US4495338A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Components of catalysts for the polymerization of olefins
Assignee: Montedison SpA
•
Filing: 1980-09-24
•
Granted: 1985-01-22
•
Expires: 2000-09-24
Abstract
Abstract Catalysts useful in the polymerization of olefins, more particularly of ethylene and mixtures thereof with alpha-olefins and/or diolefins, are disclosed. The new catalysts are obtained by mixing a halide of titanium or vanadium in which the metal has a valency lower than 4, with a support comprising an anhydrous magnesium or zinc halide in an active form under particular conditions, and then activating the resulting product with a hydride or organometallic compound of a metal belonging to Groups I to III, inclusive, of the Mendelyeev Periodic System.
Inventors
- 👤 Adolfo Mayr
- 👤 Ermanno Susa
- 👤 Ettore Giachetti
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 14:03
CPC Classifications
C; C08; C08F; C08F10/00; C08F4/00; C08F4/02; C08F4/022; Y; Y10; Y10S; Y10S526/00; Y10S526/906
Claims Analysis
Total Claims: 63
Claim 1
Independent Claim
104 words
Components of catalysts for the polymerization of olefins comprising the product obtained by contacting a transition metal halide selected from titanium and vanadium halides in which the metal has a valence lower than 4, with an active form of an anhydrous magnesium dihalide, the titanium or vanadium halide being used in an amount less than 50% by weight with respect to the magnesium dihalide, and the active magnesium dihalide being characterized in that, in its X-rays powder spectrum, the most intense diffraction line present in the spectrum of the normal, non-active magnesium dihalide is less intense and, in its place, a broadened halo appears.
Claim 2
Dependent Claim
104 words
Components of catalysts for the polymerization of olefins comprising the product obtained by contacting a transition metal halide selected from titanium and vanadium halides in which the metal has a valence lower than 4, with an active form of an anhydrous magnesium dihalide, the titanium or vanadium halide being used in an amount less than 50% by weight with respect to the magnesium dihalide, and the active magnesium dihalide being characterized in that, in its X-rays powder spectrum, the most intense diffraction line present in the spectrum of the normal, non-active magnesium dihalide is less intense and, in its place, a broadened halo appears.
Claim 3
Dependent Claim
26 words
Components of catalysts according to claim 1, and comprising the product obtained by contacting the transition metal halide with anhydrous magnesium dichloride or anhydrous magnesium dibromide.
Claim 4
Dependent Claim
21 words
Components of catalysts according to claim 1, and comprising the product obtained by contacting TiCl 3 with the anhydrous magnesium dihalide.
Claim 5
Dependent Claim
25 words
Components of catalysts according to claim 1, and comprising the product obtained by contacting TiCl 3 with anhydrous MgCl 2 or anhydrous MgBr 2 .
Claim 6
Dependent Claim
142 words
A component useful in preparing a catalyst for the polymerization of olefins, said component being obtained by contacting a transition metal halide which is a titanium or vanadium halide in which the metal has a valence lower than 4, with a support the essential support material of which is an active MgCl 2 , the titanium or vanadium halide being used in an amount less than 50% by weight with respect to the MgCl 2 , and the MgCl 2 being characterized in that, in its X-rays powder spectrum, the diffraction line which, in the spectrum for the normal inert MgCl 2 , has the highest intensity and appears at a lattice distance (d) of 2.56 Å is less intense and in its place a broadened halo appears in a range of lattice distances (d) comprised from d=2.56 Å to d=2.95 Å.
Claim 7
Dependent Claim
142 words
A component useful in preparing a catalyst for the polymerization of olefins, said component being obtained by contacting a transition metal halide which is a titanium or vanadium halide in which the metal has a valence lower than 4, with a support the essential support material of which is an active MgCl 2 , the titanium or vanadium halide being used in an amount less than 50% by weight with respect to the MgCl 2 , and the MgCl 2 being characterized in that, in its X-rays powder spectrum, the diffraction line which, in the spectrum for the normal inert MgCl 2 , has the highest intensity and appears at a lattice distance (d) of 2.56 Å is less intense and in its place a broadened halo appears in a range of lattice distances (d) comprised from d=2.56 Å to d=2.95 Å.
