EP0000748A1 - Procédé de préparation de polymères d'éthylène - Google Patents
Procédé de préparation de polymères d'éthylène Download PDFInfo
- Publication number
- EP0000748A1 EP0000748A1 EP78100534A EP78100534A EP0000748A1 EP 0000748 A1 EP0000748 A1 EP 0000748A1 EP 78100534 A EP78100534 A EP 78100534A EP 78100534 A EP78100534 A EP 78100534A EP 0000748 A1 EP0000748 A1 EP 0000748A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxygen
- chromium
- carbon monoxide
- catalyst precursor
- stage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
Definitions
- Processes of this type are known to have a number of advantageous aspects compared to comparable other processes, but on the other hand also leave one or two wishes unfulfilled.
- This desire is particularly understandable in that, with increasing catalyst yield, polymers with a decreasing content of residual catalyst are obtained; - The latter should be as small as possible that a - complex - cleaning step to remove the residues can be omitted.
- the centerpiece is the use of a special chromium oxide supported catalyst, which is obtained from a specific intermediate catalyst product in two stages in a specific way.
- the catalyst intermediate as such is not associated with any special features; it can be one which is customary in the polymerization of olefins by means of supported chromium oxide catalysts.
- the preliminary product is based on a carrier which has a particle size of 0.02 to 3, in particular of C, 04 to 1.5 mm.
- the carrier consists of silicon dioxide or is a silicon dioxide which is chemically or physically linked to a component consisting of the elements aluminum, titanium, zirconium, molybdenum, vanadium or thor, which component is an oxide of the element concerned or one under the conditions step (1) into an oxide composition of the affected element.
- this (calculated as oxide) can make up to 20, in particular up to 15, percent by weight, based on the total weight of the carrier.
- Silicon dioxide mixed oxides which contain 0.1 to 15 percent by weight, based on the total weight of the carrier, of aluminum oxide are particularly suitable as carriers.
- the catalyst precursor i.e. the carrier loaded with a chromium compound, which is chromium trioxide or a chromium compound which converts to chromium trioxide under the conditions of stage (1), is treated in a known manner with oxygen in a first stage (1) in a certain manner as defined above . It is of particular importance that the solid is left in the form of a fluidized bed; - Where you can use such devices and procedures, as are common in fluidized bed processes. As has been shown, air is the preferred carrier gas. As has also been shown, the period of whirling is not critical, apart from the minimum period of 30 minutes, but should generally be 2 to 15 hours for convenience.
- the oxygen treatment in stage (1) is combined with treatment by a promoter.
- the promoters can be the relevant ones be usual, such as in particular ammonium silicofluoride '(NH 4 ) 2 SiF 6 , and can be added to the catalyst precursor before or during the vortexing.
- stage (2) the product obtained from stage (1), which is preferably flushed free of oxygen, is treated with carbon monoxide in a specific manner defined above and thus converted into the actual supported chromium oxide catalyst.
- stage (1) which is preferably flushed free of oxygen
- carbon monoxide in a specific manner defined above and thus converted into the actual supported chromium oxide catalyst.
- the solid is left in the form of a fluidized bed, and that the carrier gas is anhydrous and oxygen-free.
- Polymers of ethylene are produced using the new catalysts by means of the so-called “solution polymerization process”, cyclohexane in particular being considered as a solvent.
- solution polymerization process cyclohexane in particular being considered as a solvent.
- the polymerization process as such has no special features and can be carried out in the relevant customary technological configurations.
- a catalyst precursor consists of a homogeneously loaded silica / alumina mixed oxide containing chromium trioxide in a weight ratio of carrier: chromium trioxide of 100: 4.4, which contains 0.4 percent by weight, based on the total weight of the mixed oxide, and one Has particle size of 0.04 to 1.5 mm.
- This preliminary product is mixed with a promoter (ammonium silicon fluoride) in a weight ratio of catalyst preliminary product: promoter of 100: 2.5.
- promoter ammonium silicon fluoride
- a stirred autoclave is charged with 1000 parts by weight of cyclohexane, whereupon it is flushed with nitrogen and 0.1 part by weight of catalyst is added.
- a thermostatically controlled temperature of 150 ° C. pure ethylene is pressed up to a pressure of 35 bar, the process is continued until the pressure has dropped to 25 bar due to the formation of polyethylene, and then ethylene is pressed again up to a pressure of 35 bar and so on for 90 minutes.
- the polymerization is then terminated by cooling to room temperature and relaxing.
- a preliminary catalyst product consists of a silica / alumina mixed oxide loaded homogeneously with chromium trioxide in a weight ratio of carrier: chromium trioxide of 100: 2.0, which contains 0.1 percent by weight, based on the total weight of the mixed oxide, and one Has particle size of 0.04 to 1.5 mm.
- This preliminary product is mixed with a promoter (ammonium silicon fluoride) in a weight ratio of catalyst preliminary product: promoter of 100: 1.5.
