; каждый X независимо представляет собой хлорид-ион, бромид-ион, C1-С10 ал кил, С2-С12 алкенил, карбоксилат, ацетилацетонат или алкоксид; и п представляет собой целое число от 1 до 3.
35. Катализатор по п. 24, отличающийся тем, что катализатор, которым пропитана подложка, имеет формулу
где М представляет собой переходный металл группы 3-12 или металл основной группы 13 или 14; каждый X независимо представляет собой анионную уходящую группу; у равен 0 или 1; п представляет собой степень окисления М; m представляет собой формальный заряд лиганда, представленного как YZL или YZL'; L представляет собой элемент группы 15 или 16; L' представляет собой элемент группы 15 или 16, или группу, содержащую элемент группы 14; Y представляет собой элемент группы 15; Z представляет собой элемент группы 15; R1 и R2 независимо представляют собой C1-С20 углеводородную группу или группу, содержащую гетероатом, содержащую до двадцати атомов углерода, кремний, германий, олово, свинец или фосфор; R1 и R2 могут быть взаимосвязаны друг с другом; R3 отсутствует, представляет собой углеводородную группу, водород, галоген или группу, содержащую гетероатом; R4 и R5 независимо представляют собой алкильную группу, арильную группу, замещенную арильную группу, циклическую алкильную группу, замещенную циклическую алкильную группу, циклическую аралкильную группу, замещенную циклическую аралкильную группу или многокольцевую систему; R4 и R5 могут быть взаимосвязаны друг с другом; R6 и R7 независимо отсутствуют, представляют собой водород, алкильную группу, галоген, гетероатом или углеводородную группу; и R* отсутствует, представляет собой водород, группу, содержащую атом группы 14, галоген или группу, содержащую гетероатом.
36. Катализатор по п. 24, отличающийся тем, что полученный сополимер полиэтилена имеет молекулярно-массовое соотношение высокомолекулярного компонента к низкомолекулярному компоненту, составляющее от примерно 1:2 до 1:5.
37. Катализатор по п. 24, отличающийся тем, что полученный сополимер полиэтилена имеет плотность высокомолекулярного компонента, которая примерно на 0,02-0,05 меньше плотности низкомолекулярного компонента.
38. Катализатор по п. 24, отличающийся тем, что полученный сополимер полиэтилена имеет высокомолекулярный компонент со средневесовой молекулярной массой от примерно 75000 до примерно 150000.
39. Катализатор по п. 24, отличающийся тем, что полученный сополимер полиэтилена имеет низкомолекулярный компонент со средневесовой молекулярной массой от примерно 10000 до примерно 40000.
40. Катализатор по п. 24, отличающийся тем, что полученный сополимер полиэтилена имеет средневесовую молекулярную массу от примерно 90000 до примерно 110000.
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