US4471066A
Expired / Lapsed
US
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Polymerization of olefins
Assignee: Asahi Kasei Corp
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Filing: 1983-02-03
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Granted: 1984-09-11
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Expires: 2003-02-03
Abstract
Abstract A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) an organometallic compound with (2) a transition metal compound selected from the group consisting of a titanium compound, a vanadium compound, a mixture of a titanium compound and a vanadium compound and a mixture of a titanium compound and a zirconium compound, in the presence of (3) a solid reaction product of (a) an organomagnesium compound of the formula M.sub.α MgR.sub.p X.sub.q.D.sub.r wherein α, p, q and r each independently is 0 or a number greater than 0, p+q=mα+2 0≦q/(α+1)<2 m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R is at least one hydrocarbon group having 1 to 20 carbon atoms, X is at least one member selected from the group consisting of a hydrogen atom and electronegative groups containing an oxygen atom, a nitrogen atom or a sulfur atom, D is an electron donative organic compound, with (b) at least one compound selected from the group consisting of halides of boron, silicon, germanium, tin, phosphorus, antimony, bismuth or zinc and hydrogen chloride; and a polymerization process employing such a catalyst.
Inventors
- 👤 Hisaya Sakurai
- 👤 Yoshihiko Katayama
- 👤 Tadashi Ikegami
- 👤 Masayasu Furusato
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 06:14
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 52
Claim 1
Independent Claim
203 words
A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) an organometallic compound with (2) a transition metal compound selected from the group consisting of a titanium compound, a vanadium compound, a mixture of a titanium compound and a vanadium compound and a mixture of a titanium compound and a zirconium compound, in the presence of (3) a solid reaction product of (a) an organomagnesium compound of the formula M.sub.α MgR.sub.p X.sub.q.D.sub.r wherein α, p, q and r each independently is 0 or a number greater than 0, p+q=mα+2 0≦q/(α+1)<2 m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R is at least one hydrocarbon group having 1 to 20 carbon atoms, X is at least one member selected from the group consisting of a hydrogen atom and electronegative groups containing an oxygen atom, a nitrogen atom or a sulfur atom, D is an electron donative organic compound, with (b) at least one compound selected from the group consisting of halides of boron, silicon, germanium, tin, phosphorus, antimony, bismuth or zinc and hydrogen chloride.
Claim 2
Dependent Claim
203 words
A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) an organometallic compound with (2) a transition metal compound selected from the group consisting of a titanium compound, a vanadium compound, a mixture of a titanium compound and a vanadium compound and a mixture of a titanium compound and a zirconium compound, in the presence of (3) a solid reaction product of (a) an organomagnesium compound of the formula M.sub.α MgR.sub.p X.sub.q.D.sub.r wherein α, p, q and r each independently is 0 or a number greater than 0, p+q=mα+2 0≦q/(α+1)<2 m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R is at least one hydrocarbon group having 1 to 20 carbon atoms, X is at least one member selected from the group consisting of a hydrogen atom and electronegative groups containing an oxygen atom, a nitrogen atom or a sulfur atom, D is an electron donative organic compound, with (b) at least one compound selected from the group consisting of halides of boron, silicon, germanium, tin, phosphorus, antimony, bismuth or zinc and hydrogen chloride.
Claim 3
Dependent Claim
29 words
The catalyst of claim 1, wherein the solid reaction product (3) is a reaction product of the organomagnesium compound (a), the compound (b) and a solid inorganic oxide (c).
Claim 4
Dependent Claim
31 words
The catalyst of claim 1, wherein the solid reaction product (3) is a reaction product of the organomagnesium compound (a) and the compound (b) with an electron donative organic compound (d).
Claim 5
Dependent Claim
36 words
The catalyst of claim 2, wherein the solid reaction product (3) is a reaction product of the organomagnesium compound (a), the compound (b) and the solid inorganic oxide (c) with an electron donative organic compound (d).
Claim 6
Dependent Claim
33 words
The catalyst of claim 1, wherein the organometallic compound (1) is reacted with the transition metal compound in the presence of the solid reaction product (3) having been separated from the reaction solution.
Claim 7
Dependent Claim
26 words
The catalyst of claim 1, wherein M in the organomagnesium compound (a) of the solid reaction product (3) is lithium, beryllium, boron, aluminum or zinc metal.
