CA1090765A - Ethylene polymerization catalyst and method - Google Patents
Ethylene polymerization catalyst and methodInfo
- Publication number
- CA1090765A CA1090765A CA289,822A CA289822A CA1090765A CA 1090765 A CA1090765 A CA 1090765A CA 289822 A CA289822 A CA 289822A CA 1090765 A CA1090765 A CA 1090765A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- polyethylene
- mixture
- molecular weight
- weight distribution
- 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.)
- Expired
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
Abstract
Abstract of the Disclosure A highly active catalyst for polymerizing ethylene to polyethylene having a narrow molecular weight distribution, a method of making the catalyst and a method of polymerizing ethyl-one to such a polyethylene in which the catalyst is prepared by forming a mixture of a porous support of silica, alumina, zirconia, thoria or mixtures and a chromium compound and an alkyl ester of boron containing 1-7 carbon atoms in the alkyl group or a halide of boron capable of reacting with the chromium compound and acti-vating this mixture at an elevated temperature in a fluidized bed with a substantially dry reducing gas followed by fluidizing with an oxidizing gas at an elevated temperature.
Description
~09()7~
ETHYLENE POLYMERIZATION CATALYST AND METHOD
Background of the Invention In prior U.S. patent 3,780,011, assigned to the assignee hereof, there is described and claimed a catalyst and method in which the catalyst is prepared by treating a mixtureof a support such as silica and chromium trioxide with an ester of titanium, boron or vanadium or mixtures while fluidizing the resulting bed followed by activating the bed with a dry gas that contains oxygen at elevated temperatures.
This catalyst is useful in producing polyolefins and particu-larly polyethylene with controllable visco-elastic properties.
When the ester is boron the activity in ethylene polymerization is satisfactory but preferably should be higher and the poly-ethylene has narrow molecular weight distribution. In the present invention the catalyst which contains boron as well as chromium has greatly increased activity while still producing polyethylene having a narrow molecular weight distribution.
7~i~
In one broad aspect, the invention comprehends a highlyactive catalyst for polymerizing ethylene to polyethylene which catalyst has a narrow molecular weight distribution and is prepared by forming a mixture of a porous support of the class consisting of silica, alumina, zirconia, thoria and mixtures thereof, a chromium compound and an alkyl ester of boron containing 1 to about 7 carbon atoms in the alkyl group or a halide of boron. The chromium compound is reactive with the alkyl ester to form a chromium-boron compound upon heating, the mixture containing about 0.1 - 10 wt. % of boron and about 0.5 - 10 wt.% of chromium and this mixture is then activated at an elevated temperature in a fluidized bed with a substantially dry reducing gas and then fluidized with an oxidizing gas at an elevated temperature.
The invention further comprehends a method of making a highly active catalyst for polymerizing ethylene to poly-ethylene which has a narrow molecular weight distribution and comprises forming a mixture of a porous support of the class 20 consisting of silica, alumina, zirconia, thoria and mixtures -thereof, a chromium compound and an alkyl ester of boron containing 1 to about 7 carbon atoms in the alkyl group or a halide of boron. The chromium compound is reactive with the alkyl ester to form a chromium-boron compound upon heating, the mixture containing about 0.1 - 10 wt. % of boron and about 0.5 - 10 wt.% of chromium. This mixture is activated at an elevated temperature in a fluidized bed with a substantially dry reducing gas and then fluidized with an oxidizing gas at an elevated temperature.
Description of the Preferred Embodiment In this invention the porous support is either silica, U'7ti5 alumina, zirconia, thoria or mixtures thereof. This support is mixed with a chromium compound such as chromium trioxide, chromic nitrate, ammonium chromate or an organochromate that is reactive with the boron ester that is added later.
Then the mixture is preferably heated by fluidizing the resulting bed with a gas that is inert to the bed and its ingredients wh;le heating at an elevated temperature. Then an alkyl ester of boron containing about 1-7 carbon atoms in the alkyl group or a halide of boron is added to the chromium containing bed with the two ingredients being present in an amount to give about 0.1 - 10 wt.% of boron. Then the bed is activated at an elevated temperature by fluidizing the bed with a substantially dry reducing gas and finally fluidizing with an oxidizing gas at an elevated temperature.
