US4335229A
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Process for polymerizing an α-olefin
Assignee: Asahi Kasei Corp
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Filing: 1980-08-13
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Granted: 1982-06-15
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Expires: 2000-08-13
Abstract
Abstract A process for polymerizing an α-olefin comprising contacting the olefin in liquid phase at a temperature of about 120° to about 320° C. with a catalyst comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formula, M.sub.α MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2 D t wherein α, p, q, r and s each independently is 0 or a number greater than 0, t is a number greater than 0, p+q+r+s=mα+2, O≦(r+s)/(α+1)<2, m is the valance of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 and R 2 each independently is a hydrocarbon group having 1 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom, a halogen atom or an organic electronegative group containing O, N, or S, D is an electron donor, with (ii) a halide of boron, silicon, germanium, tin, phosphorus, antimony, bismuth or zinc, and contacting the product of (i)+(ii) with (iii) a compound of titanium and/or a compound of vanadium at a concentration of titanium plus vanadium of at most about 2 mols per liter of the inert reaction solvent, the atomic ratio of Mg/(Ti+V) in (A) being about 3 to about 500.
Inventors
- 👤 Hisaya Sakurai
- 👤 Yoshihiko Katayama
- 👤 Tadashi Ikegami
- 👤 Masayasu Furusato
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 23:24
CPC Classifications
C; C08; C08F; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/904
Claims Analysis
Total Claims: 42
Claim 1
Independent Claim
219 words
A process for polymerizing an α-olefin comprising contacting the olefin in liquid phase at a temperature of about 120° to 320° C. with a catalyst comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formula, M.sub.α MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2 D.sub.t wherein α, p, q, r and s each independently is 0 or a number greater than 0, t is about 0.05 to about 10, p+q+r+s=mα+2, 0≦(r+s)/(α+β)<2, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 and R 2 each independently is a hydrocarbon group having 1 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom, a halogen atom or an organic electronegative group containing 0, N or S, D is an electron donor, with (ii) a halide boron, silicon, germanium, tin, phosphorus, antimony, bismuth or zinc, and contacting the product of (i)+(ii) in an inert reaction solvent with (iii) a compound of tetravalent titanium and/or a compound of pentavalent or tetravalent vanadium at a concentration of titanium plus vanadium of at most about 2 mols per liter of the inert reaction solvent, the atomic ratio of Mg/(Ti+V) in (A) being about 3 to about 500.
Claim 2
Dependent Claim
219 words
A process for polymerizing an α-olefin comprising contacting the olefin in liquid phase at a temperature of about 120° to 320° C. with a catalyst comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formula, M.sub.α MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2 D.sub.t wherein α, p, q, r and s each independently is 0 or a number greater than 0, t is about 0.05 to about 10, p+q+r+s=mα+2, 0≦(r+s)/(α+β)<2, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 and R 2 each independently is a hydrocarbon group having 1 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom, a halogen atom or an organic electronegative group containing 0, N or S, D is an electron donor, with (ii) a halide boron, silicon, germanium, tin, phosphorus, antimony, bismuth or zinc, and contacting the product of (i)+(ii) in an inert reaction solvent with (iii) a compound of tetravalent titanium and/or a compound of pentavalent or tetravalent vanadium at a concentration of titanium plus vanadium of at most about 2 mols per liter of the inert reaction solvent, the atomic ratio of Mg/(Ti+V) in (A) being about 3 to about 500.
Claim 3
Dependent Claim
24 words
A process of claim 1, wherein M in the organomagnesium component (i) of the component (A) is lithium, berylium, boron, aluminum or zinc metal.
Claim 4
Dependent Claim
19 words
A process of claim 2, wherein M in the organomagnesium component (i) of the component (A) is aluminum metal.
Claim 5
Dependent Claim
14 words
A process of claim 1, wherein α in the organomagnesium component (i) is 0≦α≦1.5.
Claim 6
Dependent Claim
14 words
A process of claim 4, wherein α in the organomagnesium component (i) is 0<α≦1.
