US4159256A
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Catalyst for polymerizing olefins and polymerization method of olefins carried out therewith
Assignee: Asahi Kasei Corp
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Filing: 1978-02-10
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Granted: 1979-06-26
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Expires: 1998-02-10
Abstract
Abstract Novel high active catalysts useful for highly stereospecific polymerization of olefin which enables to produce polymer of low content of catalyst residue, and of good grain size having a high stereoregularity can be obtained by a combination of [A] a solid catalyst component obtained by reacting and/or grinding a specified organomagnesium component (i) with a specified chlorosilane compound containing Si-H (ii) to obtain a solid (1) and reacting said solid (1) with a titanium compound containing at least one halogen atom (2) and a carboxylic acid or a derivative thereof (3) and [B] a component consisting of an organometallic compound and a carboxylic acid or a derivative thereof. The organomagnesium component is of the 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 is a number of 0 or greater than 0; β>0, p, q, r, and s are each a number of 0 or greater; p+q+r+s=mα+2β wherein m is the valency of M; M is a metal element of the 1st to the 3rd group of the Periodic Table; R 1 and R 2 are the same or different hydrocarbon radicals having 1 to 20 carbon atoms; X and Y are the same or different radicals selected from the group consisting of halogen, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 and SR 9 wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each hydrogen atom or a hydrocarbon radical having 1 to 20 carbon atoms and R 9 is a hydrocarbon radical having 1 to 20 carbon atoms, and chlorosilane is of the formula H.sub.a SiCl.sub.b R.sub.4-(a+b) wherein a and b are each a number greater than 0, having the relationships a≦2 and a+b≦4 wherein R is a hydrocarbon radical having 1 to 20 carbon atoms.
Inventors
- 👤 Hisaya Sakurai
- 👤 Hideo Morita
- 👤 Tadashi Ikegami
- 👤 Masayoshi Miya
- 👤 Katsuhiko Takaya
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 22:03
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
382 words
In a catalyst useful for polymerizing olefins comprising a magnesium compound, a titanium compound, an electron donor, and an organometallic compound, the improvement which is characterized in that a solid (1) is obtained by reacting one mole of organomagnesium component (i) represented by 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 is a number of 0 or greater than 0; β>0; p, q, r and s are each numbers 0 or greater than 0, respectively, having the relationship of p+q+r+s=mα+2β; M is a metal component of the 1st to the 3rd group of the Periodic Table; m is the valency of M; R 1 and R 2 are the same or different hydrocarbon groups having 1-20 carbon atoms; X and Y are the same or different groups selected from the group consisting of halogen, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 and SR 9 , wherein R 3 , r 4 , r 5 , r 6 , r 7 and R 8 are hydrogen atoms or hydrocarbon groups having 1-20 carbon atoms, and R 9 is a hydrocarbon group having 1-20 carbon atoms, with 0.01-100 moles of chlorosilane compound (ii) containing Si-H bonds and represented by the general formula H.sub.a SiCl.sub.b R.sub.4-(a+b) wherein < a≦2, b is a number greater than 0, a+b≦4, and R is a hydrocarbon group having 1-20 carbon atoms, that a solid catalyst component (A) is obtained by grinding, or reacting and grinding said solid (1), a titanium compound (2) selected from a tetravalent titanium halide and/or a trivalent titanium halide, and a carboxylic acid or a derivative thereof (3) selected from a carboxylic acid having up to 30 carbon atoms, an acid halide having up to 30 carbon atoms, an acid anhydride or a carboxylic acid ester having up to 30 carbon atoms in the carboxylic portion, and that said catalyst component (A) is used with a component (B) comprising an organometallic compound of a metal selected from Groups I, II, III of the Periodic Table mixed with a carboxylic acid or derivative thereof selected from a carboxylic acid having up to 30 carbon atoms, an acid halide, an acid anhydride or a carboxylic acid ester having up to 30 carbon atoms in the carboyxlic portion.