Under these conditions the boron ester reacts with the chromium oxide to form a chromium-boron compound and under the heating and with the reducing gas at a higher temperature a boron-chromium support (e.g. silica) compound. The final treatment with an oxidizing gas such as air at an elevated temperature is for a very short time to oxidize the ingredients of the bed after which the bed is cooled down in an inert atmosphere. The catalyst thusly prepared is active in ethylene polymerization to produce polyethylene of narrow molecular weight distribution and the activity of such a catalyst is greatly increased over the same catalyst without the modifica-tion and the activation of this invention.
The temperature of activating and of the final oxidizing step is above 250C. and preferably between about 600-900C. with a practical range being about 400-800C. The total time for activating and then oxidizing is preferably from about 1 minute to as much as 48 hours.
lO~V7~j After being activated, the catalyst may be used immediately in a polymerization process or can be stored under substantially anhydrous conditions until desired for use. The polymerization process is simply that of contacting the ethy-lene monomer with an effective catalytic amount of the catalyst in the presence or the absence of diluents or solvents which are known to be suitable. The polymerization process may be under known conditions of temperature, pressure-or the like.
The polymerization may be conducted in the presence of a hydrocarbon which is liquid under the reaction conditions and which acts as a diluent and not a solvent for polyethylene under the reaction conditions employed. Preferred hydrocarbon diluents are paraffins including cycloparaffins and particularly paraffins and cycloparaffins having 3-12 carbon atoms. Illus-trative of diluents are propane, isobutane, n-pentane, isopen-tane, neopentane, 2,2,4-trimethylpentane, cyclohexane and methylcyclohexane.
The thusly produced catalyst may be used to cata-lyze the polymerization of ethylene at the customary tempera-tures of, for example, about 30C. or less up to about 200C.
or more.
In the preferred process the bed containing the chromium compound is heated before adding the boron ester as - by heating in a fluidized bed with a gas at a temperature of about 100C. The boron ester is then added as specified and this may be any of the alkyl borates coming within the desig-nated group of which isopropylborate, trimethylborate and the like are examples.
The reducing gas which is used in the activating step prior to the final oxidizing can conveniently be a mixture of nitrogen and carbon monoxide containing at least 1 wt.%
carbon monoxide.
- 105~V7~
As noted, the polymerization of the ethylene with the highly active catalyst of this invention can be in a par-ticle form process, solution process or can be a gas phase process. The activity of this catalyst is greater than catalysts containing boron prepared according to the above U. S. patent 3,780,011. The resulting polyethylene which has narrow molecular weight distribution is useful in making film, thermoforming objects and the like.
The following examples are illustrative of the invention with Example 1 being a control in which the catalyst is prepared according to the above U. S. patent 3,780,011.
Example 1 (Control) In this control example the catalyst was prepared by forming a mixture of silica, chromium trioxide and iso-propylborate in an amount to give 2% boron and 1% chromium.
This mixture was then activated in air at about 610C. for about 5 hours. This catalyst which is similar to that dis-closed in the boron containing catalyst of the above U.S.
patent 3,780,011 when used to polymerize ethylene at 550 psig using isobutane as a diluent and a reaction temperature of 105C. resulted in polyèthylene at a reactivity of 1094 g/g cat/hr.
Example 2 In the following examples that are according to the present invention the same boron ester was used and the same chromium trioxide also on silica and in amounts to give 1.5% boron and 1% chromium in the resulting bed. This mix-ture was activated by fluidizing with a reducing gas compris-ing 7~ carbon monoxide and 93~ nitrogen for 5 hours at 610C.
At the end of this period the reducing gas was discontinued and air was introduced at this same 610C. for 30 minutes.
6~
At the conclusion of this period the air flow was terminated and nitrogen was introduced and the catalyst was cooled with nitrogen. Under t~e same polymerizing conditions of Example 1 the catalyst of this invention had a reactivity of 1788 g/g cat/hr.
Example 3 In this example a catalyst was prepared under the conditions of Example 2 but containing 2% boron and 1% chromium on the silica. This mixture was also activated in a fluidized bed using a reducing gas comprising 7% carbon monoxide and : -93% nitrogen at 620C. for 5 hours. At the end of this time the reducing gas flow was discontinued and air was introduced at this same temperature for an additional 30 minutes. Then the air flow was discontinued, nitrogen introduced and the catalyst cooled. Under the same polymerizing conditions, that is at a reaction temperature of 105C., the reactivity of this example was 1908 g/g cat/hr.
