US4686200A
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Catalyst for the polymerization of olefins
Assignee: Toho Titanium Co Ltd
•
Filing: 1986-11-18
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Granted: 1987-08-11
•
Expires: 2006-11-18
Abstract
Abstract A catalyst for the polymerization of olefins which comprises: (A) a solid catalyst component prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine and a dialkyl phthalate (b) and optionally existing titanium tetrachloride (c) into contact with titanium tetrachloride in the presence or absence of an aromatic hydrocarbon and/or halohydrocarbon. (B) a 2,6-dialkyl- or 2,2,6,6-tetraalkyl-piperidine derivative, and (C) an organoaluminum compound selected from a trialkyl aluminum, a dialkylaluminum halide and an alkylaluminum dihalide, as well as the solid catalyst component (A) for the catalyst. This catalyst characterized by the use of the specific solid catalyst component exhibits a high polymerization activity combined with stereospecific performance over a prolonged polymerization time and is free from any problem of corrosion and odor in the resultant polymer.
Inventors
- 👤 Minoru Terano
- 👤 Hirokazu Soga
- 👤 Masuo Inoue
- 👤 Katsuyoshi Miyoshi
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 01:02
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 73
Claim 1
Independent Claim
148 words
A catalyst for the polymerization of olefins which comprises: (A) a solid catalyst component prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine and a dialkyl phthalate (b) into contact with titanium tetrachloride; (B) a disubstituted or tetrasubstituted piperidine derivative of the general formula: ##STR10## wherein R 1 and R 3 are the same or different and each stands for an alkyl group and R 2 and R 4 both stand for hydrogen atoms or both stand for the same or different alkyl groups, and (C) an organoaluminum compound of the general formula: ##STR11## wherein R is an alkyl group, Q and Q' may be the same or different and each represents R or X, and X is a halogen atom.
Claim 2
Dependent Claim
148 words
A catalyst for the polymerization of olefins which comprises: (A) a solid catalyst component prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine and a dialkyl phthalate (b) into contact with titanium tetrachloride; (B) a disubstituted or tetrasubstituted piperidine derivative of the general formula: ##STR10## wherein R 1 and R 3 are the same or different and each stands for an alkyl group and R 2 and R 4 both stand for hydrogen atoms or both stand for the same or different alkyl groups, and (C) an organoaluminum compound of the general formula: ##STR11## wherein R is an alkyl group, Q and Q' may be the same or different and each represents R or X, and X is a halogen atom.
Claim 3
Dependent Claim
20 words
A catalyst according to claim 1, wherein the alkyl monohalide is liquid at room temperature and has 3-8 carbon atoms.
Claim 4
Dependent Claim
38 words
A catalyst according to claim 1, wherein the dialkyl phthalate (b) is dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethyl propyl phthalate.
Claim 5
Dependent Claim
15 words
A catalyst according to claim 1, wherein the piperidine derivative (B) is 2,6-dialkylpiperidine or 2,2,6,6-tetraalkylpiperidine.
Claim 6
Dependent Claim
28 words
A catalyst accoring to claim 1 or 4, wherein the piperidine derivative (B) is used in an amount of 0.005-1.0 mol per mol of the organoaluminum compound (C).
Claim 7
Dependent Claim
24 words
A catalyst according to claim 1, wherein the organoaluminum compound (C) is a trialkylaluminum, a dialkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.
Claim 8
Dependent Claim
30 words
A catalyst according to claim 1 or 6, wherein the organoaluminum compound (C) is used in an amount of 1-1000 mols per titanium atom in the solid catalyst component (A).
Claim 9
Dependent Claim
151 words
A catalyst for the polymerization of olefins which comprises: (A) a solid catalyst component prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine, a dialkyl phthalate (b) and titanium tetrachloride (c) into contact with titanium tetrachloride, (B) a disubstituted or tetrasubstituted piperidine derivative of the general formula: ##STR12## wherein R 1 and R 3 are the same or different and each stands for an alkyl group and R 2 and R 4 both stand for hydrogen atoms or both stand for the same or different alkyl groups, and (C) an organoaluminum compound of the general formula: ##STR13## wherein R is an alkyl group, Q and Q' may be the same or different and each represents R or X, and X is a halogen atom.
Claim 10
Dependent Claim
151 words
A catalyst for the polymerization of olefins which comprises: (A) a solid catalyst component prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine, a dialkyl phthalate (b) and titanium tetrachloride (c) into contact with titanium tetrachloride, (B) a disubstituted or tetrasubstituted piperidine derivative of the general formula: ##STR12## wherein R 1 and R 3 are the same or different and each stands for an alkyl group and R 2 and R 4 both stand for hydrogen atoms or both stand for the same or different alkyl groups, and (C) an organoaluminum compound of the general formula: ##STR13## wherein R is an alkyl group, Q and Q' may be the same or different and each represents R or X, and X is a halogen atom.
