US4526941A
Expired / Lapsed
US
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Polymerization of olefins
Assignee: Asahi Kasei Corp
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Filing: 1983-09-23
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Granted: 1985-07-02
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Expires: 2003-09-23
Abstract
Abstract A process for polymerizing an α-olefin which comprises contacting the α-olefin at a temperature of about 10° C. to about 100° C. with a catalyst comprising a slurry component (A) and an organometallic component (B), the component (A) being obtained, without intermediate or final solids separation, by reacting (1) a slurry reaction mixture produced by reacting one mol of (i) a hydrocarbon-soluble organomagnesium component of the general formula MαMgβR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.s or of the reaction product of MαMgβR p 1 R q 2 X r Y s with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines, with 0.1 to 10 mols of (ii) a chlorosilane compound of the formula H.sub.a SiCl.sub.b R.sub.4-(a+b).sup.10 at a temperature of about 20° C. to about 150° C., with (2) a titanium compound of the formula Ti(OR.sup.11).sub.n Z.sub.4-n and (3) a nitrogen- or sulfur-containing heterocyclic carboxylic acid ester or a hydrocarbyl carboxylic acid ester and the mol ratio of (2) the titanium compound/(3) the carboxylic acid ester being at least 0.3.
Inventors
- 👤 Hisaya Sakurai
- 👤 Tadashi Ikegami
- 👤 Masayoshi Miya
- 👤 Katsuhiko Takaya
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 06:42
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
367 words
A process for polymerizing an α-olefin which comprises contacting the α-olefin at a temperature of about 10° C. to about 100° C. with a catalyst comprising a slurry component (A) and an organometallic component (B), the component (A) being obtained, without intermediate or final solids separation, by reacting (1) a slurry reaction mixture produced by reacting one mol of (i) a hydrocarbon-soluble organomagnesium component of the general formula M.sub.α Mg.sub.β R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.s wherein α, p, q, r and s each independently is 0 or a number greater than 0, β is a number greater than 1, p+q+r+s=mα+2β, 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 and Y each independently is a hydrogen atom, a halogen atom, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 or SR 9 wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and R 9 is a hydrocarbon group having 1 to 20 carbon atoms, or of the reaction product of M.sub.α Mg.sub.β R p 1 R q 2 X r Y s with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines, with 0.1 to 10 mols of (ii) a chlorosilane compound of the formula H.sub.a SiCl.sub.b R.sub.4-.sup.10.sub.(a+b) wherein R 10 is a hydrocarbon group having 1 to 20 carbon atoms, 0<a≦2 and b is a number greater than 1 at a temperature of about 20° C. to about 150° C., with (2) a titanium compound of the formula Ti(OR.sup.11).sub.n Z.sub.4-n wherein R 11 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a halogen atom and 0≦n≦4, and (3) a nitrogen- or sulfur-containing heterocyclic carboxylic acid ester or a hydrocarbyl carboxylic acid ester and the mol ratio of (2) the titanium compound/(3) the carboxylic acid ester being at least 0.3.
Claim 2
Dependent Claim
367 words
A process for polymerizing an α-olefin which comprises contacting the α-olefin at a temperature of about 10° C. to about 100° C. with a catalyst comprising a slurry component (A) and an organometallic component (B), the component (A) being obtained, without intermediate or final solids separation, by reacting (1) a slurry reaction mixture produced by reacting one mol of (i) a hydrocarbon-soluble organomagnesium component of the general formula M.sub.α Mg.sub.β R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.s wherein α, p, q, r and s each independently is 0 or a number greater than 0, β is a number greater than 1, p+q+r+s=mα+2β, 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 and Y each independently is a hydrogen atom, a halogen atom, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 or SR 9 wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and R 9 is a hydrocarbon group having 1 to 20 carbon atoms, or of the reaction product of M.sub.α Mg.sub.β R p 1 R q 2 X r Y s with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines, with 0.1 to 10 mols of (ii) a chlorosilane compound of the formula H.sub.a SiCl.sub.b R.sub.4-.sup.10.sub.(a+b) wherein R 10 is a hydrocarbon group having 1 to 20 carbon atoms, 0<a≦2 and b is a number greater than 1 at a temperature of about 20° C. to about 150° C., with (2) a titanium compound of the formula Ti(OR.sup.11).sub.n Z.sub.4-n wherein R 11 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a halogen atom and 0≦n≦4, and (3) a nitrogen- or sulfur-containing heterocyclic carboxylic acid ester or a hydrocarbyl carboxylic acid ester and the mol ratio of (2) the titanium compound/(3) the carboxylic acid ester being at least 0.3.
Claim 3
Dependent Claim
26 words
The process of claim 1, wherein M in the hydrocarbon-soluble organomagnesium component (i) of the slurry component [A] is lithium, beryllium, boron, aluminum or zinc metal.
