GB1571491A - Supported ziegler polymerization catalyst and components thereof - Google Patents
Supported ziegler polymerization catalyst and components thereof Download PDFInfo
- Publication number
- GB1571491A GB1571491A GB8031/76A GB803176A GB1571491A GB 1571491 A GB1571491 A GB 1571491A GB 8031/76 A GB8031/76 A GB 8031/76A GB 803176 A GB803176 A GB 803176A GB 1571491 A GB1571491 A GB 1571491A
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- GB
- United Kingdom
- Prior art keywords
- magnesium
- catalyst component
- ziegler catalyst
- salt
- supported ziegler
- 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.)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
- B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) SUPPORTED ZIEGLER POLYMERISATION CATALYST AND COMPO
NENTS THEREOF (71) We, BP CHEMICALS LIMITED, of Britannic House, Moor Lane, London, EC2Y 9BU, a British company, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed to be particularly described in and by the following statement:
The present invention relates to a process for the production of a supported Ziegler catalyst component and to the use thereof in the polymerisation of olefins.
It has long been known that olefins such as ethylene can be polymerised by contacting them under polymerisation conditions with a catalyst comprising (1) a transition metal compound, e.g. titanium tetrachloride and (2) a co-catalyst or activator, e.g. an organometallic compound such as triethylaluminium. Catalysts of this type are generally referred to as Ziegler catalysts and will be so referred to throughout this specification. It is also known to deposit the transition metal compounds on support materials such as silicon carbide, calcium phosphate and magnesium or sodium carbonate.
The present invention provides a process for the production of a supported Ziegler catalyst component comprising forming a support material by heating the magnesium salt of an organic carboxylic acid under conditions so that at least part thereof is converted to magnesium oxide, and impregnating the support material with the reaction mixture obtained by reacting together titanium tetrachloride and isopropanol.
The magnesium salt employed in the process of the present invention can be the salt of a mono- or polycarboxylic acid, for example, magnesium formate, magnesium acetate, magnesium oxalate, magnesium malonate, magnesium maleate, or magnesium benzoate.
The salt can be anhydrous, hydrated or solvated.
The heating of the magnesium salt must be carried out under conditions such that at least part, for example 5%, preferably at least 50 wt %, most preferably at least 60% is converted to magnesium oxide. The degree of conversion to magnesium oxide can be determined satisfactorily by elementary analysis or by x-ray diffraction. The temperature at which a magnesium salt of an organic carboxylic acid commences to decompose to magnesium oxide will, of course, depend on the given salt, and may be for instance in the range 300 to 700"C. The decomposition temperature for any particular salt may be determined by trial and error. The heating is preferably carried out at a temperature only marginally above the decomposition temperature of the salt, for example between 5 and 100"C above the decomposition temperature. The heating can be carried out, for example, 'in vacuo', in an inert gas such as steam or nitrogen or in air. It is preferred to carry out the heating in air. If desired, a stream of gas, e.g. steam or nitrogen, can be used to fluidise the powdered salt during the heating.
The product of heating the magnesium salt of the carboxylic acid is preferably sieved or screened before impregnating it with the reaction mixture obtained by reacting together the titanium tetrachloride and isopropanol. If the product of the heating contains lumps it can, for example, be sieved to separate the product having the desired particle size and the lumps may be ground and sieved again. Preferably the product used as the support material has a particle size in the range 1 ,um to 500 llm (mean particle diameter) and most preferably in the range 50 llm to 250Rm.
The reaction mixture obtained by reacting together titanium tetrachloride and isopropanol - hereinafter referred to as "the Ti-reaction mixture" - is believed to comprise compounds of titanium having the general formula Ti(OR)n(Cl)4.n wherein n has any value from 0-4 inclusive and R is an isopropyl group, for example, titanium tetraisopropylate,
Ti(OiPr)2Cl2 or mixtures thereof.
The quantity of titanium tetrachloride employed is suitably sufficient to give a concentration of titanium in the catalyst in the range 0.5 to 15 wt So, preferably 1.5 to 9 wt % based on the total weight of catalyst component.