Having described our invention as related to the embodiments set out herein, it is our intention that the invention be not limited by any of the details of description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the appended claims.
ETHYLENE POLYMERIZATION CATALYST AND METHOD
Background of the Invention In prior U.S. patent 3,780,011, assigned to the assignee hereof, there is described and claimed a catalyst and method in which the catalyst is prepared by treating a mixtureof a support such as silica and chromium trioxide with an ester of titanium, boron or vanadium or mixtures while fluidizing the resulting bed followed by activating the bed with a dry gas that contains oxygen at elevated temperatures.
This catalyst is useful in producing polyolefins and particu-larly polyethylene with controllable visco-elastic properties.
When the ester is boron the activity in ethylene polymerization is satisfactory but preferably should be higher and the poly-ethylene has narrow molecular weight distribution. In the present invention the catalyst which contains boron as well as chromium has greatly increased activity while still producing polyethylene having a narrow molecular weight distribution.
7~i~
In one broad aspect, the invention comprehends a highlyactive catalyst for polymerizing ethylene to polyethylene which catalyst has a narrow molecular weight distribution and is prepared by forming a mixture of a porous support of the class consisting of silica, alumina, zirconia, thoria and mixtures thereof, a chromium compound and an alkyl ester of boron containing 1 to about 7 carbon atoms in the alkyl group or a halide of boron. The chromium compound is reactive with the alkyl ester to form a chromium-boron compound upon heating, the mixture containing about 0.1 - 10 wt. % of boron and about 0.5 - 10 wt.% of chromium and this mixture is then activated at an elevated temperature in a fluidized bed with a substantially dry reducing gas and then fluidized with an oxidizing gas at an elevated temperature.
The invention further comprehends a method of making a highly active catalyst for polymerizing ethylene to poly-ethylene which has a narrow molecular weight distribution and comprises forming a mixture of a porous support of the class 20 consisting of silica, alumina, zirconia, thoria and mixtures -thereof, a chromium compound and an alkyl ester of boron containing 1 to about 7 carbon atoms in the alkyl group or a halide of boron. The chromium compound is reactive with the alkyl ester to form a chromium-boron compound upon heating, the mixture containing about 0.1 - 10 wt. % of boron and about 0.5 - 10 wt.% of chromium. This mixture is activated at an elevated temperature in a fluidized bed with a substantially dry reducing gas and then fluidized with an oxidizing gas at an elevated temperature.
Description of the Preferred Embodiment In this invention the porous support is either silica, U'7ti5 alumina, zirconia, thoria or mixtures thereof. This support is mixed with a chromium compound such as chromium trioxide, chromic nitrate, ammonium chromate or an organochromate that is reactive with the boron ester that is added later.
Then the mixture is preferably heated by fluidizing the resulting bed with a gas that is inert to the bed and its ingredients wh;le heating at an elevated temperature. Then an alkyl ester of boron containing about 1-7 carbon atoms in the alkyl group or a halide of boron is added to the chromium containing bed with the two ingredients being present in an amount to give about 0.1 - 10 wt.% of boron. Then the bed is activated at an elevated temperature by fluidizing the bed with a substantially dry reducing gas and finally fluidizing with an oxidizing gas at an elevated temperature.
Under these conditions the boron ester reacts with the chromium oxide to form a chromium-boron compound and under the heating and with the reducing gas at a higher temperature a boron-chromium support (e.g. silica) compound. The final treatment with an oxidizing gas such as air at an elevated temperature is for a very short time to oxidize the ingredients of the bed after which the bed is cooled down in an inert atmosphere. The catalyst thusly prepared is active in ethylene polymerization to produce polyethylene of narrow molecular weight distribution and the activity of such a catalyst is greatly increased over the same catalyst without the modifica-tion and the activation of this invention.