Claim 8
Dependent Claim
16 words
A component according to claim 5, in which the transition metal halide is TiCl 3 .
Claim 9
Dependent Claim
141 words
A component useful in preparing a catalyst for the polymerization of olefins, said component being prepared by contacting a transition metal halide which is a titanium or vanadium halide in which the metal has a valence lower than 4, with a support the essential support material of which is an active MgBr 2 , the titanium or vanadium halide being used in an amount less than 50% by weight with respect to the MgBr 2 , and the MgBr 2 being characterized in that, in its X-rays powder spectrum, the diffraction line which in the spectrum for the normal inert MgBr 2 has the highest intensity and appears at a lattice distance d of 2.93 Å is less intense and in its place a broadened halo appears in a range of lattice distances (d) comprised from d=2.80 Å to d=3.25 Å.
Claim 10
Dependent Claim
141 words
A component useful in preparing a catalyst for the polymerization of olefins, said component being prepared by contacting a transition metal halide which is a titanium or vanadium halide in which the metal has a valence lower than 4, with a support the essential support material of which is an active MgBr 2 , the titanium or vanadium halide being used in an amount less than 50% by weight with respect to the MgBr 2 , and the MgBr 2 being characterized in that, in its X-rays powder spectrum, the diffraction line which in the spectrum for the normal inert MgBr 2 has the highest intensity and appears at a lattice distance d of 2.93 Å is less intense and in its place a broadened halo appears in a range of lattice distances (d) comprised from d=2.80 Å to d=3.25 Å.
Claim 11
Dependent Claim
16 words
A component according to claim 7, in which the transition metal halide is TiCl 3 .
Claim 12
Dependent Claim
127 words
Catalysts for the polymerization of olefins, consisting of the product obtained by mixing (a) a hydride or organometallic compound of a metal belonging to one of Groups I to III inclusive of the Mendelyeev Periodic System with (b) the product obtained by contacting a titanium or vanadium halide in which the metal has a valence lower than 4, with an active form of an anhydrous magnesium dihalide, the transition metal halide being used in an amount less than 50% by weight with respect to the magnesium dihalide, and the active magnesium dihalide being characterized in that in its X-rays powder spectrum the most intense diffraction line present in the spectrum of the normal non-active magnesium dihalide is less intense and, in its place, a broadened halo appears.
Claim 13
Dependent Claim
127 words
Catalysts for the polymerization of olefins, consisting of the product obtained by mixing (a) a hydride or organometallic compound of a metal belonging to one of Groups I to III inclusive of the Mendelyeev Periodic System with (b) the product obtained by contacting a titanium or vanadium halide in which the metal has a valence lower than 4, with an active form of an anhydrous magnesium dihalide, the transition metal halide being used in an amount less than 50% by weight with respect to the magnesium dihalide, and the active magnesium dihalide being characterized in that in its X-rays powder spectrum the most intense diffraction line present in the spectrum of the normal non-active magnesium dihalide is less intense and, in its place, a broadened halo appears.
Claim 14
Dependent Claim
14 words
Catalysts according to claim 9, in which the magnesium dihalide is MgCl 2 .
Claim 15
Dependent Claim
14 words
Catalysts according to claim 9, in which the magnesium dihalide is MgBr 2 .
Claim 16
Dependent Claim
22 words
Catalysts according to claim 9, in which the transition metal halide is TiCl 3 and the magnesium dihalide is MgCl 2 .
Claim 17
Dependent Claim
22 words
Catalysts according to claim 9, in which the transition metal halide is TiCl 3 and the magnesium dihalide is MgBr 2 .