Claim 8
Dependent Claim
21 words
The catalyst of claim 6, wherein M in the organomagnesium compound (a) of the solid reaction product (3) is aluminum metal.
Claim 9
Dependent Claim
20 words
The catalyst of claim 1, wherein α in the organomagnesium compound (a) of the solid reaction product (3) is 0≦α≦1.
Claim 10
Dependent Claim
20 words
The catalyst of claim 8, wherein α in the organomagnesium compound (a) of the solid reaction product (3) is 0.01≦α≦0.5.
Claim 11
Dependent Claim
95 words
The catalyst of claim 1, wherein X in the organomagnesium compound (a) of the solid reaction (3) is OR 1 , OSiR 2 R 3 R 4 , NR 5 R 6 , SR 7 or ##STR2## wherein R 1 , R 7 , R 8 and R 10 each independently is a hydrocarbon group having 1 to 20 carbon atoms and R 2 , R 3 , R 4 , R 5 , R 6 and R 9 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Claim 12
Dependent Claim
34 words
The catalyst of claim 10, wherein X in the organomagnesium compound (a) of the solid reaction product (3) is OR 1 wherein R 1 is a hydrocarbon atom having 1 to 20 carbon atoms.
Claim 13
Dependent Claim
49 words
The catalyst of claim 10, wherein X in the organomagnesium compound (a) of the solid reaction product (3) is OSiR 2 R 3 R 4 wherein R 2 , R 3 and R 4 each is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Claim 14
Dependent Claim
21 words
The catalyst of claim 1, wherein D is an ether, a siloxane, an amine or an ester of an organic acid.
Claim 15
Dependent Claim
20 words
The catalyst of claim 1, wherein q in the organomagnesium compound (a) of the solid reaction product (3) is 0≦q/(α+1)≦1.5.
Claim 16
Dependent Claim
20 words
The catalyst of claim 1, wherein r in the organomagnesium compound (a) of the solid reaction product (3) is 0≦r≦10.
Claim 17
Dependent Claim
20 words
The catalyst of claim 15, wherein r in the organomagnesium compound (a) of the solid reaction product (3) is 0≦r≦2.
Claim 18
Dependent Claim
19 words
The catalyst of claim 1, wherein the compound (b) of the solid reaction product (3) is a boron halide.
Claim 19
Dependent Claim
19 words
The catalyst of claim 1, wherein the compound (b) of the solid reaction product (3) is a tin halide.
Claim 20
Dependent Claim
19 words
The catalyst of claim 1, wherein the compound (b) of the solid reaction product (3) is a silicon halide.
Claim 21
Dependent Claim
19 words
The catalyst of claim 1, wherein the compound (b) of the solid reaction product (3) is a germanium halide.
Claim 22
Dependent Claim
24 words
The catalyst of claim 1, wherein the organometallic compound (1) is an organolithium compound, an organomagnesium compound, an organoaluminum compound or an organozic compound.
Claim 23
Dependent Claim
14 words
The catalyst of claim 21, wherein the organometallic compound (1) is an organoaluminum compound.
Claim 24
Dependent Claim
21 words
The catalyst of claim 22, wherein the organometallic compound (1) is an alkylaluminum containing a halogen atom or an electronegative group.
Claim 25
Dependent Claim
21 words
The catalyst of claim 1, wherein the transition metal compound (2) is a titanium compound having at least one halogen atom.
Claim 26
Dependent Claim
21 words
The catalyst of claim 1, wherein the transition metal compound (2) is a vanadium compound having at least one halogen atom.
Claim 27
Dependent Claim
34 words
The catalyst of claim 1, wherein the transition metal compound (2) is a mixture of a titanium compound having at least one halogen atom and a vanadium compound having at least one halogen atom.
Claim 28
Dependent Claim
16 words
The catalyst of claim 26, wherein the atomic ratio of vanadium to titanium is about 0.02-50:1.
Claim 29
Dependent Claim
34 words
The catalyst of claim 1, wherein the transition metal compound (2) is a mixture of a titanium compound having at least three alkoxy groups and a zirconium compound having at least three alkoxy groups.
Claim 30
Dependent Claim
16 words
The catalyst of claim 28, wherein the atomic ratio of zirconium to titanium is about 0.2-10:1.
Claim 31
Dependent Claim
26 words
The catalyst of claim 24, wherein the mol ratio of the titanium compound to the magnesium atom in the solid reaction product (3) is about 0.005-5:1.