The temperature of activating and of the final oxidizing step is above 250C. and preferably between about 600-900C. with a practical range being about 400-800C. The total time for activating and then oxidizing is preferably from about 1 minute to as much as 48 hours.
lO~V7~j After being activated, the catalyst may be used immediately in a polymerization process or can be stored under substantially anhydrous conditions until desired for use. The polymerization process is simply that of contacting the ethy-lene monomer with an effective catalytic amount of the catalyst in the presence or the absence of diluents or solvents which are known to be suitable. The polymerization process may be under known conditions of temperature, pressure-or the like.
The polymerization may be conducted in the presence of a hydrocarbon which is liquid under the reaction conditions and which acts as a diluent and not a solvent for polyethylene under the reaction conditions employed. Preferred hydrocarbon diluents are paraffins including cycloparaffins and particularly paraffins and cycloparaffins having 3-12 carbon atoms. Illus-trative of diluents are propane, isobutane, n-pentane, isopen-tane, neopentane, 2,2,4-trimethylpentane, cyclohexane and methylcyclohexane.
The thusly produced catalyst may be used to cata-lyze the polymerization of ethylene at the customary tempera-tures of, for example, about 30C. or less up to about 200C.
or more.
In the preferred process the bed containing the chromium compound is heated before adding the boron ester as - by heating in a fluidized bed with a gas at a temperature of about 100C. The boron ester is then added as specified and this may be any of the alkyl borates coming within the desig-nated group of which isopropylborate, trimethylborate and the like are examples.
The reducing gas which is used in the activating step prior to the final oxidizing can conveniently be a mixture of nitrogen and carbon monoxide containing at least 1 wt.%
carbon monoxide.
- 105~V7~
As noted, the polymerization of the ethylene with the highly active catalyst of this invention can be in a par-ticle form process, solution process or can be a gas phase process. The activity of this catalyst is greater than catalysts containing boron prepared according to the above U. S. patent 3,780,011. The resulting polyethylene which has narrow molecular weight distribution is useful in making film, thermoforming objects and the like.
The following examples are illustrative of the invention with Example 1 being a control in which the catalyst is prepared according to the above U. S. patent 3,780,011.
Example 1 (Control) In this control example the catalyst was prepared by forming a mixture of silica, chromium trioxide and iso-propylborate in an amount to give 2% boron and 1% chromium.
This mixture was then activated in air at about 610C. for about 5 hours. This catalyst which is similar to that dis-closed in the boron containing catalyst of the above U.S.
patent 3,780,011 when used to polymerize ethylene at 550 psig using isobutane as a diluent and a reaction temperature of 105C. resulted in polyèthylene at a reactivity of 1094 g/g cat/hr.
Example 2 In the following examples that are according to the present invention the same boron ester was used and the same chromium trioxide also on silica and in amounts to give 1.5% boron and 1% chromium in the resulting bed. This mix-ture was activated by fluidizing with a reducing gas compris-ing 7~ carbon monoxide and 93~ nitrogen for 5 hours at 610C.
At the end of this period the reducing gas was discontinued and air was introduced at this same 610C. for 30 minutes.
6~
At the conclusion of this period the air flow was terminated and nitrogen was introduced and the catalyst was cooled with nitrogen. Under t~e same polymerizing conditions of Example 1 the catalyst of this invention had a reactivity of 1788 g/g cat/hr.
Example 3 In this example a catalyst was prepared under the conditions of Example 2 but containing 2% boron and 1% chromium on the silica. This mixture was also activated in a fluidized bed using a reducing gas comprising 7% carbon monoxide and : -93% nitrogen at 620C. for 5 hours. At the end of this time the reducing gas flow was discontinued and air was introduced at this same temperature for an additional 30 minutes. Then the air flow was discontinued, nitrogen introduced and the catalyst cooled. Under the same polymerizing conditions, that is at a reaction temperature of 105C., the reactivity of this example was 1908 g/g cat/hr.
Having described our invention as related to the embodiments set out herein, it is our intention that the invention be not limited by any of the details of description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the appended claims.
Claims (36)
1. A highly active catalyst for polymerizing ethylene to polyethylene having a narrow molecular weight distribution, prepared by: forming a mixture of (1) a porous support of the class consisting of silica, alumina, zirconia, thoria and mixtures thereof, (2) a chromium compound and (3) an alkyl ester of boron containing 1 to about 7 carbon atoms in the alkyl group or a halide of boron, said (2) being reactive with (3) to form a chromium-boron compound upon heating, said mixture containing about 0.1 - 10 wt.% of boron and about 0.5 - 10 wt.% of chromium and (4) activating said mixture at an elevated temperature in a fluidized bed with a sub-stantially dry reducing gas and then fluidizing (4) with (5) an oxidizing gas at an elevated temperature.