Claim 18
Dependent Claim
36 words
Catalysts according to claim 9, in which the transition metal halide is delta-TiCl 3 obtained by reducing TiCl 4 with aluminum metal and then grinding the reduction product to convert TiCl 3 to the delta form.
Claim 19
Dependent Claim
14 words
Catalysts according to claim 9, in which component (a) is an alkyl Al compound.
Claim 20
Dependent Claim
30 words
Catalysts according to claim 9, in which the transition metal halide is TiCl 3 , the magnesium dihalide is MgCl 2 , and component (a) is an alkyl Al compound.
Claim 21
Dependent Claim
30 words
Catalysts according to claim 9, in which the transition metal halide is TiCl 3 , the magnesium dihalide is MgBr 2 , and component (a) is an alkyl Al compound.
Claim 22
Dependent Claim
22 words
Catalysts according to claim 9, in which the transition metal halide is TiCl 3 and the magnesium dihalide is MgCl 2 .
Claim 23
Dependent Claim
22 words
Catalysts according to claim 9, in which the transition metal halide is TiCl 3 and the magnesium dihalide is MgBr 2 .
Claim 24
Dependent Claim
36 words
Catalysts according to claim 9, in which the transition metal halide is delta-TiCl 3 obtained by reducing TiCl 4 with aluminum metal and then grinding the reduction product to convert TiCl 3 to the delta form.
Claim 25
Dependent Claim
30 words
Catalysts according to claim 9, in which the transition metal halide is TiCl 3 , the magnesium dihalide is MgCl 2 , and component (a) is an alkyl Al compound.
Claim 26
Dependent Claim
30 words
Catalysts according to claim 9, in which the transition metal halide is TiCl 3 , the magnesium dihalide is MgBr 2 , and component (a) is an alkyl Al compound.
Claim 27
Dependent Claim
46 words
Method for preparing the catalysts as defined in claim 9, characterized in that catalyst-forming component (a) is mixed with a catalyst-forming component (b) prepared by co-grinding the titanium or vanadium halide with an anhydrous magnesium dihalide, to thereby convert the magnesium dihalide to the active form.
Claim 28
Dependent Claim
24 words
The method according to claim 23, further characterized in that the co-grinding is performed in a ball mill in the absence of inert diluents.
Claim 29
Dependent Claim
26 words
The method according to claim 23, characterized in that catalyst-forming component (b) is prepared by grinding a mixture of a titanium trihalide and anhydrous magnesium dihalide.
Claim 30
Dependent Claim
41 words
The method according to claim 23, characterized in that catalyst-forming component (b) is prepared by grinding anhydrous magnesium dichloride or anhydrous magnesium dibromide with delata-TiCl 3 obtained by reduction of TiCl 4 with aluminum and conversion to the delta-form by grinding.
Claim 31
Dependent Claim
59 words
The method for preparing the catalysts as defined in claim 9, characterized in that catalyst-forming component (a) is mixed with a catalyst-forming component (b) prepared by contacting the titanium or vanadium halide with a magnesium dihalide obtained by decomposition of an organometallic compound of the formula RMgX in which R is a hydrocarbon radical and X is a halogen.
Claim 32
Dependent Claim
35 words
The method according to claim 27, further characterized in that the magnesium dihalide is obtained from the organometallic compound RMgX by reaction of the latter with at least the stoichiometric amount of anhydrous hydrogen chloride.
Claim 33
Dependent Claim
27 words
The method according to claim 27, characterized in that the titanium or vanadium halide is brought into contact with an inert solvent suspension of the magnesium dihalide.
Claim 34
Dependent Claim
38 words
The method according to claim 29, further characterized in that catalyst-forming component (b) is prepared from a titanium trichloride formed in the suspension containing the magnesium dihalide by reduction of TiCl 4 with an organometallic compound of aluminum.