Claim 11
Dependent Claim
20 words
A catalyst according to claim 8, wherein the alkyl monohalide is liquid at room temperature and has 3-8 carbon atoms.
Claim 12
Dependent Claim
38 words
A catalyst according to claim 8, wherein the dialkyl phthalate (b) is dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethyl propyl phthalate.
Claim 13
Dependent Claim
15 words
A catalyst according to claim 8, wherein the piperidine derivative (B) is 2,6-dialkylpiperidine or 2,2,6,6-tetraalkylpiperidine.
Claim 14
Dependent Claim
28 words
A catalyst according to claim 8 or 11, wherein the piperidine derivative (B) is used in an amount of 0.005-1.0 mol per mol of the organoaluminum compound (C).
Claim 15
Dependent Claim
24 words
A catalyst according to claim 8, wherein the organoaluminum compound (C) is a trialkylaluminum, a dialkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.
Claim 16
Dependent Claim
30 words
A catalyst according to claim 8 or 13, wherein the organoaluminum compound (C) is used in an amount of 1-1000 mols per titanium atom in the solid catalyst component (A).
Claim 17
Dependent Claim
167 words
A catalyst for the polymerization of olefins which comprises: (A) a solid catalyst component prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine, a dialkyl phthalate (b) and titanium tetrachloride (c) into contact with titanium tetrachloride in the presence of (d) an aromatic hydrocarbon and/or halohydrocarbon which is liquid at room temperature; (B) a disubstituted or tetrasubstituted piperidine derivative of the general formula: ##STR14## wherein R 1 and R 3 are the same or different and each stands for an alkyl group and R 2 and R 4 both stand for hydrogen atoms or both stand for the same or different alkyl groups, and (C) an organoaluminum compound of the general formula: ##STR15## wherein R is an alkyl group, Q and Q' may be the same or different and each represents R or X, and X is a halogen atom.
Claim 18
Dependent Claim
167 words
A catalyst for the polymerization of olefins which comprises: (A) a solid catalyst component prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine, a dialkyl phthalate (b) and titanium tetrachloride (c) into contact with titanium tetrachloride in the presence of (d) an aromatic hydrocarbon and/or halohydrocarbon which is liquid at room temperature; (B) a disubstituted or tetrasubstituted piperidine derivative of the general formula: ##STR14## wherein R 1 and R 3 are the same or different and each stands for an alkyl group and R 2 and R 4 both stand for hydrogen atoms or both stand for the same or different alkyl groups, and (C) an organoaluminum compound of the general formula: ##STR15## wherein R is an alkyl group, Q and Q' may be the same or different and each represents R or X, and X is a halogen atom.
Claim 19
Dependent Claim
20 words
A catalyst according to claim 15, wherein the alkyl monohalide is liquid at room temperature and has 3-8 carbon atoms.
Claim 20
Dependent Claim
38 words
A catalyst according to claim 16, wherein the dialkyl phthalate (b) is dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethyl propyl phthalate.
Claim 21
Dependent Claim
15 words
A catalyst according to claim 15, wherein the piperidine derivative (B) is 2,6-dialkylpiperidine or 2,2,6,6-tetraalkylpiperidine.
Claim 22
Dependent Claim
28 words
A catalyst according to claim 15 or 18, wherein the piperidine derivative (B) is used in an amount of 0.005-1.0 mol per mol of the organoaluminum compound (C).
Claim 23
Dependent Claim
24 words
A catalyst according to claim 15, wherein the organoaluminum compound (C) is a trialkylaluminum, a dialkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.
Claim 24
Dependent Claim
30 words
A catalyst according to claim 15 or 20, wherein the organoaluminum compound (C) is used in an amount of 1-1000 mols per titanium atom in the solid catalyst component (A).
Claim 25
Dependent Claim
61 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine and a dialkyl phthalate (b) into contact with titanium tetrachloride.
Claim 26
Dependent Claim
61 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine and a dialkyl phthalate (b) into contact with titanium tetrachloride.
Claim 27
Dependent Claim
29 words
A solid catalyst component according to claim 22, wherein the reaction for obtaining the substance (a) is carried out at a temperature above 20° C., preferably above 40° C.
Claim 28
Dependent Claim
35 words
A solid catalyst component according to claim 22 or 23, wherein the reaction for obtaining the substance (a) is carried out for a period of time longer than 10 minutes, preferably longer than 30 minutes.
Claim 29
Dependent Claim
22 words
A solid catalyst component according to claim 22, wherein the alkyl monohalide is liquid at room temperature and has 3-8 carbon atoms.
Claim 30
Dependent Claim
26 words
A catalyst according to claim 25, wherein the alkyl monohalide is n-propyl chloride, isopropyl chloride, n-butyl chloride, isobutyl chloride, pentyl chloride, hexyl chloride or octyl chloride.
