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US4330647A
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Process for polymerizing α-olefins
Assignee: Asahi Kasei Corp
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Filing: 1980-08-13
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Granted: 1982-05-18
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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 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 α, p, q, r, s and t each independently is O or a number greater than 0, p+q+r+s=mα+2 O≦(r+s)/(α+1)<2, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 is a hydrocarbon group having 1 to 20 carbon atoms, R 2 is a secondary or tertiary alkyl group having 3 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom or an organic electronegative group containing O, N or S, D is an electron donor, with a compound (ii) of the formula, R.sub.a.sup.3 C Y.sub.4-a wherein R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y is a halogen atom, a is 0 or 1, 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 21:26
CPC Classifications
C; C08; C08F; C08F10/00; C08F2410/00; C08F2410/03
Claims Analysis
Total Claims: 43
Claim 1
Independent Claim
239 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 compenent (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, s and t each independently is 0 or a number greater than 0, [< (r+s)/(α+1)<2, ]0<(r+s)/(α+1)<1.5, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 is a hydrocarbon group having 1 to 20 carbon atoms, R 2 is a secondary or tertiary alkyl group having 3 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom or an organic electronegative group containing O, N or S, D is an electron donor, with a compound (ii) of the formula, R.sub.a.sup.3 CY.sub.4-a wherein R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y is a halogen atom, a is 0 or 1, and contacting the product of (i)+(ii) 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 an inert reaction solvent, the atomic ratio of Mg/(Ti+V) in (A) being about 3 to about 500.
Claim 2
Dependent Claim
239 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 compenent (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, s and t each independently is 0 or a number greater than 0, [< (r+s)/(α+1)<2, ]0<(r+s)/(α+1)<1.5, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 is a hydrocarbon group having 1 to 20 carbon atoms, R 2 is a secondary or tertiary alkyl group having 3 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom or an organic electronegative group containing O, N or S, D is an electron donor, with a compound (ii) of the formula, R.sub.a.sup.3 CY.sub.4-a wherein R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y is a halogen atom, a is 0 or 1, and contacting the product of (i)+(ii) 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 an 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.
Claim 6
Dependent Claim
14 words
A process of claim 4, wherein α in the organomagnesium component (i) is 0<α≦0.5.
Claim 7
Dependent Claim
96 words
A process of claim 1, wherein X 1 and X 2 in the organomagnesium component (i) each independently is OR 4 , OSiR 5 R 6 R 7 , NR 8 R 9 , SR 10 or ##STR2## wherein R 4 , R 10 , R 11 and R 13 each independently is a hydrocarbon group having 1 to 20 carbon atoms and R 5 , R 6 , R 7 , R 8 , R 9 and R 12 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 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 4 .
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 5 R 6 R 7 .
Claim 10
Dependent Claim
13 words
A process of claim 1, wherein the polymerization temperature is about 180° C.
Claim 11
Dependent Claim
21 words
A process of claim 1, wherein the amount of X 1 and X 2 in the organomagnesium component (i) is 0.1≦(r+s)/(α+1)≦1.3.
Claim 12
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 13
Dependent Claim
32 words
A process of claim 11, 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 14
Dependent Claim
14 words
A process of claim 12, wherein the electron donative organic compound is an ether.
Claim 15
Dependent Claim
14 words
A process of claim 12, wherein the electron donative organic compound is a siloxane.
Claim 16
Dependent Claim
14 words
A process of claim 12, wherein the electron donative organic compound is an amine.
Claim 17
Dependent Claim
18 words
A process of claim 1, wherein t in the organomagnesium component (i) is about 0.05 to about 10.
Claim 18
Dependent Claim
18 words
A process of claim 1, wherein t in the organomagnesium component (i) is about 0.2 to about 2.
Claim 19
Dependent Claim
20 words
A process of claim 1, wherein the compound (ii) is a carbon tetrahalide, a carbon monohydrohalide or a carbon monoalkylhalide.
Claim 20
Dependent Claim
12 words
A process of claim 18, wherein the carbon tetrahalide is carbon tetrachloride.