Claim 35
Dependent Claim
37 words
The method according to claim 30, further characterized in that the organometallic compound of aluminum used for reducing the TiCl 4 has the formula R 2 AlCl or RAlCl 2 in which R is an alkyl radical.
Claim 36
Dependent Claim
44 words
A process for the polymerization of ethylene and mixtures thereof with at least one other monomer selected from the group consisting of higher alpha-olefins and diolefins, characterized in that the polymerization is carried out in the presence of a catalyst according to claim 9.
Claim 37
Dependent Claim
60 words
The process according to claim 32, further characterized in that the polymerization is carried out at a temperature of from -80° C. to +200° C., in an inert liquid and in the presence of a regulator of the molecular weight of the polymer, and in that the polymer obtained does not require any purification treatment for removal of catalyst residues.
Claim 38
Dependent Claim
22 words
The process according to claim 32, characterized in that the polymerization is carried out in the absence of an inert liquid diluent.
Claim 39
Dependent Claim
120 words
A process for the polymerization of olefins comprising polymerizing an olefin in the presence of a catalyst consisting of the product obtained by mixing (1) a hydride or organometallic compound of a metal belonging to Groups I-III inclusive of the Mendelyeev Periodic System with (2) the product obtained by mechanical co-comminution of a titanium or vanadium halide in which the metal has a valence lower than 4 with a magnesium dihalide until the most intense diffraction line in the X-rays powder spectrum of the normal non-comminuted magnesium dihalide is less intense and in its place a broadened halo appears, said titanium or vanadium halide being used in an amount less than 50% by weight with respect to the magnesium dihalide.
Claim 40
Dependent Claim
120 words
A process for the polymerization of olefins comprising polymerizing an olefin in the presence of a catalyst consisting of the product obtained by mixing (1) a hydride or organometallic compound of a metal belonging to Groups I-III inclusive of the Mendelyeev Periodic System with (2) the product obtained by mechanical co-comminution of a titanium or vanadium halide in which the metal has a valence lower than 4 with a magnesium dihalide until the most intense diffraction line in the X-rays powder spectrum of the normal non-comminuted magnesium dihalide is less intense and in its place a broadened halo appears, said titanium or vanadium halide being used in an amount less than 50% by weight with respect to the magnesium dihalide.
Claim 41
Dependent Claim
98 words
Process for preparing components of catalysts for the polymerization of olefins comprising contacting a transition metal halide selected from titanium and vanadium halides in which the metal has a valence lower than 4, with an anhydrous magnesium dihalide in an active form characterized in that in the X-rays powder spectrum thereof the most intense diffraction line present in the spectrum of the normal non-active magnesium halide is less intense and, in its place, a broadened halo appears, the titanium or vanadium halide being used in an amount less than 50% by weight with respect to the magnesium dihalide.
Claim 42
Dependent Claim
98 words
Process for preparing components of catalysts for the polymerization of olefins comprising contacting a transition metal halide selected from titanium and vanadium halides in which the metal has a valence lower than 4, with an anhydrous magnesium dihalide in an active form characterized in that in the X-rays powder spectrum thereof the most intense diffraction line present in the spectrum of the normal non-active magnesium halide is less intense and, in its place, a broadened halo appears, the titanium or vanadium halide being used in an amount less than 50% by weight with respect to the magnesium dihalide.
Claim 43
Dependent Claim
15 words
The process of claim 36, in which the transition metal halide is TiCl 3 .
Claim 44
Dependent Claim
17 words
The process of claim 36, in which the anhydrous magnesium dihalide is magnesium dichloride or magnesium dibromide.
Claim 45
Dependent Claim
26 words
The process of claim 36, in which the transition metal halide is TiCl 3 and the anhydrous magnesium dihalide is MgCl 2 or MgBr 2 .