Claim 4
Dependent Claim
21 words
The process of claim 2, wherein M in the hydrocarbon-soluble organomagnesium component (i) of the slurry component [A] is aluminum metal.
Claim 5
Dependent Claim
30 words
The process of claim 1, wherein α in the hydrocarbon-soluble organomagnesium component (i) in the slurry component [A] is a number greater than 0 and β/α is 0.5 to 10.
Claim 6
Dependent Claim
26 words
The process of claim 1, wherein the amount of X r and X s in the organomagnesium component (i) of the slurry component [A] is 0≦(r+s)/(α+β)<1.
Claim 7
Dependent Claim
103 words
The process of claim 1, wherein the hydrocarbon-soluble organomagnesium component (i) in the slurry component [A] is a hydrocarbon-soluble organomagnesium component wherein α is zero and (a) R 1 and R 2 both are alkyl groups having 4 to 6 carbon atoms and at least one of R 1 and R 2 is a secondary or tertiary alkyl group or (b) R 1 is an alkyl group having 2 or 3 carbon atoms and R 2 is an alkyl group having at least 4 carbon atoms or (c) R 1 and R 2 both are hydrocarbon groups having at least 6 carbon atoms.
Claim 8
Dependent Claim
24 words
The process of claim 1, wherein the chlorosilane compound (ii) in the slurry component [A] is a chlorosilane compound wherein 0.5≦a≦1.5, b>1 and (a+b)≦4.
Claim 9
Dependent Claim
12 words
The process of claim 7, wherein the chlorosilane compound (ii) is trichlorosilane.
Claim 10
Dependent Claim
12 words
The process of claim 7, wherein the chlorosilane compound (ii) is monomethyldichlorosilane.
Claim 11
Dependent Claim
44 words
The process of claim 1, wherein the reaction between (i) the hydrocarbon-soluble organomagnesium component or the reaction product of the hydrocarbon-soluble organomagnesium component with at least one electron donor and (ii) the chlorosilane compound is carried out in the presence of an inorganic oxide.
Claim 12
Dependent Claim
40 words
The process of claim 10, wherein the amount of the inorganic oxide is 10 g to 10 Kg per mol of the hydrocarbon-soluble organomagnesium component or the reaction product of the hydrocarbon-soluble organomagnesium component with at least one electron donor.
Claim 13
Dependent Claim
40 words
The process of claim 11, wherein the amount of the inorganic oxide is 20 g to 5 Kg per mol of the hydrocarbon-soluble organomagnesium component or the reaction product of the hydrocarbon-soluble organomagnesium component with at least one electron donor.
Claim 14
Dependent Claim
15 words
The process of claim 10, wherein the inorganic oxide is silica, silica-alumina, alumina or magnesia.
Claim 15
Dependent Claim
11 words
The process of claim 13, wherein the inorganic oxide is silica.
Claim 16
Dependent Claim
11 words
The process of claim 13, wherein the inorganic oxide is silica-alumina.
Claim 17
Dependent Claim
30 words
The process of claim 10, wherein (i) the hydrocarbon-soluble organomagnesium component or the reaction product of the hydrocarbon-soluble organomagnesium component with at least one electron donor contains OR 3 .
Claim 18
Dependent Claim
34 words
The process of claim 10, wherein (i) the hydrocarbon-soluble organomagnesium component or the reaction product of the hydrocarbon-soluble organomagnesium component with at least one electron donor contains OSiR 4 R 5 R 6 .
Claim 19
Dependent Claim
14 words
The process of claim 1, wherein n in the titanium compound (2) is 0.
Claim 20
Dependent Claim
14 words
The process of claim 18, wherein Z in the titanium compound (2) is chlorine.
Claim 21
Dependent Claim
13 words
The process of claim 19, wherein the titanium compound (2) is titanium tetrachloride.
Claim 22
Dependent Claim
14 words
The process of claim 1, wherein n in the titanium compound (2) is 4.
Claim 23
Dependent Claim
15 words
The process of claim 1, wherein the amount of the titanium compound (2) is 3≦Mg/Ti≦500.
Claim 24
Dependent Claim
38 words
The process of claim 1, wherein the sulfur-containing heterocyclic carboxylic acid ester, the nitrogen-containing heterocyclic carboxylic acid ester or the hydrocarbyl carboxylic acid ester is the ester of a lower alkyl alcohol having 1 to 5 carbon atoms.
Claim 25
Dependent Claim
32 words
The process of claim 1, wherein the mol ratio of (2) the titanium compound/(3) the nitrogen- or sulfur-containing heterocyclic carboxylic acid ester or the hydrocarbyl carboxylic acid ester is 0.4 to 5.
Claim 26
Dependent Claim
32 words
The process of claim 1, wherein the electron donor is an ether, a thioether, a ketone, an aldehyde, a hydrocarbyl carboxylic acid or its derivative, an alcohol, a thioalcohol or an amine.
Claim 27
Dependent Claim
14 words
The process of claim 1, wherein the organometallic component [B] is an organoaluminum compound.
