RU2003119544A - Способ полимеризации - Google Patents

Способ полимеризации Download PDF

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RU2003119544A
RU2003119544A RU2003119544/04A RU2003119544A RU2003119544A RU 2003119544 A RU2003119544 A RU 2003119544A RU 2003119544/04 A RU2003119544/04 A RU 2003119544/04A RU 2003119544 A RU2003119544 A RU 2003119544A RU 2003119544 A RU2003119544 A RU 2003119544A
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group
composition
change
atom
catalytic
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RU2003119544/04A
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RU2258712C2 (ru
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МОСАН Саймон (US)
МОСАН Саймон
КАО Суньчуе (US)
КАО Суньчуе
КУОЛК Тайхун (US)
КУОЛК Тайхун
Роджер ЛИНН Тимоти (US)
Роджер ЛИНН Тимоти
Х МАККОНВИЛ Дейвид (US)
Х МАККОНВИЛ Дейвид
Гэри МАККИ Мэттью (US)
Гэри МАККИ Мэттью
Фрэнсис ШУЛ Джон (US)
Фрэнсис ШУЛ Джон
Анна ТЕРРИ Керстен (US)
Анна ТЕРРИ Керстен
Т ВЕНЦЕЛЬ Тимоти (US)
Т ВЕНЦЕЛЬ Тимоти
Грегори ГУД Марк (US)
Грегори ГУД Марк
Хенри ОСКАМ Джон (US)
Хенри ОСКАМ Джон
Дж ЙОРГЕНСЕН Роберт (US)
Дж ЙОРГЕНСЕН Роберт
Харолд ФОГЕЛЬ Роберт (US)
Харолд ФОГЕЛЬ Роберт
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Юнивейшн Технолоджиз, Ллс (Us)
Юнивейшн Технолоджиз, Ллс
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Priority claimed from US09/729,550 external-priority patent/US6605675B2/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592Component 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
    • C08F4/65922Component 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
    • C08F4/65925Component 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/903Monomer polymerized in presence of transition metal containing catalyst and hydrocarbon additive affecting polymer properties of catalyst activity
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/907Specified means of reacting components of transition metal catalyst
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943Polymerization with metallocene catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerisation Methods In General (AREA)

Claims (20)