Claim 46
Dependent Claim
63 words
The process of claim 36, in which the titanium or vanadium halide is coground with a normal, non-active magnesium dihalide until said dihalide is converted to an active form characterized in that, in its X-rays powder spectrum, the most intense diffraction line present in the spectrum of the normal, non-active magnesium dihalide is less intense and, in its place, a broadened halo appears.
Claim 47
Dependent Claim
15 words
The process of claim 40, in which the transition metal halide is TiCl 3 .
Claim 48
Dependent Claim
18 words
The process of claim 40, in which the magnesium dihalide is anhydrous magnesium dichloride or anhydrous magnesium dibromide.
Claim 49
Dependent Claim
26 words
The process of claim 40, in which the transition metal halide is TiCl 3 and the anhydrous magnesium dihalide is MgCl 2 or MgBr 2 .
Claim 50
Dependent Claim
19 words
The process of claim 36, in which the transition metal halide is contacted with a preactivated anhydrous magnesium dihalide.
Claim 51
Dependent Claim
15 words
The process of claim 44, in which the anhydrous magnesium dihalide is preactivated by grinding.
Claim 52
Dependent Claim
17 words
The process of claim 45, in which TiCl 3 is contacted with the preactivated anhydrous magnesium dihalide.
Claim 53
Dependent Claim
23 words
The process of claim 45, in which the transition metal halide is contacted with preactivated anhydrous magnesium dichloride or preactivated anhydrous magnesium dibromide.
Claim 54
Dependent Claim
22 words
The process of claim 45, in which TiCl 3 is contacted with preactivated anhydrous MgCl 2 or preactivated anhydrous MgBr 2 .
Claim 55
Dependent Claim
39 words
The process of claim 44, in which the transition metal halide is contacted with a preactivated anhydrous magnesium dihalide obtained by decomposition of a compound of formula RMgX, in which R is a hydrocarbon radical and X is halogen.
Claim 56
Dependent Claim
16 words
The process of claim 49 in which, in the formula RMgX, R is alkyl or aryl.
Claim 57
Dependent Claim
43 words
The process of claim 44, in which the preactivated anhydrous magnesium dihalide is obtained by reacting a compound of formula RMgX, in which R is a hydrocarbon radical and X is halogen, with at least the stoichiometric amount of an anhydrous halogenated substance.
Claim 58
Dependent Claim
15 words
The process of claim 51, in which the anhydrous halogenated substance is anhydrous hydrogen chloride.
Claim 59
Dependent Claim
16 words
The process of claim 51, in which, in the formula RMgX, R is alkyl or aryl.
Claim 60
Dependent Claim
46 words
The process according to claim 44, in which the active magnesium dihalide is obtained from a solution of the dihalide in an organic solvent by partially evaporating the solvent and then completing removal of the solvent at a temperature above 100° C. and under reduced pressure.
Claim 61
Dependent Claim
35 words
The process of claim 36, in which the anhydrous magnesium dihalide is coground with delta-TiCl 3 obtained by reduction of TiCl 4 with aluminum and conversion of the reduction product to delta-TiCl 3 by grinding.
Claim 62
Dependent Claim
19 words
The process of claim 55, in which the anhydrous magnesium dihalide is anhydrous magnesium dichloride or anhydrous magnesium dibromide.
Claim 63
Dependent Claim
30 words
The process of claim 36, in which an inert solvent suspension of the titanium or vanadium halide is brought into contact with an inert solvent suspension of the magnesium dihalide.
References Cited (Backward Citations)
CA703847A
Cited
US3058963A
Cited
US2981725A
Cited
US3032510A
Cited
GB872142A
Cited
US3482935A
Cited
US3238146A
Cited
US3244477A
Cited
US3392159A
Cited
US3298965A
Cited
US4298718A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-01-22 | 1988-07-23 | 1989-01-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-01-22 | 1992-07-23 | 1993-01-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-01-22 | 1996-07-23 | 1997-01-22 | $7700.00 | Window Closed / Lapsed |