Claim 2
Dependent Claim
382 words
In a catalyst useful for polymerizing olefins comprising a magnesium compound, a titanium compound, an electron donor, and an organometallic compound, the improvement which is characterized in that a solid (1) is obtained by reacting one mole of organomagnesium component (i) represented by 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 is a number of 0 or greater than 0; β>0; p, q, r and s are each numbers 0 or greater than 0, respectively, having the relationship of p+q+r+s=mα+2β; M is a metal component of the 1st to the 3rd group of the Periodic Table; m is the valency of M; R 1 and R 2 are the same or different hydrocarbon groups having 1-20 carbon atoms; X and Y are the same or different groups selected from the group consisting of halogen, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 and SR 9 , wherein R 3 , r 4 , r 5 , r 6 , r 7 and R 8 are hydrogen atoms or hydrocarbon groups having 1-20 carbon atoms, and R 9 is a hydrocarbon group having 1-20 carbon atoms, with 0.01-100 moles of chlorosilane compound (ii) containing Si-H bonds and represented by the general formula H.sub.a SiCl.sub.b R.sub.4-(a+b) wherein < a≦2, b is a number greater than 0, a+b≦4, and R is a hydrocarbon group having 1-20 carbon atoms, that a solid catalyst component (A) is obtained by grinding, or reacting and grinding said solid (1), a titanium compound (2) selected from a tetravalent titanium halide and/or a trivalent titanium halide, and a carboxylic acid or a derivative thereof (3) selected from a carboxylic acid having up to 30 carbon atoms, an acid halide having up to 30 carbon atoms, an acid anhydride or a carboxylic acid ester having up to 30 carbon atoms in the carboxylic portion, and that said catalyst component (A) is used with a component (B) comprising an organometallic compound of a metal selected from Groups I, II, III of the Periodic Table mixed with a carboxylic acid or derivative thereof selected from a carboxylic acid having up to 30 carbon atoms, an acid halide, an acid anhydride or a carboxylic acid ester having up to 30 carbon atoms in the carboyxlic portion.
Claim 3
Dependent Claim
54 words
A catalyst for polymerizing olefins according to claim 1, wherein said organomagnesium component (i) is a hydrocarbon soluble organomagnesium complex compound wherein α is a number greater than 0, M is an atom selected from the group consisting of aluminum, boron, zinc and beryllium, and X and Y are groups other than halogen, respectively.
Claim 4
Dependent Claim
34 words
A catalyst for polymerizing olefins according to claim 1, wherein said organomagnesium component (i) is a hydrocarbon soluble organomagnesium compound wherein α is 0, and X and Y are groups other than halogen, respectively.
Claim 5
Dependent Claim
20 words
A catalyst for polymerizing olefins according to claim 2, wherein the ratio of β/α is in the range of 0.5-10.
Claim 6
Dependent Claim
20 words
A catalyst for polymerizing olefins according to claim 2, wherein the ratio of (r+s)/(α+β) is in the range of 0-0.8.
Claim 7
Dependent Claim
18 words
A catalyst for polymerizing olefins according to claim 1, wherein said titanium compound (A) (2) is titanium tetrachloride.
Claim 8
Dependent Claim
18 words
A catalyst for polymerizing olefins according to claim 1, wherein said titanium compound (A) (2) is titanium trichloride.
Claim 9
Dependent Claim
25 words
A catalyst for polymerizing olefins according to claim 1, wherein said titanium compound (A) (2) is a tetravalent titanium halide or a trivalent titanium halide.
Claim 10
Dependent Claim
21 words
A catalyst for polymerizing olefins according to claim 1, wherein said titanium compound (A) (2) is titanium tetrachloride or titanium trichloride.
Claim 11
Dependent Claim
46 words
A catalyst for polymerizing olefins according to claim 1, wherein said carboxylic acid or derivative thereof (A) (3) is used in 0.001-50 times the molar amount of the hydrocarbon groups included in the solid obtained by reacting the organomagnesium component and chlorosilane compound containing Si-H bonds.
Claim 12
Dependent Claim
177 words
A catalyst for polymerizing olefins according to claim 1, wherein said organometallic compound (B) is a hydrocarbon soluble organomagnesium complex compound having 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 and β are numbers greater than 0, β/α is in the range of 0.1-10, p, q, r and s are 0 or a number greater than 0, respectively, having the relationships p+q+r+s=mα+2β and 0≦(r+s)/(α+β)<1.0, wherein M is an atom selected from the group consisting of aluminum, zinc, boron and beryllium, m is the valency of M, R 1 and R 2 are the same or different hydrocarbon groups having 1-20 carbon atoms, X and Y are the same or different groups selected from the group consisting of OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 and SR 9 wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen atoms or a hydrocarbon group having 1-20 carbon atoms and R 9 is a hydrocarbon group having 1-20 carbon atons.
Claim 13
Dependent Claim
20 words
A catalyst for polymerizing olefins according to claim 11, wherein M of said organomagnesium complex compound is an aluminum atom.
Claim 14
Dependent Claim
56 words
A polymerization catalyst according to claim 1, wherein said organometallic compound (B) is an organoaluminum compound having the general formula AlR.sub.t.sup.10 Z.sub.3-t wherein R 10 is a hydrocarbon group having 1-20 carbon atoms, Z is a member selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy and a siloxy group, and t is from 2-3.