1. Способ полимеризации олефина (олефинов) включающий следующие стадии:
(а) приготовление
(I) композиции, включающей C530алкановый разбавитель и по меньшей мере одно каталитическое соединение, и
(II) композиции, включающей минеральное масло или силиконовое масло, подложку и активатор и необязательно каталитическое соединение, включающее элемент группы 15;
(б) непрерывное совмещение композиций (I) и (II) с получением каталитической композиции;
(в) введение этой каталитической композиции и одного или нескольких олефинов в работающий полимеризационный реактор и
(г) выделение полимера.
2. Способ по п.1, в котором активатор композиции (II) представляет собой нанесенный на подложку активатор, включающий подложку.
3. Способ по п.1, где каталитическое соединение, включающее элемент группы 15, содержится в композиции (II) и где по меньшей мере 50% этого соединения нанесено на материал подложки или содержится в нем.
4. Способ по п.1, где каталитический компонент, включающий элемент группы 15, сушат напылением на подложку.
5. Способ по п.1, где каталитическое соединение в композиции (I) представляет собой металлоценовое каталитическое соединение.
6. Способ по п.1, где композиция (II) обладает вязкостью при 20°С в пределах от 130 до 2000 сП.
7. Способ по п.1, в котором перед введением в реактор каталитическую композицию готовят совмещением в смесителе
8. Способ по п.1, в котором композиции (I) и (II) совмещают в течение до 120 мин.
9. Способ по п.1, в котором композиции (I) и (II) совмещают в течение времени в пределах от 5 до 40 мин.
10. Способ по п.1, в котором каталитическую композицию вводят в реакто через впрыскивающее сопло.
11. Способ по п.9, где впрыскивающее сопло сужается таким образом, что уменьшение его внутреннего диаметра находится в пределах от 5 до 50%.
12. Способ по п.1, в котором каталитическое соединение, включающее элемент группы 15, представлено
Figure 00000001
Figure 00000002
в которой
М обозначает атом металла группы 4, 5 или 6; каждый Х независимо обозначает анионную уходящую группу; у обозначает 0 или 1;
n обозначает состояние окисления М;
m обозначает формальный заряд лиганда, представленного формулой YZL или YZL’;
L обозначает атом элемента группы 15 или 16;
L" обозначает атом элемента группы 15 или 16 или группу, содержащую атом элемента группы 14;
Y обозначает атом элемента группы 15;
Z обозначает атом элемента группы 15;
R1 и R2 каждый независимо обозначает углеводородную C1-C20группу, гетероатомсодержащую группу, включающую до двадцати углеродных атомов, атом кремния, германия, олова, свинца или фосфора;
R1 и R2 могут быть также связанными между собой;
R3 отсутствует или обозначает углеводородную группу, атом водорода, галогена или гетероатомсодержащую группу;
R4 и R5 каждый независимо обозначает алкильную группу, арильную группу, замещенную арильную группу, циклическую алкильную группу, замещенную циклическую алкильную группу, циклическую аралкильную группу, замещенную циклическую аралкильную группу или полициклическую систему;
R4 и R5 могут быть связанными между собой;
R6 и R7 каждый независимо отсутствует или обозначает атом водорода, алкильную группу, атом галогена, гетероатом или гидрокарбильную группу; а
R* отсутствует или обозначает атом водорода, группу, содержащую атом элемента группы 14, атом галогена или гетероатомсодержащую группу.
13, Способ по п.1, в котором полимер изационный реактор представляет собой газофазный реактор.
14. Способ по п.1, в котором полимеризационный реактор представляет собой реактор с суспензионной фазой.
15. Способ по п.1, в котором свойства полимера регулируют вначале анализом образца полимерного продукта с определением первичного свойства продукта, последующим изменением технологического параметра для достижения вторичного свойства продукта.
16. Способ по п.15, в котором свойство продукта выбирают из ряда, включающего показатель текучести, индекс расплава, плотность, ММР, содержание сомономерных звеньев и их сочетания.
17. Способ по п.15, в котором изменение технологического параметра выбирают из ряда, включающего изменение концентрации водорода, изменение количества первого катализатора, изменение количества второго катализатора, изменение количества жидкости и/или газа, который отводят из реактора, изменение полимеризационной температуры, изменение парциального давления олефина (олефинов), изменение соотношения между олефином и сомономером, изменение соотношения между активатором и переходным металлом, изменение относительных скоростей введения суспензии каталитического компонента и/или раствора каталитического компонента, изменение продолжитнльности, степени или температуры совмещения суспензии каталитического компонента и раствора каталитического компонента и их сочетания.
18. Способ по п.1, в котором полимерный продукт разделяют на фракции в соответствии со следующей таблицей:
Число меш сита Собранные фракции Наименование фракции 10 меш >2000 мкм Фракция 1 18 меш 2000-1000 мкм Фракция 2 35 меш <1000-500 мкм Фракция 3 60 меш <500-250 мкм Фракция 4 120 меш <250-125 мкм Фракция 5 200 меш/поддон <125 мкм Фракция 6 В целом   Фракция 6
а индексы расплавов фракций 3, 4 и 5 относительно друг друга варьируются не больше чем на 30%.
19. Способ по п.1, в котором композиция (II) представляет собой композицию, включающую минеральное или силиконовое масло, подложку, активатор и необязательно каталитическое соединение, содержащее элемент группы 15.
20. Способ по п.1, в котором композиция (II) представляет собой композицию, включающую C530алкановый разбавитель и каталитическое соединение.
RU2003119544/04A 2000-12-04 2001-11-27 Способ полимеризации RU2258712C2 (ru)

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US09/729,453 US6608149B2 (en) 2000-12-04 2000-12-04 Polymerization process
US09/729,550 2000-12-04
US09/729,453 2000-12-04
US09/729,550 US6605675B2 (en) 2000-12-04 2000-12-04 Polymerization process

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