Claim 21
Dependent Claim
11 words
A process of claim 18, wherein the carbon monohydrohalide is chloroform.
Claim 22
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 23
Dependent Claim
28 words
A process of claim 1, wherein the reaction between the component (i) and the compound (ii) is conducted at a temperature of about -50° to about 150° C.
Claim 24
Dependent Claim
23 words
A process of claim 1, wherein the mol ratio of the compound (ii) to the component (i) is about 0.01 to about 100.
Claim 25
Dependent Claim
23 words
A process of claim 1, wherein the mol ratio of the compound (ii) to the component (i) is about 0.1 to about 20.
Claim 26
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 27
Dependent Claim
37 words
A process of claim 25, 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 0° to about 95° C.
Claim 28
Dependent Claim
21 words
A process of claim 1, wherein the atomic ratio of Mg/(Ti+V) in the component (A) is about 5 to about 200.
Claim 29
Dependent Claim
21 words
A process of claim 27, wherein the atomic ratio of Mg/(Ti+V) in the component (A) is about 10 to about 100.
Claim 30
Dependent Claim
52 words
A process of claim 1, wherein the reaction product of the component (i) and the compound (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 100 mmols per liter of the inert reaction solvent.
Claim 31
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 32
Dependent Claim
14 words
A process of claim 30, wherein the organometal component (B) is an organoaluminum compound.
Claim 33
Dependent Claim
32 words
A process of claim 31, 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 34
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 35
Dependent Claim
10 words
A process of claim 1, wherein the α-olefin is ethylene.
Claim 36
Dependent Claim
37 words
A process of claim 34, wherein the polymerization of ethylene is carried out at a partial pressure of ethylene of about 1 to about 25 MPa at a polymerization temperature of about 150° to about 300° C.
Claim 37
Dependent Claim
18 words
A process of claim 1, wherein copolymerization of ethylene with an α-olefin other than ethylene or a polyene.
Claim 38
Dependent Claim
16 words
A process of claim 36, wherein the α-olefin other than ethylene is a C 3-20 α-olefin.
Claim 39
Dependent Claim
12 words
A process of claim 36, wherein the polyene is butadiene or isoprene.
Claim 40
Dependent Claim
20 words
A process of claim 36, wherein the mol ratio of the α-olefin or polyene to ethylene is at most 5.
Claim 41
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 42
Dependent Claim
220 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, s and t each independently is 0 or a number greater than 0, p+q+r+s=mα=2, 0≦(r+s)/(α+1)<2,]0<(r+s)/(α+1)<1.5, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 is a hydrocarbon group having 1 to 20 carbon atoms, R 2 is a secondary or tertiary alkyl group having 3 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom or an organic electronegative group containing O, N or S, D is an electron donor, with a compound (ii) of the formula, R.sub.a.sup.3 CY.sub.4-1 wherein R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y is a halogen atom, a is 0 or 1, and contacting the product of (i)+(ii) 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 an inert reaction solvent, the atomic ratio of Mg/(Ti+V) in (A) being about 3 to about 500.
Claim 43
Dependent Claim
220 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, s and t each independently is 0 or a number greater than 0, p+q+r+s=mα=2, 0≦(r+s)/(α+1)<2,]0<(r+s)/(α+1)<1.5, m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table, R 1 is a hydrocarbon group having 1 to 20 carbon atoms, R 2 is a secondary or tertiary alkyl group having 3 to 20 carbon atoms, X 1 and X 2 each independently is a hydrogen atom or an organic electronegative group containing O, N or S, D is an electron donor, with a compound (ii) of the formula, R.sub.a.sup.3 CY.sub.4-1 wherein R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y is a halogen atom, a is 0 or 1, and contacting the product of (i)+(ii) 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 an 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) | 1985-05-17 | 1985-11-16 | 1986-05-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-05-17 | 1989-11-16 | 1990-05-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-05-17 | 1993-11-16 | 1994-05-18 | $7700.00 | Window Closed / Lapsed |