- promoter ammonium silicon fluoride
- a catalyst pre-product consists of a silica / alumina mixed oxide loaded homogeneously with chromium trioxide in a weight ratio of carrier: chromium trioxide of 100: 4.5, which is 0.3% by weight, based on the total weight of the mixed oxide-aluminum oxide contains and has a particle size of 0.04 to 1.5 mm.
- Example 3 The procedure is as in Example 3, with the exception that the first stage (1) is carried out at a temperature of 570 ° C. (instead of 680 ° C.).
- Example 2 The procedure is as in Example 1, with the exceptions that a temperature of 146 ° C. (instead of 150 ° C.) is used and that instead of ethylene, a mixture of 98.5 parts by weight of ethylene and 1.5 parts by weight of butene-1 is polymerized .
Landscapes
- 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)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772734909 DE2734909A1 (de) | 1977-08-03 | 1977-08-03 | Verfahren zum herstellen von polymerisaten des aethylens |
DE2734909 | 1977-08-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0000748A1 true EP0000748A1 (fr) | 1979-02-21 |
Family
ID=6015486
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100534A Withdrawn EP0000748A1 (fr) | 1977-08-03 | 1978-07-28 | Procédé de préparation de polymères d'éthylène |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0000748A1 (fr) |
JP (1) | JPS5428380A (fr) |
AT (1) | ATA559578A (fr) |
DE (1) | DE2734909A1 (fr) |
DK (1) | DK342078A (fr) |
ES (1) | ES472325A1 (fr) |
FI (1) | FI782362A (fr) |
IT (1) | IT7825982A0 (fr) |
NO (1) | NO782639L (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0279890A2 (fr) * | 1986-06-16 | 1988-08-31 | Phillips Petroleum Company | Génération "in situ" de comonomères lors de la polymérisation d'oléfines |
EP0307907A2 (fr) * | 1987-09-18 | 1989-03-22 | Phillips Petroleum Company | Procédé de polymérisation d'oléfines |
WO1989012662A1 (fr) * | 1988-06-23 | 1989-12-28 | Mobil Oil Corporation | Oligomeres olefiniques ayant des proprietes lubrifiantes et leur procede de production |
EP0361363A2 (fr) * | 1988-09-26 | 1990-04-04 | Phillips Petroleum Company | Procédé de polymérisation de polyéthylène basse densité à haute résistance mécanique et film à partir de celui-ci (film phénoménal) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5866661A (en) * | 1996-12-13 | 1999-02-02 | Phillips Petroleum Company | Ethylene polymerization processes and products thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1115023B (de) * | 1955-10-14 | 1961-10-12 | Phillips Petroleum Co | Verfahren und Vorrichtung zum Aktivieren oder Regenerieren eines chromoxydhaltigen Olefin-polymerisationskatalysators |
FR1302764A (fr) * | 1960-10-07 | 1962-08-31 | Phillips Petroleum Co | Procédé de polymérisation des oléfines et catalyseur utilisé dans ce procédé |
US3362946A (en) * | 1964-06-01 | 1968-01-09 | Phillips Petroleum Co | Method of treating supported chromium oxide catalyst and polymerization therewith |
DE1906175B1 (de) * | 1968-02-08 | 1970-08-27 | Phillips Petroleum Co | Verfahren zur Aktivierung eines Chromoxyd-Traegerkatalysators |
SU373986A1 (ru) * | 1971-06-01 | 1975-02-05 | Институт Катализа Сибирского Отделения Ан Ссср | Способ приготовлени катализатора дл полимеризации этилена |
-
1977
- 1977-08-03 DE DE19772734909 patent/DE2734909A1/de active Pending
-
1978
- 1978-07-21 IT IT7825982A patent/IT7825982A0/it unknown
- 1978-07-28 EP EP78100534A patent/EP0000748A1/fr not_active Withdrawn
- 1978-07-31 FI FI782362A patent/FI782362A/fi not_active Application Discontinuation
- 1978-08-02 AT AT559578A patent/ATA559578A/de not_active Application Discontinuation
- 1978-08-02 NO NO782639A patent/NO782639L/no unknown
- 1978-08-02 JP JP9371178A patent/JPS5428380A/ja active Pending
- 1978-08-02 DK DK342078A patent/DK342078A/da unknown
- 1978-08-03 ES ES472325A patent/ES472325A1/es not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1115023B (de) * | 1955-10-14 | 1961-10-12 | Phillips Petroleum Co | Verfahren und Vorrichtung zum Aktivieren oder Regenerieren eines chromoxydhaltigen Olefin-polymerisationskatalysators |
FR1302764A (fr) * | 1960-10-07 | 1962-08-31 | Phillips Petroleum Co | Procédé de polymérisation des oléfines et catalyseur utilisé dans ce procédé |
US3362946A (en) * | 1964-06-01 | 1968-01-09 | Phillips Petroleum Co | Method of treating supported chromium oxide catalyst and polymerization therewith |