The impregnation of the support material of the present invention with the Ti-reaction mixture may be carried out using any convenient technique. Suitably the support material is treated with the Ti-reaction mixture at a temperature in the range -40" to 1500C, and preferably between 20C to 1000C. This can be carried out, for example, by mixing the support material and the Ti-reaction mixture with or without an inert diluent or a solvent for the said reaction mixture. It is preferred to heat the support material and the Ti-reaction mixture together at a temperature in the range 70 to 100"C for 1/2 to 5 hours in the presence of an inert diluent or a solvent for the said reaction mixture. Suitable inert diluents (which are in some cases also solvents for the Ti-reaction mixture) are, for example, saturated aliphatic hydrocarbons such as petroleum ether, butane, pentane, hexane, heptane, methylcyclohexane and cyclohexane and aromatic hydrocarbons such as benzene, toluene and xylene.
Any excess titanium compound remaining in the catalyst after the impregnation step is preferably removed from the catalyst, for example, by solvent washing, distillation or other convenient techniques which do not have a deleterious effect on the catalyst.
The preparation and impregnation of the Ti-reaction mixture is preferably carried out in the absence of oxygen or moisture.
The present invention further provides a process for polymerising 1-olefins comprising contacting the monomer under polymerisation conditions with the supported Ziegler catalyst component of the present invention in the presence of a Ziegler catalyst activator.
The polymerisation process according to the present invention can be applied to the polymerisation of 1-olefins e.g. ethylene or propylene or mixtures of olefins, e.g. ethylene with other 1-olefins, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4 methylpentene-1 1-3-butadiene or isoprene. The process is particularly suitable for the polymerisation of ethylene or copolymerisation of ethylene with up to 40 weight % (based on total monomer) of comonomers i.e. one or more other 1-olefins.
Ziegler catalyst activators and the methods by which they are used to activate Ziegler catalysts are well-known. Examples of Ziegler catalyst activators are organic derivatives or hydrides of metals of Groups I, II, III and IV of the Periodic Table. Particularly preferred are the trialkylaluminiums, e.g. triethyl- or tributylaluminium, or alkylaluminium halides.
The polymerisation conditions can be in accordance with known techniques used in supported Ziegler polymerisation. The polymerisation can be carried out in the gaseous phase or in the presence of a dispersion medium in which the monomer is soluble. As a liquid dispersion medium use can be made of an inert hydrocarbon which is liquid under the polymerisation conditions, or of the monomer or monomers themselves maintained in the liquid state under their saturation pressure. The polymerisation can, if desired, be carried out in the presence of hydrogen gas or other chain transfer agent to vary the molecular weight of the produced polymer.
The polymerisation is preferably carried out under conditions wherein the supported
Ziegler catalyst component is suspended in a liquid diluent in the presence of a Ziegler catalyst activator so that the polymer is formed as solid particles suspended in the liquid diluent. Suitable diluents are, for example, selected from paraffins and cycloparaffins having from 3-30 carbon atoms per molecule. Examples of diluents include isopentane, isobutane, and cyclohexane. Isobutane is preferred.
The polymerisation can be carried out under continuous or batch conditions.
Methods of recovering the product polyolefin are well-known in the art.
The polymerisation catalyst of the present invention can be used to make high density ethylene polymers and copolymers at high productivity having properties which render them suitable for injection moulding.
The invention is illustrated by the following examples:
In the Examples the melt index (MI2.16) and high load melt index (M121.6) were
determined according to ASTM method 1238 using 2.16 kg and 21.6 kg loads respectively: the units are grammes per 10 minutes. "MIR" is the melt index ratio MI21.MI2.16.
Example 1A 80 g of dried magnesium acetate (BDH laboratory Reagent) were placed in an oven at 200"C. The oven was rapidly heated to 375"C and maintained at that temperature for 20 hours to convert at least part of the acetate to oxide. The oven was purged with nitrogen for the first six hours. 21.3 g of a rough pale grey powder were obtained. The powder was ground with a mortar and pestle to produce a support material of the desired particle size.
Before use, 10 g of the support were placed in an oven at 15()C under vacuum for 2 hours to ensure dryness. No further weight loss was observed.
57 ml of isopropanol and 150 ml of cyclohexane were stirred under an atmosphere of dry nitrogen and 36.4 ml of TiCl4 were slowly added. The resultant yellow solution was refluxed for 2 hours. The solution was allowed to cool to 55 C and 10 g of the support, prepared as described above, were added. The mixture was refluxed for 3 hours and the catalyst component slurry washed seven times with cyclohexane to ensure that the concentration of titanium in the solvent was less than 1g/litre. The volume was made up to 500 ml with dry cyclohexane and the catalyst component handled as a slurry with a solids content of 51 mg/ml. Analysis of the catalyst component yielded (w/w) - Ti 4.77%, Cl 34.26%.