Claim 28
Dependent Claim
16 words
The process of claim 26, wherein the organoaluminum compound is a trialkylaluminum or a dialkylaluminum hydride.
Claim 29
Dependent Claim
35 words
The process of claim 1, wherein the mol ratio of M in the slurry component [A] plus the metal in the organometallic component [B] to Ti in the slurry component [A] is 3/1 to 1000/1.
Claim 30
Dependent Claim
26 words
The process of claim 1, wherein the α-olefin is at least one member selected from the group consisting of ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1 and 3-methylbutene-1.
Claim 31
Dependent Claim
10 words
The process of claim 29, wherein the α-olefin is propylene.
Claim 32
Dependent Claim
350 words
A catalyst suitable for producing a poly-α-olefin which comprises a slurry component (A) and an organometallic component (B), the component (A) being obtained without intermediate or final solids separation, by reacting (1) a slurry reaction mixture produced by reacting one mol of (i) a hydrocarbon-soluble organomagnesium component of the general formula M.sub.α Mg.sub.β R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.s wherein α, p, q, r and s each independently is 0 or a number greater than 0, β is a number greater than 1, p+q+r+s=mα+2β, 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 and Y each independently is a hydrogen atom, a halogen atom, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 or SR 9 wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and R 9 is a hydrocarbon group having 1 to 20 carbon atoms or of the reaction product of M.sub.α Mg.sub.β R p 1 R q 2 X r Y s with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines, with 0.1 to 10 mols of (ii) a chlorosilane compound of the formula H.sub.a SiCl.sub.b R.sub.4-.sup.10.sub.(a+b) wherein R 10 is a hydrocarbon group having 1 to 20 carbon atoms, 0<a≦2 and b is a number greater than 1 at a temperature of about 20° C. to about 150° C., with (2) a titanium compound of the formula Ti(OR.sup.11).sub.n Z.sub.4-n wherein R 11 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a halogen atom and 0≦n≦4, and (3) a nitrogen- or sulfur-containing heterocyclic carboxylic acid ester or a hydrocarbyl carboxylic acid ester and the mol ratio of (2) the titanium compound/(3) the carboxylic acid ester being at least 0.3.
Claim 33
Dependent Claim
350 words
A catalyst suitable for producing a poly-α-olefin which comprises a slurry component (A) and an organometallic component (B), the component (A) being obtained without intermediate or final solids separation, by reacting (1) a slurry reaction mixture produced by reacting one mol of (i) a hydrocarbon-soluble organomagnesium component of the general formula M.sub.α Mg.sub.β R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r Y.sub.s wherein α, p, q, r and s each independently is 0 or a number greater than 0, β is a number greater than 1, p+q+r+s=mα+2β, 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 and Y each independently is a hydrogen atom, a halogen atom, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 or SR 9 wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and R 9 is a hydrocarbon group having 1 to 20 carbon atoms or of the reaction product of M.sub.α Mg.sub.β R p 1 R q 2 X r Y s with at least one electron donor selected from the group consisting of ethers, thioethers, ketones, aldehydes, carboxylic acids or derivatives thereof, alcohols, thioalcohols and amines, with 0.1 to 10 mols of (ii) a chlorosilane compound of the formula H.sub.a SiCl.sub.b R.sub.4-.sup.10.sub.(a+b) wherein R 10 is a hydrocarbon group having 1 to 20 carbon atoms, 0<a≦2 and b is a number greater than 1 at a temperature of about 20° C. to about 150° C., with (2) a titanium compound of the formula Ti(OR.sup.11).sub.n Z.sub.4-n wherein R 11 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a halogen atom and 0≦n≦4, and (3) a nitrogen- or sulfur-containing heterocyclic carboxylic acid ester or a hydrocarbyl carboxylic acid ester and the mol ratio of (2) the titanium compound/(3) the carboxylic acid ester being at least 0.3.
Claim 34
Dependent Claim
47 words
A process according to claim 1, in which (i) is AlMg 6 .0 (C 2 H 5 ) 3 .1 (n-OC 4 H 9 ) 11 .9, (ii) is HSiCl 3 , (2) is TiCl 4 , (3) is thiophene-2-carboxylic acid ethyl ester, and (B) is triisobutylaluminum.
Claim 35
Dependent Claim
51 words
A process according to claim 1, in which (i) is AlMg 6 .0 (C 2 H 5 ) 3 .0 (n-C 4 H 9 ) 12 .0, (ii) is HSiCl 3 , (2) is Ti(O-n-C 3 H 7 ) 4 , (3) is thiophene-2-carboxylic acid ethyl ester, and (B) is triisobutylaluminum.
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) | 1988-07-01 | 1988-12-31 | 1989-07-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-07-01 | 1992-12-31 | 1993-07-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-07-01 | 1996-12-31 | 1997-07-02 | $7700.00 | Window Closed / Lapsed |