2. The catalyst of Claim 1 wherein (1) comprises silica.
3. The catalyst of Claim 1 wherein (2) is a member of the class consisting of chromium trioxide, chromic nitrate, ammonium chromate and organochromates reactive with said boron ester.
4. The catalyst of Claim 1 wherein said mixture of (1) and (2) is dried in a fluidized bed with a gas at a drying temperature prior to the addition of (3).
5. The catalyst of Claim 1 wherein said gas of (4) comprises a mixture of nitrogen and carbon monoxide.
6. The catalyst of claim 5 wherein (4) contains at least 1 wt.% of carbon monoxide.
7. The catalyst of claim 1 wherein said elevated activation temperature of (4) is about 600-900°C.
8. The catalyst of claim 1 wherein (5) comprises air followed by (6) cooling said mixture in an atmosphere of an inert gas.
9. The catalyst of claim 8 wherein said inert gas comprises nitrogen.
10. The catalyst of claim 1 wherein (1) comprises silica, (2) is a member of the class consisting of chromium trioxide, chromic nitrate, ammonium chromate and organochro-mates reactive with said boron ester and said elevated tem-perature of (4) is about 600-900°C.
11. The catalyst of claim 10 wherein said mixture of (1) and (2) is dried in a fluidized bed with a gas at a drying temperaute prior to the addition of (3).
12. The catalyst of claim 10 wherein (5) comprises air followed by (6) cooling said mixture in an atmosphere of an inert gas.
13. The method of making a highly active catalyst for polymerizing ethylene to polyethylene having a narrow molecular weight distribution, comprising: forming a mixture of (1) a porous support of the class consisting of silica, alumina, zirconia, thoria and mixtures thereof, (2) a chromium compound and (3) an alkyl ester of boron containing 1 to about 7 carbon atoms in the alkyl group or a halide of boron, said (2) being reactive with (3) to form a chromium-boron compound upon heating, said mixture containing about 0.1 - 10 wt.
% of boron and about 0.5 - 10 wt.% of chromium, and (4) activating said mixture at an elevated temperature in a fluid-ized bed with a substantially dry reducing gas and then fluidizing (4) with (5) an oxidizing gas at an elevated temperature.
% of boron and about 0.5 - 10 wt.% of chromium, and (4) activating said mixture at an elevated temperature in a fluid-ized bed with a substantially dry reducing gas and then fluidizing (4) with (5) an oxidizing gas at an elevated temperature.
14. The method of Claim 13 wherein (1) comprises silica.
15. The method of Claim 13 wherein (2) is a member of the class consisting of chromium trioxide, chromic nitrate, ammonium chromate and organochromates reactive with said boron ester.
16. The method of Claim 13 wherein said mixture of (1) and (2) is dried in a fluidized bed with a gas at a drying temperature prior to the addition of (3).
17. The method of Claim 13 wherein said gas of (4) comprises a mixture of nitrogen and carbon monoxide.
18. The method of claim 17 wherein (4) contains at least about 1 wt.% of carbon monoxide and the remainder an inert gas.
19. The method of claim 13 wherein said elevated activation temperature of (4) is about 600-900°C.
20. The method of claim 13 wherein (5) comprises air followed by (6) cooling said mixture in an atmosphere of an inert gas.
21. The method of claim 20 wherein said inert gas comprises nitrogen.
22. The method of claim 13 wherein (1) comprises silica, (2) is a member of the class consisting of chromium trioxide, chromic nitrate, ammonium chromate and organochro-mates reactive with said boron ester and said elevated tem-perature of (4) is about 600-900°C.
23. The method of claim 22 wherein said mixture of (1) and (2) is dried in a fluidized bed with a gas at a drying temperature prior to the addition of (3).
24. The method of claim 22 wherein (5) comprises air followed by (6) cooling said mixture in an atmosphere of an inert gas.
25. The method of making polyethylene having a narrow molecular weight distribution, comprising: polymeriz-ing ethylene under polymerizing conditions with the catalyst of claim 1 and recovering said polyethylene.
26. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 2 and recovering said polyethylene.
27. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 3 and recovering said polyethylene.
28. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 4 and recovering said polyethylene.
29. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 5 and recovering said polyethylene.
30. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 6 and recovering said polyethylene.
31. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 7 and recovering said polyethylene.
32. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 8 and recovering said polyethylene.
33. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 9 and recovering said polyethylene.
34. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 10 and recovering said polyethylene.
35. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 11 and recovering said polyethylene.
36. The method of making a polyethylene having a narrow molecular weight distribution, comprising: polymerizing ethylene under polymerizing conditions with the catalyst of claim 12 and recovering said polyethylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76491477A | 1977-02-02 | 1977-02-02 | |
| US764,914 | 1977-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090765A true CA1090765A (en) | 1980-12-02 |
Family
ID=25072151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA289,822A Expired CA1090765A (en) | 1977-02-02 | 1977-10-28 | Ethylene polymerization catalyst and method |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5396986A (en) |
| BE (1) | BE861275A (en) |
| CA (1) | CA1090765A (en) |
| DE (1) | DE2752354C3 (en) |
| FR (1) | FR2379554A1 (en) |
| GB (1) | GB1541188A (en) |
| IT (1) | IT1093077B (en) |
| SE (1) | SE7801209L (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7803736B2 (en) | 2002-12-10 | 2010-09-28 | Basell Polyolefine Gmbh | Supported chromium catalyst and its use for preparing homopolymers and copolymers of ethylene |
| ATE369911T1 (en) | 2004-04-30 | 2007-09-15 | Basell Polyolefine Gmbh | METHOD FOR THE REDUCTION AND SAFE DISPOSAL OF AN ACTIVATED CHROME OXIDE CATALYST |
| WO2005123792A1 (en) | 2004-06-16 | 2005-12-29 | Basell Polyolefine Gmbh | Process for preparing a chromium-based catalyst for the polymerization and/or copolymerization of olefins |
| DE102004028765A1 (en) | 2004-06-16 | 2006-01-05 | Basell Polyolefine Gmbh | Catalyst for polymerization and/or copolymerization of olefins used in producing fibers, films, and moldings, is obtainable by application to finely divided inorganic support and concluding calcination |
| DE102005019393A1 (en) | 2005-04-25 | 2006-10-26 | Basell Polyolefine Gmbh | Molding material, useful for the preparation of injection-molded body and screw valve, comprises ethylene monomer |
| DE102006004705A1 (en) | 2006-01-31 | 2007-08-02 | Basell Polyolefine Gmbh | Production of (co)polyethylene for blown film uses chromium catalyst on silicate support heat-activated under oxidative conditions and melt mixing with sterically-hindered phenol and phosphite antioxidants at sufficient energy input |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1505818A (en) * | 1974-06-11 | 1978-03-30 | British Petroleum Co | Polymerisation process |
-
1977
- 1977-10-28 CA CA289,822A patent/CA1090765A/en not_active Expired
- 1977-11-23 GB GB48823/77A patent/GB1541188A/en not_active Expired
- 1977-11-23 DE DE2752354A patent/DE2752354C3/en not_active Expired
- 1977-11-28 BE BE182986A patent/BE861275A/en unknown
- 1977-12-19 FR FR7738229A patent/FR2379554A1/en active Granted
- 1977-12-20 IT IT52293/77A patent/IT1093077B/en active
-
1978
- 1978-02-01 SE SE7801209A patent/SE7801209L/en unknown
- 1978-02-02 JP JP993778A patent/JPS5396986A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2752354B2 (en) | 1980-03-06 |
| FR2379554B1 (en) | 1980-10-10 |
| DE2752354C3 (en) | 1980-11-06 |
| JPS5396986A (en) | 1978-08-24 |
| FR2379554A1 (en) | 1978-09-01 |
| GB1541188A (en) | 1979-02-21 |
| JPS5515486B2 (en) | 1980-04-24 |
| DE2752354A1 (en) | 1978-08-03 |
| BE861275A (en) | 1978-03-16 |
| SE7801209L (en) | 1978-08-03 |
| IT1093077B (en) | 1985-07-19 |
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