DE1906175B1 (de) * | 1968-02-08 | 1970-08-27 | Phillips Petroleum Co | Verfahren zur Aktivierung eines Chromoxyd-Traegerkatalysators |
SU373986A1 (ru) * | 1971-06-01 | 1975-02-05 | Институт Катализа Сибирского Отделения Ан Ссср | Способ приготовлени катализатора дл полимеризации этилена |
Non-Patent Citations (1)
Title |
---|
DERWENT "Soviet inventtions illustrated", Chemical Seection 1, vol. W, Nr. 31 (1975) & SU-A-373 986 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0279890A2 (fr) * | 1986-06-16 | 1988-08-31 | Phillips Petroleum Company | Génération "in situ" de comonomères lors de la polymérisation d'oléfines |
EP0279890A3 (en) * | 1986-06-16 | 1989-09-13 | Phillips Petroleum Company | In situ comonomer generation in olefin polymerization |
EP0307907A2 (fr) * | 1987-09-18 | 1989-03-22 | Phillips Petroleum Company | Procédé de polymérisation d'oléfines |
EP0307907A3 (en) * | 1987-09-18 | 1989-09-27 | Phillips Petroleum Company | Process for olefin polymerization |
WO1989012662A1 (fr) * | 1988-06-23 | 1989-12-28 | Mobil Oil Corporation | Oligomeres olefiniques ayant des proprietes lubrifiantes et leur procede de production |
EP0361363A2 (fr) * | 1988-09-26 | 1990-04-04 | Phillips Petroleum Company | Procédé de polymérisation de polyéthylène basse densité à haute résistance mécanique et film à partir de celui-ci (film phénoménal) |
EP0361363A3 (fr) * | 1988-09-26 | 1991-08-07 | Phillips Petroleum Company | Procédé de polymérisation de polyéthylène basse densité à haute résistance mécanique et film à partir de celui-ci (film phénoménal) |
Also Published As
Publication number | Publication date |
---|---|
FI782362A (fi) | 1979-02-04 |
NO782639L (no) | 1979-02-06 |
IT7825982A0 (it) | 1978-07-21 |
DK342078A (da) | 1979-02-04 |
ATA559578A (de) | 1980-08-15 |
ES472325A1 (es) | 1979-02-16 |
DE2734909A1 (de) | 1979-02-15 |
JPS5428380A (en) | 1979-03-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE2802517C2 (fr) | ||
DE2711911C3 (de) | Verfahren zur Herstellung von Chromoxyd-Träger-Katalysatoren für die Olefinpolymerisation und Verfahren zur Polymerisation von Äthylen | |
DE2729122C3 (de) | Katalysatorzusammensetzung und Verfahren zur Homo- oder Mischpolymerisation von Äthylen | |
DE2210959C2 (de) | Chromoxidkatalysatoren für die Polymerisation von Äthylen allein bzw. im Gemisch mit einem α-Olefin mit 3 bis 8 Kohlenstoffatomen | |
DE2540278C2 (de) | Verfahren zum Herstellen von Olefinpolymerisaten | |
EP0757044B1 (fr) | Procédé pour la regénération d'un catalyseur | |
DE1903148C3 (de) | Verfahren zum Calcinieren eines Polymerisationskatalysators | |
EP0000751A1 (fr) | Procédé de préparation d'un catalyseur à l'oxyde de chrome sur un support pour la polymérisation des oléfines | |
EP0000748A1 (fr) | Procédé de préparation de polymères d'éthylène | |
DE2531899A1 (de) | Verfahren zur herstellung von polyolefinen | |
EP0263525B1 (fr) | Procédé de préparation d'homo- et de copolymères d'éthylène au moyen d'un catalyseur au trioxyde de chrome | |
EP0003321B1 (fr) | Procédé pour la préparation d'un catalyseur et son utilisation pour la polymérisation d'1-oléfines | |
DE2461187A1 (de) | Verfahren zur herstellung von polyolefinen | |
EP0004533A2 (fr) | Procédé pour la préparation d'une polyoléfine | |
DE2314412A1 (de) | Verfahren zum polymerisieren von olefinen | |
DE69112901T2 (de) | Polymerisationskatalysator und Verfahren. | |
DE69212789T2 (de) | Olefinpolymerisation | |
EP0250860A2 (fr) | Procédé de préparation de polymères de l'éthylène par catalyse Phillips | |
DE1133890B (de) | Verfahren zur Polymerisation von Olefinen | |
DE2314594C3 (de) | Verfahren zur Polymerisation von Äthylen und Katalysator zu seiner Durchführung | |
EP0827969A2 (fr) | Catalyseurs de chrome supportés par des tamis moléculaires mésoporeux | |
DE2263124A1 (de) | Verfahren zur herstellung von katalysatoren zur polymerisation von olefinen | |
DE2614325A1 (de) | Verfahren zur herstellung von polyolefinen | |
DE1048414B (de) | Verfahren zur Herstellung von hochmolekularen Polyolefinen | |
DE1229733B (de) | Verfahren zur Herstellung von Mischpolymerisaten des AEthylens mit aliphatischen 1-Olefinen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): BE CH DE FR GB NL SE |
|
17P | Request for examination filed | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SCHULZE, KURT |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19810729 |