Example 1 B
70 g of dried magnesium acetate (BDH Laboratory Reagent) were placed in an oven at 200 C. The temperature was quickly raised to 600 C. No gas purge was employed. This temperature was maintained for 16 hours and 18.7g of a rough grey powder (similar to that formed in the first example) were obtained. This was ground in a mortar and pestle and the catalyst component prepared as in Example 1A. The solids content of this catalyst component was 60.5 mg/ml. Analysis of the catalyst component yielded (w/w) - Ti 5.60%,
Cl - 25.90%.
Example 2
80 g of hydrated magnesium oxalate, MgC2O4.2H2O (BDH Laboratory Reagent) were placed in an oven at 1250C. The oven was rapidly heated to 6000C and maintained at that temperature for 17 hours. The oven was purged with nitrogen for the first six hours to prevent a dangerous build-up of carbon monoxide. The produced support material was a fine white powder weighing 20.5 g. The support was predried and the catalyst prepared as described in Example 1A. Six washes were required to remove free Ti salts. The solids content of the catalyst component slurry was 79 mg/ml. Analysis of the catalyst component yielded Ti 4.866 Cl 33.64%.
Pol,'inerisation Polymerisations were carried out using the catalyst components of Example 1 and 2 in a 2.3 litre stainless steel stirred autoclave. The reactor was purged with nitrogen, heated to 7() C and then 2 ml of the catalyst component slurry added with a syringe. This was followed by the triethylaluminium co-catalyst in 1 litre of isobutane. The temperature was raised to 85 C. The required pressure of hydrogen was added, followed by ethylene to bring the total pressure of the reactor contents to 41.4 bar. Ethylene was added continuously to maintain this pressure during the reaction. Polymerisation and polymer property data are shown in the Table.
TABLE
Catalyst Catalyst Co-Catalyst H2 Partial Productivity MI2.6 MIR Polymer Size (%) Polymer Size (%)
Prep. component Wt. Wt. (mg) Pressure (g/g hour) (g/10 min) > 500 m (w/w) < 100 (w/w) (mg) (bar)
Ex. 1A 102 251 5.2 5602 5.52 25.8 10.8 1.3 " 102 251 7.6 4156 18.48 23.9 17.4 3.2
Ex. 1B 121 251 5.2 3813 3.54 31.8 48.1 0.1 " 121 251 6.9 2975 4.38 28.2 51.9 Nil
Ex. 2 158 251 5.2 1981 3.24 26.5 96.0 Nil " 158 251 6.9 1373 9.60 26.7 91.6 Nil
Claims (17)
1. A process for the production of a supported Ziegler catalyst component comprising forming a support material by heating the magnesium salt of an organic carboxylic acid under conditions so that at least part thereof is converted to magnesium oxide, and impregnating the support material with the reaction mixture obtained by reacting together titanium tetrachloride and isopropanol.
2. A process as claimed in Claim 1 wherein the magnesium salt is magnesium formate, magnesium acetate, magnesium oxalate, magnesium malonate, magnesium maleate or magnesium benzoate.
3. A process as claimed in Claim 1 or 2 wherein at least 50 wt % of the magnesium salt is converted to magnesium oxide.
4. A process as claimed in any preceding claim wherein at least 60 wt Yo of the magnesium salt is converted to magnesium oxide.
5. A process as claimed in any preceding claim wherein the heating is carried out at a temperature only marginally above the decomposition temperature of the salt.
6. A process as claimed in any preceding claim wherein the quantity of titanium tetrachloride employed is sufficient to give a concentration of titanium in the catalyst in the range 1.5 to 9 wt % based on the total weight of catalyst component.
7. A process as claimed in any one of the preceding claims wherein the titanium tetrachloride and isopropanol -are reacted together in the presence of a diluent.
8. A process as claimed in claim 7 wherein the diluent is a saturated aliphatic hydrocarbon.
9. A process as claimed in claim 7 wherein the diluent is cyclohexane.
10. A process for preparing a supported Ziegler catalyst component substantially as described in Example 1A, 1B, or 2.
11. A supported Ziegler catalyst component prepared by the process claimed in any one of the preceding claims.
12. A process for polymerising 1-olefins comprising contacting the monomer under polymerisation conditions with the supported Ziegler catalyst component of the present invention in the presence of a Ziegler catalyst activator.
