Patent US4123386A successfully refreshed from Google Patents.
US4123386A
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Chemically reducing solids which may be applied to the polymerization of olefins
Assignee: BP Chemicals Ltd
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Filing: 1976-12-09
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Granted: 1978-10-31
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Expires: 1996-12-09
Abstract
Abstract An olefin polymerization catalyst is prepared in two steps. In the first step, a chemically reducing solid is prepared by polymerizing an olefin in contact with solid particles of a compound of a transition metal from sub-groups IV A, V A and VI A in a lower valency state in the presence of an organomagnesium compound and terminating the polymerization when the quantity of olefin polymerized is from 50 mg.-50 g. per mg-atom of transition metal. In the second step, the chemically reducing solid prepared in the first step is contacted with reducible compounds of transition metals from sub-groups IV A, V A and VI A to effect reduction thereof.
Inventors
- 👤 Michel M. Avaro
- 👤 Pierre M. Mangin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 15:45
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
176 words
A method for preparing catalysts for polymerizing olefins, comprising two successive main steps, the first step comprising the preparation of chemically reducing solids by polymerizing an olefin of the formula ACH ═ CH 2 , wherein A is hydrogen or an alkyl radical containing 1 to 8 carbon atoms, in contact with solid particles of a compound of a transition metal from sub-groups IVa, Va and VIa of the periodic table in a lower valency state, and in the presence of an organomagnesium compound in the form of a C 1 -C 12 alkyl magnesium compound in the relative proportion such that the molar ratio of organic groups of the alkyl magnesium compound to the transition metal is 0.2-2.0/1, and the second step comprising contacting the chemically reducing solids from the first step with reducible compounds of transition metals from sub-groups IVa, Va and VIa of the periodic table to effect reduction thereof, terminating the polymerization in the first step when the quantity of olefin polymerized is from 50 mg.-50 g. per mg.-atom of transition metal.
Claim 2
Independent Claim
176 words
A method for preparing catalysts for polymerizing olefins, comprising two successive main steps, the first step comprising the preparation of chemically reducing solids by polymerizing an olefin of the formula ACH ═ CH 2 , wherein A is hydrogen or an alkyl radical containing 1 to 8 carbon atoms, in contact with solid particles of a compound of a transition metal from sub-groups IVa, Va and VIa of the periodic table in a lower valency state, and in the presence of an organomagnesium compound in the form of a C 1 -C 12 alkyl magnesium compound in the relative proportion such that the molar ratio of organic groups of the alkyl magnesium compound to the transition metal is 0.2-2.0/1, and the second step comprising contacting the chemically reducing solids from the first step with reducible compounds of transition metals from sub-groups IVa, Va and VIa of the periodic table to effect reduction thereof, terminating the polymerization in the first step when the quantity of olefin polymerized is from 50 mg.-50 g. per mg.-atom of transition metal.
Claim 3
Dependent Claim
40 words
A method according to claim 1, in which the solid particles of a transition metal compound used in the first step are previously obtained by reducing a transition metal compound having an initial state of valency of at least four.
Claim 4
Dependent Claim
94 words
A method according to claim 2, in which the solid particles of a transition metal compound comprise a trivalent titanium compound of the formula Ti(OR) n X 3-n , wherein R represents an alkyl group containing 2 to 8 carbon atoms, X represents an atom of a halogen, and n a whole number or fraction which may have any value of from 0 to 3, and in which said compound is obtained by reducing a transition metal compound having an initial state of valency of at least four, by means of an organoaluminum compound.
Claim 5
Dependent Claim
63 words
A method according to claim 3 in which the organoaluminum compound is represented by the general formula AlR m V X 3-m wherein R V represents a univalent hydrocarbon group with 1 to 10 carbon atoms, X represents an atom of hydrogen or of a halogen, and m represents a whole number or fraction which may have any value from 1 to 3.
Claim 6
Dependent Claim
12 words
A method according to claim 3, in which the halogen is chlorine.
Claim 7
Dependent Claim
41 words
A method according to claim 1, in which the organomagnesium compound used in the first step is of the formula R'MgX, wherein R' represents a hydrocarbon radical containing 1 to 12 carbon atoms and X represents an atom of a halogen.
