RU2031901C1 - Способ получения катализатора полимеризации этилена - Google Patents

Способ получения катализатора полимеризации этилена Download PDF

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RU2031901C1
RU2031901C1 SU904743351A SU4743351A RU2031901C1 RU 2031901 C1 RU2031901 C1 RU 2031901C1 SU 904743351 A SU904743351 A SU 904743351A SU 4743351 A SU4743351 A SU 4743351A RU 2031901 C1 RU2031901 C1 RU 2031901C1
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Russia
Prior art keywords
synthesis
catalyst
aluminium
aluminum
polymerization
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SU904743351A
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English (en)
Inventor
Рескони Луиджи
Джанини Умберто
Альбицати Энрико
Original Assignee
Аусимонт С.р.л.
Хаймонт Инкорпорейтед
Монтедисон С.п.А.
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Priority to IT8919253A priority Critical patent/IT1237398B/it
Priority to US07/471,902 priority patent/US5126303A/en
Priority to IL93204A priority patent/IL93204A/xx
Priority to ZA90639A priority patent/ZA90639B/xx
Priority to CA002008906A priority patent/CA2008906C/en
Priority to YU00173/90A priority patent/YU17390A/xx
Priority to FI900467A priority patent/FI103123B1/fi
Priority to NO900435A priority patent/NO174106C/no
Priority to CS90428A priority patent/CZ281689B6/cs
Priority to IN83CA1990 priority patent/IN173199B/en
Priority to HU94/90A priority patent/HU218844B/hu
Priority to MX19309A priority patent/MX19309A/es
Priority to AU48892/90A priority patent/AU626628B2/en
Priority to BR909000415A priority patent/BR9000415A/pt
Priority to ES199090101893T priority patent/ES2041053T3/es
Priority to AT90101893T priority patent/ATE89290T1/de
Priority to CN90101414A priority patent/CN1019579B/zh
Priority to DE90101893T priority patent/DE69001565T2/de
Priority to JP2021874A priority patent/JP2954251B2/ja
Priority to PT93023A priority patent/PT93023B/pt
Priority to KR1019900001116A priority patent/KR0145291B1/ko
Priority to EP90101893A priority patent/EP0384171B1/en
Application filed by Аусимонт С.р.л., Хаймонт Инкорпорейтед, Монтедисон С.п.А. filed Critical Аусимонт С.р.л.
Priority to SU904743351A priority patent/RU2031901C1/ru
Publication of RU2031901C1 publication Critical patent/RU2031901C1/ru
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—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
    • C08F4/65922—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
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

Использование изобретения: получение полиэтилена низкого давления. Сущность изобретения: проводят взаимодействие в среде растворителя цирконоцена общей формулы L2Zr X2, где L - пентаметилциклопентадиенил или инденил, X - Cl, - CH3 или - OH, с соединением алюминия: триалкилом или диалкилмоногидридом алюминия. Атомное соотношение алюминия: цирконий от 869:1 до 8670:1. 1 табл.