Claim 7
Dependent Claim
85 words
A process of claim 1, wherein X 1 and X 2 in the organomagnesium component (i) each independently is OR 3 , OsiR 4 R 5 R 6 , NR 7 R 8 or SR 9 wherein R 3 , R 7 , R 8 and R 9 each independently is a hydrocarbon group having 1 to 15 carbon atoms and R 4 , R 5 and R 6 each independently is a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms.
Claim 8
Dependent Claim
22 words
A process of claim 6, wherein X 1 and X 2 in the organomagnesium component (i) each independently is OR 3 .
Claim 9
Dependent Claim
26 words
A process of claim 6, wherein X 1 and X 2 in the organomagnesium component (i) each independently is OSiR 4 R 5 R 6 .
Claim 10
Dependent Claim
30 words
A process of claim 1, wherein at least one of X 1 and X 2 is a halogen atom and the amount of X 1 and X 2 is (r+s)/(α+1)≦1.
Claim 11
Dependent Claim
24 words
A process of claim 1, wherein the electron donor represented by D is an electron donative organic compound containing O, N, S or P.
Claim 12
Dependent Claim
32 words
A process of claim 10, wherein the electron donative organic compound is an ether, a siloxane, a tertiary amine, a nitrile, an amide, a pyridine, a thioether, a sulfoxide or a phosphine.
Claim 13
Dependent Claim
14 words
A process of claim 11, wherein the electron donative organic compound is an ether.
Claim 14
Dependent Claim
14 words
A process of claim 11, wherein the electron donative organic compound is a siloxane.
Claim 15
Dependent Claim
14 words
A process of claim 11, wherein the electron donative organic compound is an amine.
Claim 16
Dependent Claim
13 words
A process of claim 1, wherein the polymerization temperature is about 200° C.
Claim 17
Dependent Claim
18 words
A process of claim 1, wherein t in the organomagnesium component (i) is about 0.2 to about 2.
Claim 18
Dependent Claim
14 words
A process of claim 9, wherein t in the organomagnesium component (i) is t/(r+s)≧1.
Claim 19
Dependent Claim
17 words
A process of claim 1, wherein the halide (ii) is a chloride of boron, silicon or germanium.
Claim 20
Dependent Claim
12 words
A process of claim 18, wherein the halide (ii) is a chlorosilane.
Claim 21
Dependent Claim
22 words
A process of claim 1, wherein (iii) the compound of titanium and/or the compound of vanadium contains at least one chlorine atom.
Claim 22
Dependent Claim
28 words
A process of claim 1, wherein the reaction between the component (i) and the halide (ii) is conducted at a temperature of about -50° to about 150° C.
Claim 23
Dependent Claim
23 words
A process of claim 1, wherein the mol ratio of the halide (ii) to the component (i) is about 0.01 to about 100.
Claim 24
Dependent Claim
23 words
A process of claim 1, wherein the mol ratio of the halide (ii) to the component (i) is about 0.1 to about 20.
Claim 25
Dependent Claim
37 words
A process of claim 1, wherein the contact of the reaction product of (i)+(ii) with (iii) the compound of titanium and/or the compound of vanadium is conducted at a temperature of about -50° to about 150° C.
Claim 26
Dependent Claim
44 words
A process of claim 24, wherein the contact of the reaction product of (i)+(ii) with (iii) the compound of titanium or (iii) the compound of titanium plus the compound of vanadium is conducted at a temperature of from about 0° to about 95° C.
Claim 27
Dependent Claim
22 words
A process of claim 1, wherein the atomic ratio of Mg/(Ti+V) in the component (A) is from about 5 to about 200.
Claim 28
Dependent Claim
22 words
A process of claim 26, wherein the atomic ratio of Mg/(Ti+V) in the component (A) is from about 10 to about 100.