Claim 32
Dependent Claim
26 words
The catalyst of claim 25, wherein the mol ratio of the vanadium compound to the magnesium atom in the solid reaction product (3) is about 0.005-5:1.
Claim 33
Dependent Claim
30 words
The catalyst of claim 26, wherein the mol ratio of the titanium compound plus the vanadium compound to the magnesium atom in the solid reaction product (3) is about 0.005-1:1.
Claim 34
Dependent Claim
30 words
The catalyst of claim 28, wherein the mol ratio of the titanium compound plus the zirconium compound to the magnesium atom in the solid reaction product (3) is about 0.001-0.35:1.
Claim 35
Dependent Claim
21 words
The catalyst of claim 24, wherein the mol ratio of the organometallic compound (1) to the titanium compound is about 0.05-20:1.
Claim 36
Dependent Claim
21 words
The catalyst of claim 25, wherein the mol ratio of the organometallic compound (1) to the vanadium compound is about 0.05-20:1.
Claim 37
Dependent Claim
25 words
The catalyst of claim 26, wherein the mol ratio of the organometallic compound (1) to the titanium compound plus the vanadium compound is about 0.05-20:1.
Claim 38
Dependent Claim
25 words
The catalyst of claim 28, wherein the mol ratio of the organometallic compound (1) to the titanium compound plus the zirconium compound is about 0.1-100:1.
Claim 39
Dependent Claim
30 words
The catalyst of claim 1, wherein the reaction between the organomagnesium compound (a) and the compound (b) is conducted at a temperature of about -50° C. to about 150° C.
Claim 40
Dependent Claim
21 words
The catalyst of claim 1, wherein the mol ratio of the compound (b) to the organomagnesium compound (a) is about 0.01-100:1.
Claim 41
Dependent Claim
29 words
The catalyst of claim 2, wherein the solid inorganic oxide (c) is at least one compound selected from the group consisting of silica, alumina, silica-alumina, magnesia, thoria and zirconia.
Claim 42
Dependent Claim
29 words
The catalyst of claim 38, wherein the amount of the organomagnesium compound (a) is about 0.05 mmol to about 100 mmols per gram of the solid inorganic oxide (c).
Claim 43
Dependent Claim
26 words
The catalyst of claim 3, wherein the electron donative organic compound (d) is an ether, a siloxane, an amine or an ester of an organic acid.
Claim 44
Dependent Claim
29 words
The catalyst of claim 42, wherein the mol ratio of the electron donative organic compound (d) to the magnesium atom in the solid reaction product (3) is about 0.01-100:1.
Claim 45
Dependent Claim
31 words
The catalyst of claim 1, wherein the organometallic component [B] is at least one compound selected from the group consisting of an organoaluminum compound, an organozinc compound and an organomagnesium compound.
Claim 46
Dependent Claim
14 words
The catalyst of claim 44, wherein the organometallic compound [B] is an organoaluminum compound.
Claim 47
Dependent Claim
35 words
The catalyst of claim 45, wherein the organoaluminum compound is a trialkylaluminum, an alkylaluminum hydride, an alkylaluminum halide, an alkylaluminum alkoxide, an alkyl-aluminum siloxide and a reaction product of an alkylaluminum and a conjugated diene.
Claim 48
Dependent Claim
11 words
The catalyst of claim 46, wherein organoaluminum compound is a trialkylaluminum.
Claim 49
Dependent Claim
13 words
The catalyst of claim 46, wherein the organoaluminum compound is an alkylaluminum hydride.
Claim 50
Dependent Claim
27 words
The catalyst of claim 1, wherein the mol ratio of the organometallic component [B] to the transition metal in the solid catalyst component [A] is about 3-1000:1.
Claim 51
Dependent Claim
20 words
The catalyst of claim 1, which comprises the catalyst component [A], the organometallic component [B] and a halogenated hydrocarbon [C].
Claim 52
Dependent Claim
22 words
The catalyst of claim 50, wherein the mol ratio of the halogenated hydrocarbon [C] to the organometallic component [B] is about 0.01-100:1.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-09-11 | 1988-03-12 | 1988-09-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-09-11 | 1992-03-12 | 1992-09-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-09-11 | 1996-03-12 | 1996-09-11 | $7700.00 | Window Closed / Lapsed |