Description

Изобретение относится к полимерной химии и может найти использование при получении полиэтилена низкого давления.
Известен способ получения катализатора полимеризации олефинов взаимодействием цирконоценов с алюминиевыми соединениями [1].
Наиболее близким по технической сущности и достигаемому результату является известный способ получения катализатора полимеризации этилена взаимодействием в среде растворителя цирконоцена с соединением алюминия [2].
В качестве последнего используют алюмоксаны. Наиболее высокая активность катализатора достигается при полимеризации С3 - и более α -олефинов.
Технической задачей изобретения является повышение активности катализатора при полимеризации этилена с использованием в качестве соединения алюминия триалкилалюминиевых соединений.
Указанный технический результат достигается тем, что по способу получения катализатора полимеризации этилена взаимодействием в среде растворителя цирконоцена с соединением алюминия в качестве цирконоцена используют соединение общей формулы
L2ZrX2, где L - пентаметилциклопентадиенил или инденил;
X - -Сl, -CH3 или ОН, в качестве соединения алюминия - триалкил или диалкилмоногидрид алюминия и процесс осуществляют при атомном соотношении алюминий:цирконий от 869:1 до 8670:1.
Полимеризацию проводят в жидкой фазе в присутствии или без инертного углеводородного растворителя, или в газовой фазе. Температура полимеризации обычно составляет 0-150оС, предпочтительно 40-80оС.
В качестве углеводородных растворителей могут быть использованы, например, толуол, гексан, гептан, или хлорированные углеводороды такие, как СН2Сl2 или С2Н4Cl2.
Варьировать молекулярный вес полимера можно простым изменением температуры полимеризации, типа и концентрации компонентов катализатора или, используя регуляторы молекулярной массы, например водород.
Особенно хорошие результаты получают в случае, когда компоненты катализатора подвергают контактированию друг с другом перед проведением полимеризации; время контактирования обычно варьируют в пределах от 1 мин до 1 ч, предпочтительно 5-10 мин, концентрация цирконоценового соединения составляет 10-3-10-8 моль/л, а концентрация алкилалюминия - 10-10-3 моль/л.
Изобретение иллюстрируется следующими примерами.
П р и м е р 1. В автоклаве объемом 1 л, снабженном кожухом для регулирования теплообмена, термопарой, клапанами для подачи азота и этилена, манометром и стальной магнитной мешалкой, термостатированной при 50оС, вводят этилен до давления 1 ати и 350 мл толуола, поддерживая температуру на уровне 50оС.
В 50 мл толуола в атмосфере азота подвергают взаимодействию 2 ммоль триметилалюминия и 1 мг [C5(CH3)5] 2ZrCl2. Через 5 мин выдерживания при комнатной температуре раствор вводят в автоклав, в котором затем с помощью этилена создают давление 4 ати. Полимеризацию проводят в течение 1 ч при температуре 50оС, поддерживая постоянное давление этилена. Скорость перемешивания 1100 об/мин. Полученные результаты приведены в таблице.
П р и м е р ы 2-9. Повторяют процедуру из примера 1, используя различные алкилалюминиевые соединения и цирконоцены. Использованные соединения и полученные результаты показаны в таблице.

Claims (1)

  1. СПОСОБ ПОЛУЧЕНИЯ КАТАЛИЗАТОРА ПОЛИМЕРИЗАЦИИ ЭТИЛЕНА взаимодействием в среде растворителя цирконоцена с соединением алюминия, отличающийся тем, что в качестве цирконоцена используют соединение формулы
    L2ZrX2,
    где L - пентаметилциклопентадиенил или инденил;
    X - -Cl, -CH3 или -OH,
    в качестве соединения алюминия - триалкил или диалкилмоногидрид алюминия и процесс осуществляют при атомном соотношении алюминий : цирконий (869 : 1) - (8670 : 1).
SU904743351A 1989-01-31 1990-02-27 Способ получения катализатора полимеризации этилена RU2031901C1 (ru)

Priority Applications (23)

Application Number Priority Date Filing Date Title
IT8919253A IT1237398B (it) 1989-01-31 1989-01-31 Catalizzatori per la polimerizzazione di olefine.
IL93204A IL93204A (en) 1989-01-31 1990-01-29 Catalysts for the polymerization of olefins
ZA90639A ZA90639B (en) 1989-01-31 1990-01-29 Catalysts for the polymerization of olefins
US07/471,902 US5126303A (en) 1989-01-31 1990-01-29 Catalysts for the polymerization of olefins
MX19309A MX19309A (es) 1989-01-31 1990-01-30 Catalizador para la polimerizacion de olefinas
FI900467A FI103123B1 (fi) 1989-01-31 1990-01-30 Olefiinien polymeroinnissa käytettäviä katalyyttejä
NO900435A NO174106C (no) 1989-01-31 1990-01-30 Katalysatorer for polymerisering av olefiner
CS90428A CZ281689B6 (cs) 1989-01-31 1990-01-30 Katalyzátor polymerace olefinů
IN83CA1990 IN173199B (ru) 1989-01-31 1990-01-30
HU94/90A HU218844B (hu) 1989-01-31 1990-01-30 Metallocénvegyületből és alumoxánvegyületből készített olefin polimerizációs katalizátor és eljárás előállítására
CA002008906A CA2008906C (en) 1989-01-31 1990-01-30 Catalysts for the polymerization of olefins
AU48892/90A AU626628B2 (en) 1989-01-31 1990-01-30 Catalysts for the polymerization of olefins
YU00173/90A YU17390A (en) 1989-01-31 1990-01-30 Catalysts for olephins polymerization
ES199090101893T ES2041053T3 (es) 1989-01-31 1990-01-31 Catalizadores para la polimerizacion de olefinas.
BR909000415A BR9000415A (pt) 1989-01-31 1990-01-31 Catalisadores para polimerizacao de olefinas
AT90101893T ATE89290T1 (de) 1989-01-31 1990-01-31 Katalysator fuer olefinpolymerisation.
CN90101414A CN1019579B (zh) 1989-01-31 1990-01-31 制备烯烃聚合催化剂的方法
DE90101893T DE69001565T2 (de) 1989-01-31 1990-01-31 Katalysator für Olefinpolymerisation.
JP2021874A JP2954251B2 (ja) 1989-01-31 1990-01-31 オレフィン重合用触媒
PT93023A PT93023B (pt) 1989-01-31 1990-01-31 Processo de preparacao de catalisadores para polimerizacao de olefinas
KR1019900001116A KR0145291B1 (ko) 1989-01-31 1990-01-31 올레핀류의 중합용 촉매
EP90101893A EP0384171B1 (en) 1989-01-31 1990-01-31 Catalysts for the polymerization of olefins.
SU904743351A RU2031901C1 (ru) 1989-01-31 1990-02-27 Способ получения катализатора полимеризации этилена