Claim 8
Dependent Claim
20 words
A method according to claim 6, in which the halogen is selected from the group consisting of chlorine and bromine.
Claim 9
Dependent Claim
37 words
A method according to claim 1, in which the organomagnesium compound used in the first step is of the formula R'MgR", wherein R' and R" represent identical or different hydrocarbon radicals containing 1 to 12 carbon atoms.
Claim 10
Dependent Claim
104 words
A method according to claim 1, comprising feeding the solid particles of transition metal compound and the organomagnesium compound into a reactor, containing a non-reactive liquid, keeping the reactor at from 40° to 150° C. and feeding the olefin, which has to be polymerized, into it at a rate of 0.01 to 100 g per hour per milligram atom of transition metal, until from 50 mg to 50 g of olefin per milligram atom of transition metal is polymerized; reacting the chemically reducing solids with transition metal compounds from sub-groups IVa, Va and VIa of the periodic table at from -10° to 100° C.
Claim 11
Dependent Claim
17 words
A method as claimed in claim 9 in which the non-reactive liquid is a saturated aliphatic hydrocarbon.
Claim 12
Dependent Claim
35 words
A method as claimed in claim 9, comprising replacing the organomagnesium compound with an equal molar quantity of magnesium and of an alkyl monochloride in which the alkyl group contains 1 to 12 carbon atoms.
Claim 13
Dependent Claim
35 words
A method as claimed in claim 9, comprising replacing the organomagnesium compound with an equal molar quantity of magnesium and of an alkyl monobromide in which the alkyl group contains 1 to 12 carbon atoms.
Claim 14
Dependent Claim
106 words
A method according to claim 1, comprising feeding the solid particles of the compound of a transition metal and the organomagnesium compound into a reactor, containing a non-reactive liquid, keeping the reactor at from 40° to 150° C. and feeding into it 0.1 to 0.9 moles, per mole of organomagnesium compound, of a hydrocarbon halide of the formula R'"--CH 2 X wherein R'" represents an alkyl group containing 1 to 10 carbon atoms and X represents an atom of a halogen; reacting the chemically reducing solids with transition metal compounds from sub-groups IVa, Va and VIa of the periodic table at from -10° to 100° C.
Claim 15
Dependent Claim
13 words
A method as claimed in claim 13, in which the halogen is chlorine.
Claim 16
Dependent Claim
18 words
A method as claimed in claim 13, in which the non-reactive liquid is a liquid saturated aliphatic hydrocarbon.
Claim 17
Dependent Claim
35 words
A method as claimed in claim 13, comprising replacing the organomagnesium compound with an equal molar quantity of magnesium and of an alkyl monochloride in which the alkyl group contains 1 to 12 carbon atoms.
Claim 18
Dependent Claim
35 words
A method as claimed in claim 13, comprising replacing the organomagnesium compound with an equal molar quantity of magnesium and of an alkyl monobromide in which the alkyl group contains 1 to 12 carbon atoms.
Claim 19
Dependent Claim
62 words
A method as claimed in claim 1, wherein the transition metal compounds used in the second step are titanium compounds of the formula Ti(OR) n X 4-n , wherein R represents an alkyl group containing 2 to 8 carbon atoms, X an atom of a halogen, and n a whole number or fraction which may have any value from 0 to 4.
Claim 20
Dependent Claim
58 words
A method as claimed in claim 1 in which the quantity of reducing agent employed in the second step, expressed in grams per milligrams atom of transition metal is 1/10 P to 10 P in which P is the number of millimoles of titanium tetrochloride reduced in one hour at 60° C. by 1 gram of reducing agent.
Claim 21
Dependent Claim
12 words
A catalyst for polymerizing olefins as prepared in the preceding claim 1.
References Cited (Backward Citations)
US3878124A
Cited
US3922322A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-10-30 | 1982-05-01 | 1982-10-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-10-30 | 1986-05-01 | 1986-10-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-10-30 | 1990-05-01 | 1990-10-31 | $7700.00 | Window Closed / Lapsed |