Claim 31
Dependent Claim
24 words
A solid catalyst component according to claim 22, wherein the iodine is used in an amount of 0.001-1 g per gram of the magnesium.
Claim 32
Dependent Claim
40 words
A solid catalyst component according to claim 22, wherein the dialkyl phthalate (b) is dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethyl propyl phthalate.
Claim 33
Dependent Claim
41 words
A solid catalyst component according to claim 22, wherein the proportion of the dialkyl phthalate (b) to the substance (a) is such that the dialkyl phthalate (b) is used in an amount of 0.01-1 g per gram of the substance (a).
Claim 34
Dependent Claim
46 words
A solid catalyst component according to claim 22, wherein the proportion of the titanium tetrachloride to the substance (a) is such that the titanium tetrachloride is used in an amount of at least 0.1 g, preferably at least 1 g per gram of the substance (a).
Claim 35
Dependent Claim
35 words
A solid catalyst component according to claim 22, wherein the contact of the co-ground product with the titanium tetrachloride is effected at a temperature from -10° C. to the boiling point of the titanium tetrachloride.
Claim 36
Dependent Claim
24 words
A solid catalyst component according to claim 22 or 31, wherein the contact is effected for a period from 10 minutes to 100 hours.
Claim 37
Dependent Claim
16 words
A solid catalyst component according to claim 22, or 31, wherein the contact is effected repeatedly.
Claim 38
Dependent Claim
64 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine, a dialkyl phthalate (b) and titanium tetrachloride (c) into contact with titanium tetrachloride.
Claim 39
Dependent Claim
64 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine, a dialkyl phthalate (b) and titanium tetrachloride (c) into contact with titanium tetrachloride.
Claim 40
Dependent Claim
29 words
A solid catalyst component according to claim 34, wherein the reaction for obtaining the substance (a) is carried out at a temperature above 20° C., preferably above 40° C.
Claim 41
Dependent Claim
35 words
A solid catalyst component according to claim 34 or 35, wherein the reaction for obtaining the substance (a) is carried out for a period of time longer than 10 minutes, preferably longer than 30 minutes.
Claim 42
Dependent Claim
22 words
A solid catalyst component according to claim 34, wherein the alkyl monohalide is liquid at room temperature and has 3-8 carbon atoms.
Claim 43
Dependent Claim
28 words
A solid catalyst component according to claim 37, wherein the alkyl monohalide is n-propyl chloride, isopropyl chloride, n-butyl chloride, isobutyl chloride, pentyl chloride, hexyl chloride or octyl chloride.
Claim 44
Dependent Claim
24 words
A solid catalyst component according to claim 34, wherein the iodine is used in an amount of 0.001-1 g per gram of the magnesium.
Claim 45
Dependent Claim
40 words
A solid catalyst component according to claim 34, wherein the dialkyl phthalate (b) is dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethyl propyl phthalate.
Claim 46
Dependent Claim
41 words
A solid catalyst component according to claim 34, wherein the proportion of the dialkyl phthalate (b) to the substance (a) is such that the dialkyl phthalate (b) is used in an amount of 0.01-1 g per gram of the substance (a).
Claim 47
Dependent Claim
53 words
A solid catalyst component according to claim 34, wherein the proportion of the titanium tetrachloride (c) to be co-ground with the substance (a) and the dialkyl phthalate (b) to the substance (a) is such that the titanium tetrachloride (c) is used in an amount of 0.01-1 g per gram of the substance (a).
Claim 48
Dependent Claim
33 words
A solid catalyst component according to claim 34, wherein the titanium tetrachloride is used in an amount of at least 0.1 g, preferably at least 1 g per gram of the co-ground product.
Claim 49
Dependent Claim
37 words
A solid catalyst component according to claim 34 or 43, wherein the contact of the co-ground product with the titanium tetrachloride is effected at a temperature from -10° C. to the boiling point of the titanium tetrachloride.
Claim 50
Dependent Claim
32 words
A solid catalyst component according to claim 34 or 43, wherein the contact of the co-ground product with the titanium tetrachloride is effected for a period from 10 minutes to 100 hours.
Claim 51
Dependent Claim
16 words
A solid catalyst component according to claim 34 or 43 wherein the contact is effected repeatedly.
Claim 52
Dependent Claim
80 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine and dialkyl phthalate (b) and titanium tetrachloride (c) into contact with titanium tetrachloride in the presence of an aromatic hydrocarbon and/or halohydrocarbon (d) which is liquid at room temperature.
Claim 53
Dependent Claim
80 words
A solid catalyst component for catalysts utilizable for the polymerization of olefins which has been prepared by bringing a co-ground product of a substance (a) obtained by reacting magnesium with at least two molar proportion of an alkyl monohalide in the absence of a solvent but in the presence of iodine and dialkyl phthalate (b) and titanium tetrachloride (c) into contact with titanium tetrachloride in the presence of an aromatic hydrocarbon and/or halohydrocarbon (d) which is liquid at room temperature.