Claim 15
Dependent Claim
18 words
A polymerization catalyst according to claim 13, wherein said organoaluminum compound is a trialkylaluminum or a dialkylaluminum hydride.
Claim 16
Dependent Claim
88 words
A polymerization catalyst according to claim 1, wherein said component (B) consisting of an organoaluminum compound and a carboxylic acid or its derivative is used by adding separately the product obtained by first reacting one part of an organoaluminum component having the general formula AlR.sub.t.sup.10 Z.sub.3-t wherein R 10 is a hydrocarbon group having 1-20 carbon atoms, Z is a member selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy and siloxy groups, with a carboxylic acid or its derivative, and then adding the remaining organoaluminum compound.
Claim 17
Dependent Claim
351 words
In a catalyst useful for polymerizing olefins comprising a magnesium compound, a titanium compound, an electron donor, and an organometallic compound, the improvement which is characterized in that a solid (1) is obtained by reacting one mole of organomagnesium component (i) represented by 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 is a number of 0 or greater than 0; β>0; p, q, r and s are each numbers 0 or greater than 0, respectively, having the relationship of p+q+r+s=mα+2β; M is a metal component of the 1st to the 3rd group of the Periodic Table; m is the valency of M; R 1 and R 2 are the same or different hydrocarbon groups having 1-20 carbon atoms; X and Y are the same or different groups selected from the group consisting of halogen, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 and SR 9 , wherein R 3 , r 4 , r 5 , r 6 , r 7 and R 8 are hydrogen atoms or hydrocarbon groups having 1-20 carbon atoms, and R 9 is a hydrocarbon group having 1-20 carbon atoms, with 0.01-100 moles of chlorosilane compound (ii) containing Si-H bonds and represented by the general formula H.sub.a SiCl.sub.b R.sub.4-(a+b) wherein 0<a≦2, b is a number greater than 0, a+b≦4, and R is a hydrocarbon group having 1-20 carbon atoms, that a solid catalyst component (A) is obtained by reacting and/or grinding said solid 1, a titanium compound (2) selected from a tetravalent titanium halide and/or a trivalent titanium halide, and a carboxylic acid or a derivative thereof (3) selected from a carboxylic acid having up to 30 carbon atoms, an acid halide having up to 30 carbon atoms, an acid anhydride or a carboxylic acid ester having up to 30 carbon atoms in the carboxylic portion, and then treating the resulting solid with a tetravalent titanium halide (4), and that said catalyst component (A) is used with a component (B) comprising an organometallic compound of a metal selected from Groups I, II, III of the Periodic Table.
Claim 18
Dependent Claim
351 words
In a catalyst useful for polymerizing olefins comprising a magnesium compound, a titanium compound, an electron donor, and an organometallic compound, the improvement which is characterized in that a solid (1) is obtained by reacting one mole of organomagnesium component (i) represented by 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 is a number of 0 or greater than 0; β>0; p, q, r and s are each numbers 0 or greater than 0, respectively, having the relationship of p+q+r+s=mα+2β; M is a metal component of the 1st to the 3rd group of the Periodic Table; m is the valency of M; R 1 and R 2 are the same or different hydrocarbon groups having 1-20 carbon atoms; X and Y are the same or different groups selected from the group consisting of halogen, OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 and SR 9 , wherein R 3 , r 4 , r 5 , r 6 , r 7 and R 8 are hydrogen atoms or hydrocarbon groups having 1-20 carbon atoms, and R 9 is a hydrocarbon group having 1-20 carbon atoms, with 0.01-100 moles of chlorosilane compound (ii) containing Si-H bonds and represented by the general formula H.sub.a SiCl.sub.b R.sub.4-(a+b) wherein 0<a≦2, b is a number greater than 0, a+b≦4, and R is a hydrocarbon group having 1-20 carbon atoms, that a solid catalyst component (A) is obtained by reacting and/or grinding said solid 1, a titanium compound (2) selected from a tetravalent titanium halide and/or a trivalent titanium halide, and a carboxylic acid or a derivative thereof (3) selected from a carboxylic acid having up to 30 carbon atoms, an acid halide having up to 30 carbon atoms, an acid anhydride or a carboxylic acid ester having up to 30 carbon atoms in the carboxylic portion, and then treating the resulting solid with a tetravalent titanium halide (4), and that said catalyst component (A) is used with a component (B) comprising an organometallic compound of a metal selected from Groups I, II, III of the Periodic Table.
Claim 19
Dependent Claim
54 words
A catalyst for polymerizing olefins according to claim 16, wherein said organomagnesium component (i) is a hydrocarbon soluble organomagnesium complex compound wherein α is a number greater than 0, M is an atom selected from the group consisting of aluminum, boron, zinc and beryllium, and X and Y are groups other than halogen, respectively.