Claim 29
Dependent Claim
52 words
A process of claim 1, wherein the reaction product of the component (i) and the halide (ii) is contacted with (iii) the compound of titanium and/or the compound of vanadium at a concentration of titanium plus vanadium of about 0.01 mmol to about 900 mmols per liter of the inert reaction solvent.
Claim 30
Dependent Claim
24 words
A process of claim 1, wherein the organometal component (B) is an organoaluminum compound, an organoboron compound, an organozinc compound or an organomagnesium compound.
Claim 31
Dependent Claim
14 words
A process of claim 29, wherein the organometal component (B) is an organoaluminum compound.
Claim 32
Dependent Claim
32 words
A process of claim 30, wherein the organoaluminum compound is a trialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide, an alkylaluminum siloxide and a reaction product of a trialkylaluminum and a conjugated diene.
Claim 33
Dependent Claim
26 words
A process of claim 1, wherein the mol ratio of the organometal compound (B) to (Ti+V) in the component (A) is about 3 to about 1000.
Claim 34
Dependent Claim
10 words
A process of claim 1, wherein the α-olefin is ethylene.
Claim 35
Dependent Claim
38 words
A process of claim 33, wherein the polymerization of ethylene is carried out at a partial pressure of ethylene of from about 1 to about 25 MPa at a polymerization temperature of about 150° to about 300° C.
Claim 36
Dependent Claim
18 words
A process of claim 1, wherein copolymerization of ethylene with an α-olefin other than ethylene or a polyene.
Claim 37
Dependent Claim
16 words
A process of claim 35, wherein the α-olefin other than ethylene is a C 3-20 α-olefin.
Claim 38
Dependent Claim
12 words
A process of claim 36, wherein the polyene is butadiene or isoprene.
Claim 39
Dependent Claim
20 words
A process of claim 35, wherein the mol ratio of the α-olefin or polyene to ethylene is at most 5.
Claim 40
Dependent Claim
19 words
A process of claim 1, wherein the polymerization of an α-olefin is conducted in a plurality of polymerization zones.
Claim 41
Dependent Claim
201 words
A catalyst useful for polymerizing an α-olefin comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formula M.sub.α MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2 D.sub.t wherein α, p, q, r and s each independently is 0 or a number greater than 0, t is about 0.05 to about 10, p+q+r+s=mα+2, 0≦(r+s)/(α+β)<2, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 and R 2 each independently is a hydrocarbon group having 1 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom, a halogen atom or an organic electronegative group containing O, N or S, D is an electron donor, with (ii) a halide boron, silicon, germanium, tin, phosphorus, antimony, bismuth or zinc, and contacting the product of (i)+(ii) in an inert reaction solvent with (iii) a compound of tetravalent titanium and/or a compound of pentavalent or tetravalent vanadium at a concentration of titanium plus vanadium of at most about 2 mols per liter of the inert reaction solvent, the atomic ratio of Mg/(Ti+V) in (A) being about 3 to about 500.
Claim 42
Dependent Claim
201 words
A catalyst useful for polymerizing an α-olefin comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formula M.sub.α MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2 D.sub.t wherein α, p, q, r and s each independently is 0 or a number greater than 0, t is about 0.05 to about 10, p+q+r+s=mα+2, 0≦(r+s)/(α+β)<2, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 and R 2 each independently is a hydrocarbon group having 1 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom, a halogen atom or an organic electronegative group containing O, N or S, D is an electron donor, with (ii) a halide boron, silicon, germanium, tin, phosphorus, antimony, bismuth or zinc, and contacting the product of (i)+(ii) in an inert reaction solvent with (iii) a compound of tetravalent titanium and/or a compound of pentavalent or tetravalent vanadium at a concentration of titanium plus vanadium of at most about 2 mols per liter of the inert reaction solvent, the atomic ratio of Mg/(Ti+V) in (A) being about 3 to about 500.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-06-14 | 1985-12-14 | 1986-06-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-06-14 | 1989-12-14 | 1990-06-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-06-14 | 1993-12-14 | 1994-06-15 | $7700.00 | Window Closed / Lapsed |