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT8919253A IT1237398B (it) 1989-01-31 1989-01-31 Catalizzatori per la polimerizzazione di olefine.
IN83CA1990 IN173199B (ru) 1989-01-31 1990-01-30
SU904743351A RU2031901C1 (ru) 1989-01-31 1990-02-27 Способ получения катализатора полимеризации этилена

Publications (1)

Publication Number Publication Date
RU2031901C1 true RU2031901C1 (ru) 1995-03-27

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SU904743351A RU2031901C1 (ru) 1989-01-31 1990-02-27 Способ получения катализатора полимеризации этилена

Country Status (23)

Country Link
US (1) US5126303A (ru)
EP (1) EP0384171B1 (ru)
JP (1) JP2954251B2 (ru)
KR (1) KR0145291B1 (ru)
CN (1) CN1019579B (ru)
AT (1) ATE89290T1 (ru)
AU (1) AU626628B2 (ru)
BR (1) BR9000415A (ru)
CA (1) CA2008906C (ru)
CZ (1) CZ281689B6 (ru)
DE (1) DE69001565T2 (ru)
ES (1) ES2041053T3 (ru)
FI (1) FI103123B1 (ru)
HU (1) HU218844B (ru)
IL (1) IL93204A (ru)
IN (1) IN173199B (ru)
IT (1) IT1237398B (ru)
MX (1) MX19309A (ru)
NO (1) NO174106C (ru)
PT (1) PT93023B (ru)
RU (1) RU2031901C1 (ru)
YU (1) YU17390A (ru)
ZA (1) ZA90639B (ru)

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PT93023A (pt) 1990-07-31
EP0384171A1 (en) 1990-08-29
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JP2954251B2 (ja) 1999-09-27
CZ42890A3 (en) 1996-07-17
HUT53132A (en) 1990-09-28
FI103123B (fi) 1999-04-30
FI900467A0 (fi) 1990-01-30
HU218844B (hu) 2000-12-28
IT1237398B (it) 1993-06-01
KR0145291B1 (ko) 1998-07-15
PT93023B (pt) 1998-04-30
ATE89290T1 (de) 1993-05-15
MX19309A (es) 1994-03-31
EP0384171B1 (en) 1993-05-12
BR9000415A (pt) 1991-01-15
DE69001565D1 (de) 1993-06-17
FI103123B1 (fi) 1999-04-30
NO900435L (no) 1990-08-01
CA2008906A1 (en) 1990-07-31
AU4889290A (en) 1990-08-09
NO900435D0 (no) 1990-01-30
JPH03197514A (ja) 1991-08-28
YU17390A (en) 1991-08-31
CN1019579B (zh) 1992-12-23
DE69001565T2 (de) 1993-11-18
CA2008906C (en) 1999-11-16
NO174106C (no) 1994-03-16
IL93204A (en) 1993-03-15
IL93204A0 (en) 1990-11-05
KR900011794A (ko) 1990-08-02
AU626628B2 (en) 1992-08-06
HU900594D0 (en) 1990-04-28
CZ281689B6 (cs) 1996-12-11
IT8919253A0 (it) 1989-01-31
NO174106B (no) 1993-12-06
ES2041053T3 (es) 1993-11-01
US5126303A (en) 1992-06-30
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