Claim 20
Dependent Claim
34 words
A catalyst for polymerizing olefins according to claim 16, wherein said organomagnesium component (i) is a hydrocarbon soluble organomagnesium compound wherein α is 0, and X and Y are groups other than halogen, respectively.
Claim 21
Dependent Claim
20 words
A catalyst for polymerizing olefins according to claim 16, wherein the ratio of β/α is in the range of 0.5-10.
Claim 22
Dependent Claim
20 words
A catalyst for polymerizing olefins according to claim 16, wherein the ratio of (r+s)/(α+β) is in the range of 0-0.8.
Claim 23
Dependent Claim
18 words
A catalyst for polymerizing olefins according to claim 16, wherein said titanium compound (A) (4) is titanium tetrachloride.
Claim 24
Dependent Claim
18 words
A catalyst for polymerizing olefins according to claim 16, wherein said titanium compound (A) (2) is titanium tetrachloride.
Claim 25
Dependent Claim
18 words
A catalyst for polymerizing olefins according to claim 16, wherein said titanium compound (A) (2) is titanium trichloride.
Claim 26
Dependent Claim
25 words
A catalyst for polymerizing olefins according to claim 16, wherein said titanium compound (A) (2) is a tetravalent titanium halide or a trivalent titanium halide.
Claim 27
Dependent Claim
21 words
A catalyst for polymerizing olefins according to claim 16, wherein said titanium compound (A) (2) is titanium tetrachloride or titanium trichloride.
Claim 28
Dependent Claim
46 words
A catalyst for polymerizing olefins according to claim 16, wherein said carboxylic acid or derivative thereof (A) (3) is used in 0.001-50 times the molar amount of the hydrocarbon groups included in the solid obtained by reacting the organomagnesium component and chlorosilane compound containing Si-H bonds.
Claim 29
Dependent Claim
177 words
A catalyst for polymerizing olefins according to claim 15, wherein said organometallic compound (B) is a hydrocarbon soluble organomagnesium complex compound having 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 and β are numbers greater than 0, β/α is in the range of 0.1-10, p, q, r and s are 0 or a number greater than 0, respectively, having the relationships p+q+r+s=mα+2β and 0≦(r+s)/(α+β)<1.0, wherein M is an atom selected from the group consisting of aluminum, zinc, boron and beryllium, m is the valency of M, R 1 and R 2 are the same or different hydrocarbon groups having 1-20 carbon atoms, X and Y are the same or different groups selected from the group consisting of OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 and SR 9 wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen atoms or a hydrocarbon group having 1-20 carbon atoms and R 9 is a hydrocarbon group having 1-20 carbon atoms.
Claim 30
Dependent Claim
20 words
A catalyst for polymerizing olefins according to claim 27, wherein M of said organomagnesium complex compound is an aluminum atom.
Claim 31
Dependent Claim
56 words
A polymerization catalyst according to claim 16, wherein said organometallic compound (B) is an organoaluminum compound having the general formula AlR.sub.t.sup.10 Z.sub.3-t wherein R 10 is a hydrocarbon group having 1-20 carbon atoms, Z is a member selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy and a siloxy group, and t is from 2-3.
Claim 32
Dependent Claim
18 words
A polymerization catalyst according to claim 29, wherein said organoaluminum compound is a trialkylaluminum or a dialkylaluminum hydride.
Claim 33
Dependent Claim
87 words
A polymerizaion catalyst according to claim 16, wherein said component (B) consisting of an organoaluminum compound and a carboxylic acid or its derivative is used by adding separately the product obtained by first reacting one part an organoaluminum component having the general formula AlR.sub.t.sup.10 Z.sub.3-t wherein R 10 is a hydrocarbon group having 1-20 carbon atoms, Z is a member selected from the group consisting of hydrogen, halogen, alkoxy, aryloxy and siloxy groups, with a carboxylic acid or its derivative, and then adding the remaining organoaluminum compound.
Claim 34
Dependent Claim
57 words
A catalyst for polymerizing olefins according to claim 16, wherein component (B) in addition to the organometallic compound includes a carboxylic acid or derivative thereof selected from the carboxylic acid having up to 30 carbon atoms, an acid halide, an acid anhydride or a carboxylic acid ester having up to 30 carbon atoms in the carboxylic portion.
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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) | 1982-06-25 | 1982-12-25 | 1983-06-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-06-25 | 1986-12-25 | 1987-06-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-06-25 | 1990-12-25 | 1991-06-26 | $7700.00 | Window Closed / Lapsed |