13. A process as claimed in Claim 12 wherein the 1-olefinic monomer is ethylene or a mixture qf ethylene with up to 40 wt % (based on total monomer) of one or more other 1-olefins.
14. A process as claimed in Claim 12 or 13 wherein the Ziegler catalyst activator is triethyl or tributylaluminium.
15. A process as claimed in Claim 12, 13, or 14 wherein the polymerisation process is carried out under particle form process conditions.
16. A process for polymerising ethylene substantially as described in any one of
Examples 1A, 1B or 2.
17. Polyolefins when prepared by the process claimed in any one of Claims 12 to 16.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8031/76A GB1571491A (en) | 1976-03-01 | 1976-03-01 | Supported ziegler polymerization catalyst and components thereof |
| SE7701950A SE7701950L (en) | 1976-03-01 | 1977-02-22 | METHOD OF MANUFACTURING A CARRIED ZIEGLER CATALYST |
| NL7702031A NL7702031A (en) | 1976-03-01 | 1977-02-25 | PROCEDURE FOR THE PREPARATION OF A ZIEGLER CATALYST ON A CARRIER. |
| ES456369A ES456369A1 (en) | 1976-03-01 | 1977-02-28 | Supported ziegler polymerization catalyst and components thereof |
| DE19772708647 DE2708647A1 (en) | 1976-03-01 | 1977-02-28 | ZIEGLER CATALYSTS, THEIR PRODUCTION AND USE |
| BE175331A BE851908A (en) | 1976-03-01 | 1977-02-28 | POLYMERIZATION CATALYST |
| FR7705735A FR2342993A1 (en) | 1976-03-01 | 1977-02-28 | METHOD OF MANUFACTURING A ZIEGLER CATALYST FOR POLYMERIZATION OF OLEFINS |
| NO770675A NO770675L (en) | 1976-03-01 | 1977-02-28 | PROCEDURES FOR PRODUCING A CATALYST. |
| JP2211277A JPS52105592A (en) | 1976-03-01 | 1977-03-01 | Manufacture of carried ziegler catalysts |
| US05/883,639 US4170568A (en) | 1976-03-01 | 1978-03-06 | Polymerization catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8031/76A GB1571491A (en) | 1976-03-01 | 1976-03-01 | Supported ziegler polymerization catalyst and components thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1571491A true GB1571491A (en) | 1980-07-16 |
Family
ID=9844449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8031/76A Expired GB1571491A (en) | 1976-03-01 | 1976-03-01 | Supported ziegler polymerization catalyst and components thereof |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS52105592A (en) |
| BE (1) | BE851908A (en) |
| DE (1) | DE2708647A1 (en) |
| ES (1) | ES456369A1 (en) |
| FR (1) | FR2342993A1 (en) |
| GB (1) | GB1571491A (en) |
| NL (1) | NL7702031A (en) |
| NO (1) | NO770675L (en) |
| SE (1) | SE7701950L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439537A (en) * | 1981-06-29 | 1984-03-27 | Toho Titanium Co., Ltd. | Process for the preparation of catalyst component for the polymerization of olefins |
-
1976
- 1976-03-01 GB GB8031/76A patent/GB1571491A/en not_active Expired
-
1977
- 1977-02-22 SE SE7701950A patent/SE7701950L/en not_active Application Discontinuation
- 1977-02-25 NL NL7702031A patent/NL7702031A/en not_active Application Discontinuation
- 1977-02-28 ES ES456369A patent/ES456369A1/en not_active Expired
- 1977-02-28 FR FR7705735A patent/FR2342993A1/en not_active Withdrawn
- 1977-02-28 NO NO770675A patent/NO770675L/en unknown
- 1977-02-28 BE BE175331A patent/BE851908A/en unknown
- 1977-02-28 DE DE19772708647 patent/DE2708647A1/en not_active Withdrawn
- 1977-03-01 JP JP2211277A patent/JPS52105592A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439537A (en) * | 1981-06-29 | 1984-03-27 | Toho Titanium Co., Ltd. | Process for the preparation of catalyst component for the polymerization of olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| ES456369A1 (en) | 1978-01-16 |
| NO770675L (en) | 1977-09-02 |
| BE851908A (en) | 1977-08-29 |
| FR2342993A1 (en) | 1977-09-30 |
| JPS52105592A (en) | 1977-09-05 |
| NL7702031A (en) | 1977-09-05 |
| SE7701950L (en) | 1977-09-02 |
| DE2708647A1 (en) | 1977-09-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |