US3821186A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Polymerisation catalyst
Assignee: International Synthetic Rubber Co Ltd
•
Filing: 1971-12-15
•
Granted: 1974-06-28
•
Expires: 1991-12-15
Abstract
Abstract A process for the preparation of a polymerization catalyst, particularly an olefin polymerisation catalyst, comprises the steps of 1. FORMING A MIXTURE COMPRISING AN ORGANO-MAGNESIUM COMPOUND, AN ETHER AND AN INERT HYDROCARBON LIQUID, 2. REMOVING SUBSTANTIALLY ALL THE FREE ETHER WHILE SUBJECTING THE MIXTURE TO SHEAR, AND 3. INCLUDING A HYDROCARBON-SOLUBLE TITANIUM OR ZIRCONIUM COMPOUND IN THE MIXTURE BEFORE, DURING OR AFTER STEP (2). Preferably a mixture of the organo-magnesium compound is admixed with the hydrocarbon liquid in the presence of a particulate support and this mixture subjected to shear at elevated temperature for a period of hours before cooling. Preferably the titanium or zirconium compound is added after step (2) and the mixture subjected to a prolonged period of further shear at ambient temperature. The whole process is preferably carried out under an inert gas and is useful for the formation of a highly active catalyst, particularly catalysts for the preparation of polyethylene and ethylene-propylene polymers.
Inventors
- 👤 D Grant
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 20:01
CPC Classifications
C; C08; C08F; C08F36/00; C08F36/02; C08F36/04; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/907
Claims Analysis
Total Claims: 44
Claim 1
Independent Claim
14 words
FORMING A MIXTURE COMPRISING AN ORGANO-MAGNESIUM COMPOUND, AN ETHER AND AN INERT HYDROCARBON LIQUID,
Claim 2
Dependent Claim
14 words
FORMING A MIXTURE COMPRISING AN ORGANO-MAGNESIUM COMPOUND, AN ETHER AND AN INERT HYDROCARBON LIQUID,
Claim 3
Dependent Claim
13 words
REMOVING SUBSTANTIALLY ALL THE FREE ETHER WHILE SUBJECTING THE MIXTURE TO SHEAR, AND
Claim 4
Dependent Claim
13 words
REMOVING SUBSTANTIALLY ALL THE FREE ETHER WHILE SUBJECTING THE MIXTURE TO SHEAR, AND
Claim 5
Dependent Claim
28 words
A process according to claim 1 wherein step (1) of the process comprises admixing a mixture of an organo-magnesium compound and an ether with an inert hydrocarbon liquid.
Claim 6
Dependent Claim
28 words
removing substantially all the free ether whilst subjecting the mixture to shear under conditions such that some of the ether is retained co-ordinated with the organomagnesium compound, and
Claim 7
Dependent Claim
28 words
removing substantially all the free ether whilst subjecting the mixture to shear under conditions such that some of the ether is retained co-ordinated with the organomagnesium compound, and
Claim 8
Dependent Claim
35 words
subjecting the mixture to shear at a temperature of 100* to 150* C whilst removing substantially all the free ether under conditions such that some of the ether is retained coordinated with the Grignard reagent,
Claim 9
Dependent Claim
35 words
subjecting the mixture to shear at a temperature of 100* to 150* C whilst removing substantially all the free ether under conditions such that some of the ether is retained coordinated with the Grignard reagent,
Claim 10
Dependent Claim
12 words
cooling the mixture to below 30* C and admixing titanium tetrachloride, and
Claim 11
Dependent Claim
12 words
cooling the mixture to below 30* C and admixing titanium tetrachloride, and
Claim 12
Dependent Claim
108 words
INCLUDING A HYDROCARBON-SOLUBLE TITANIUM OR ZIRCONIUM COMPOUND IN THE MIXTURE BEFORE, DURING OR AFTER STEP (2). PREFERABLY A MIXTURE OF THE ORGANO-MAGNESIUM COMPOUND IS ADMIXED WITH THE HYDROCARBON LIQUID IN THE PRESENCE OF A PARTICULATE SUPPORT AND THIS MIXTURE SUBJECTED TO SHEAR AT ELEVATED TEMPERATURE FOR A PERIOD OF HOURS BEFORE COOLING. PREFERABLY THE TITANIUM OR ZIRCONIUM COMPOUND IS ADDED AFTER STEP (2) AND THE MIXTURE SUBJECTED TO A PROLONGED PERIOD OF FURTHER SHEAR AT AMBIENT TEMPERATURE. THE WHOLE PROCESS IS PREFERABLY CARRIED OUT UNDER INERT GAS AND IS USEFUL FOR THE FORMATION OF A HIGHLY ACITVE CATALYST, PARTICULARLY CATALYSTS FOR THE PREPARATION OF POLYETHYLENE AND ETHYLENE-PROPYLENE POLYMERS.
Claim 13
Dependent Claim
108 words
INCLUDING A HYDROCARBON-SOLUBLE TITANIUM OR ZIRCONIUM COMPOUND IN THE MIXTURE BEFORE, DURING OR AFTER STEP (2). PREFERABLY A MIXTURE OF THE ORGANO-MAGNESIUM COMPOUND IS ADMIXED WITH THE HYDROCARBON LIQUID IN THE PRESENCE OF A PARTICULATE SUPPORT AND THIS MIXTURE SUBJECTED TO SHEAR AT ELEVATED TEMPERATURE FOR A PERIOD OF HOURS BEFORE COOLING. PREFERABLY THE TITANIUM OR ZIRCONIUM COMPOUND IS ADDED AFTER STEP (2) AND THE MIXTURE SUBJECTED TO A PROLONGED PERIOD OF FURTHER SHEAR AT AMBIENT TEMPERATURE. THE WHOLE PROCESS IS PREFERABLY CARRIED OUT UNDER INERT GAS AND IS USEFUL FOR THE FORMATION OF A HIGHLY ACITVE CATALYST, PARTICULARLY CATALYSTS FOR THE PREPARATION OF POLYETHYLENE AND ETHYLENE-PROPYLENE POLYMERS.
Claim 14
Dependent Claim
16 words
including a hydrocarbon-soluble titanium or zirconium compound in the mixture before, during or after step (2).
Claim 15
Dependent Claim
16 words
including a hydrocarbon-soluble titanium or zirconium compound in the mixture before, during or after step (2).
Claim 16
Dependent Claim
17 words
A process according to claim 1 wherein the temperature is 100* to 150* C. in step (2).
Claim 17
Dependent Claim
14 words
A process according to claim 1 wherein the temperature is 100* to 120* C.
Claim 18
Dependent Claim
27 words
subjecting the mixture containing the titanium tetrachloride to a further period of shear of at least 10 hours, the process being carried out under an inert gas.
Claim 19
Dependent Claim
27 words
subjecting the mixture containing the titanium tetrachloride to a further period of shear of at least 10 hours, the process being carried out under an inert gas.
Claim 20
Dependent Claim
44 words
A process according to claim 1 wherein the hydrocarbon-soluble titanium or zirconium compound is included in the mixture after step (2) of the process at a temperature of less than 60* C and the catalyst is thereafter subjected to further shear below that temperature.
Claim 21
Dependent Claim
26 words
A process according to claim 5 wherein the catalyst is subjected to the further shear below 60* C for a period of at least 10 hours.
Claim 22
Dependent Claim
28 words
A process according to claim 1 wherein the hydrocarbon/organo-magnesium compound/ether mixture is subjected to shear in step (2) of the process in the presence of a particulate support.
Claim 23
Dependent Claim
53 words
A process according to claim 1 wherein, in step (1) of the process, a mixture of the inert hydrocarbon liquid and an organo metal compound of a metal from Group IA, IIA, IIB, IIIB, IVB or VB which compound contains no halogen, is formed and the organo-magnesium compound and ether mixture is added.
Claim 24
Dependent Claim
38 words
A process according to claim 1 wherein the organo-magnesium compound is selected from a Grignard reagent of formula RMgX or a dihydrocarbyl magnesium compound of formula R2Mg, where R is hydrocarbyl and X is chlorine bromine or iodine.
Claim 25
Dependent Claim
38 words
A process according to claim 1 wherein the organo-magnesium compound is selected from phenyl magnesium bromide, methyl magnesium bromide, ethyl magnesium bromide, allyl magnesium bromide, cyclopentadienyl magnesium chloride, ethyl magnesium iodide, t-butyl magnesium chloride and n-propyl magnesium bromide.
Claim 26
Dependent Claim
14 words
A process according to claim 1 wherein the ether is diethyl ether or tetrahydrofuran.
Claim 27
Dependent Claim
12 words
A process according to claim 1 wherein the hydrocarbon liquid is aliphatic.
Claim 28
Dependent Claim
18 words
A process according to claim 1 wherein step (2) of the process is carried out under reduced pressure.
Claim 29
Dependent Claim
16 words
A process according to claim 1 wherein titanium tetrachloride is the compound used in step (3).
Claim 30
Dependent Claim
22 words
A process according to claim 1 wherein the mole ratio of organo-magnesium compound to titanium or zirconium compound is 10:1 to 1:10.
Claim 31
Dependent Claim
15 words
A process according to claim 15 wherein the mole ratio is 2: 1 to 1:2.
Claim 32
Dependent Claim
14 words
A process according to claim 1 carried out substantially totally under an inert gas.
Claim 33
Dependent Claim
10 words
A process for the preparation of a polymerisation catalyst comprising:
Claim 34
Dependent Claim
10 words
A process for the preparation of a polymerisation catalyst comprising:
Claim 35
Dependent Claim
11 words
A catalyst when prepared by a process according to claim 15.
Claim 36
Dependent Claim
25 words
A catalyst when prepared by a process according to claim 18 wherein the mole ratio of organo-magnesium compound to titanium compound is 10:1 to 1:10.
Claim 37
Dependent Claim
40 words
A process for the polymerisation of one or more olefins by means of a catalyst according to claim 19 together with an organic compound of the general formula R''R''''R''''''Al wherein R'', R'''' and R'''''' are hydrogen or a hydrocarbyl radical.
Claim 38
Dependent Claim
11 words
A process according to claim 21 wherein the olefin is ethylene.
Claim 39
Dependent Claim
40 words
A process for the polymerisation of one or more olefins by means of a catalyst according to claim 20 together with an organic compound of the general formula R''R''''R''''''Al wherein R'', R'''' and R'''''' are hydrogen or a hydrocarbyl radical.
Claim 40
Dependent Claim
11 words
A process according to claim 23 wherein the olefin is ethylene.
Claim 41
Dependent Claim
25 words
A catalyst having the formula TiCl4PhMgBr(Et2O)0.40 where Ph is the phenyl group and Et is the ethyl group prepared by the process of claim 18.
Claim 42
Dependent Claim
19 words
A process for the polymerisation of at least one olefin by means of a catalyst according to claim 25.
Claim 43
Dependent Claim
19 words
A process according to claim 5 wherein the shearing step is carried out by shearing in a ball mill.
Claim 44
Dependent Claim
19 words
A process according to claim 1 wherein, in step (2) the period of shear is 1 to 6 hours.
References Cited (Backward Citations)
No citation records indexed.
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1977-06-27 | 1977-12-27 | 1978-06-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1981-06-27 | 1981-12-27 | 1982-06-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1985-06-27 | 1985-12-27 | 1986-06-28 | $7700.00 | Window Closed / Lapsed |