Claim 54
Dependent Claim
29 words
A solid catalyst component according to claim 47, wherein the reaction for obtaining the substance (a) is carried out at a temperature above 20° C., preferably above 40° C.
Claim 55
Dependent Claim
35 words
A solid catalyst component according to claim 47 or 48, wherein the reaction for obtaining the substance (a) is carried out for a period of time longer than 10 minutes, preferably longer than 30 minutes.
Claim 56
Dependent Claim
22 words
A solid catalyst component according to claim 47, wherein the alkyl monohalide is liquid at room temperature and has 3-8 carbon atoms.
Claim 57
Dependent Claim
28 words
A solid catalyst component according to claim 50, wherein the alkyl monohalide is n-propyl chloride, isopropyl chloride, n-butyl chloride, isobutyl chloride, pentyl chloride, hexyl chloride or octyl chloride.
Claim 58
Dependent Claim
24 words
A solid catalyst component according to claim 47, wherein the iodine is used in an amount of 0.001-1 g per gram of the magnesium.
Claim 59
Dependent Claim
40 words
A solid catalyst component according to claim 47, wherein the dialkyl phthalate (b) is dimethyl phthalate, diethyl phthalate, diisopropyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, diisoamyl phthalate, ethyl butyl phthalate, ethyl isobutyl phthalate and ethyl propyl phthalate.
Claim 60
Dependent Claim
41 words
A solid catalyst component according to claim 47, wherein the proportion of the dialkyl phthalate (b) to the substance (a) is such that the dialkyl phthalate (b) is used in an amount of 0.01-1 g per gram of the substance (a).
Claim 61
Dependent Claim
53 words
A solid catalyst component according to claim 47, wherein the proportion of the titanium tetrachloride (c) to be co-ground with the substance (a) and the dialkyl phthalate (b) to the substance (a) is such that the titanium tetrachloride (c) is used in an amount of 0.01-1 g per gram of the substance (a).
Claim 62
Dependent Claim
33 words
A solid catalyst component according to claim 47, wherein the titanium tetrachloride is used in an amount of at least 0.1 g, preferably at least 1 g per gram of the co-ground product.
Claim 63
Dependent Claim
52 words
A solid catalyst component according to claim 47 or 56, wherein the contact of the co-ground product with the titanium tetrachloride is effected at a temperature from -10° C. to the boiling point of the titanium tetrachloride in the presence of an aromatic hydrocarbon and/or halohydrocarbon which is liquid at room temperature.
Claim 64
Dependent Claim
33 words
A solid catalyst component according to claim 47 or 56, wherein the contact is effected for a period from 10 minutes to 100 hours in the presence of the aromatic hydrocarbon and/or halohydrocarbon.
Claim 65
Dependent Claim
25 words
A solid catalyst component according to claim 47 or 56, wherein the contact is effected repeatedly, in the presence of the aromatic hydrocarbon and/or halohydrocarbon.
Claim 66
Dependent Claim
28 words
A solid catalyst component according to claim 47, wherein the aromatic hydrocarbon and/or aromatic halohydrocarbon is benzene, toluene, xylene, chlorobenzene, bromobenzene, o-dichlorobenzene, o-chlorotoluene or a mixture of these.
Claim 67
Dependent Claim
14 words
A solid catalyst component according to claim 32, wherein the contact is effected repeatedly.
Claim 68
Dependent Claim
30 words
A solid catalyst component according to claim 44, wherein the contact of the co-ground product with the titanium tetrachloride is effected for a period from 10 minutes to 100 hours.
Claim 69
Dependent Claim
14 words
A solid catalyst component according to claim 44, wherein the contact is effected repeatedly.
Claim 70
Dependent Claim
14 words
A solid catalyst component according to claim 45, wherein the contact is effected repeatedly.
Claim 71
Dependent Claim
31 words
A solid catalyst component according to claim 57, wherein the contact is effected for a period from 10 minutes to 100 hours in the presence of the aromatic hydrocarbon and/or halohydrocarbon.
Claim 72
Dependent Claim
23 words
A solid catalyst component according to claim 57, wherein the contact is effected repeatedly, in the presence of the aromatic hydrocarbon and/or halohydrocarbon.
Claim 73
Dependent Claim
23 words
A solid catalyst component according to claim 58, wherein the contact is effected repeatedly, in the presence of the aromatic hydrocarbon and/or halohydrocarbon.
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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) | 1990-08-10 | 1991-02-09 | 1991-08-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-08-10 | 1995-02-09 | 1995-08-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-08-10 | 1999-02-09 | 1999-08-11 | $7700.00 | Window Closed / Lapsed |