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US4072809A
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US
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Catalyst and process for the polymerization of alpha-olefins
Assignee: BP Corp North America Inc
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Filing: 1975-03-03
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Granted: 1978-02-07
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Expires: 1995-03-03
Abstract
Abstract Novel catalysts and processes are disclosed for producing highly crystalline polypropylene and highly crystalline copolymers of propylene with ethylene or propylene with other alpha-olefins. Such catalysts can reduce the amount of low-molecular-weight and, particularly, amorphous polymers formed without serious effect on the polymerization yield. These novel catalysts and processes involve improving an alkylaluminum compound-titanium chloride catalyst by using in combination small amounts of hydrogen sulfide and a sterically hindered, lower alkyl substituted, cyclic, tertiary amine, a sterically hindered, lower alkyl substituted, cyclic, amine oxide, or a trihydrocarbylphosphite. Such catalyst systems are useful in slurry polymerization, bulk polymerization and techniques in which polymerization is accomplished utilizing monomer substantially in the vapor phase.
Inventors
- 👤 John B. Rogan
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 21:27
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
130 words
A polymerization catalyst composition which comprises: (a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide; (b) an effective amount up to about 10 mol percent of hydrogen sulfide based upon the amount of alkylaluminum compound present; (c) an activated titanium trichloride; and (d) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines and sterically hindered, lower alkyl substituted, cyclic, amine oxides; said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of polymer.
Claim 2
Dependent Claim
130 words
A polymerization catalyst composition which comprises: (a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide; (b) an effective amount up to about 10 mol percent of hydrogen sulfide based upon the amount of alkylaluminum compound present; (c) an activated titanium trichloride; and (d) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines and sterically hindered, lower alkyl substituted, cyclic, amine oxides; said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of polymer.
Claim 3
Dependent Claim
19 words
The composition of claim 1 wherein said alkylaluminum compound is a dialkylaluminum chloride and said additive is a trihydrocarbylphosphite.
Claim 4
Dependent Claim
26 words
The composition of claim 1 wherein said alkylaluminum compound is a dialkylaluminum chloride and said additive is a sterically hindered, lower alkyl substituted, cyclic, tertiary amine.
Claim 5
Dependent Claim
26 words
The composition of claim 1 wherein said alkylaluminum compound is a dialkylaluminum chloride and said second is a sterically hindered, lower alkyl substituted, cyclic, amine oxide.
Claim 6
Dependent Claim
13 words
The composition of claim 2 wherein said additive is a lower alkyl, trialkylphosphite.
Claim 7
Dependent Claim
20 words
The composition of claim 3 wherein said additive is a sterically hindered, di- or tri-lower alkyl substituted, cyclic, tertiary amine.
Claim 8
Dependent Claim
10 words
The composition of claim 4 wherein said additive is 2,6-lutidine-N-oxide.
Claim 9
Dependent Claim
10 words
The composition of claim 5 wherein said additive is tributylphosphite.
Claim 10
Dependent Claim
10 words
The composition of claim 6 wherein said additive is 2,4,6-collidine.
Claim 11
Dependent Claim
171 words
A process for the polymerization of propylene or a mixture of propylene and ethylene or propylene and another C 4 to C 8 alpha-olefin to form a highly crystalline polymeric substance, said process involving contacting under polymerizing conditions said propylene or said mixture with a catalyst comprising: (a) an alkylaluminum compound selected from the group consisting of a trialkylaluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide; (b) an effective amount up to about 10 mol percent hydrogen sulfide based upon the amount of alkylaluminum compound present; (c) an activated titanium trichloride; and (d) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines and sterically hindered, lower alkyl substituted, cyclic, amine oxides; said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of said polymeric substance.
Claim 12
Dependent Claim
171 words
A process for the polymerization of propylene or a mixture of propylene and ethylene or propylene and another C 4 to C 8 alpha-olefin to form a highly crystalline polymeric substance, said process involving contacting under polymerizing conditions said propylene or said mixture with a catalyst comprising: (a) an alkylaluminum compound selected from the group consisting of a trialkylaluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide; (b) an effective amount up to about 10 mol percent hydrogen sulfide based upon the amount of alkylaluminum compound present; (c) an activated titanium trichloride; and (d) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines and sterically hindered, lower alkyl substituted, cyclic, amine oxides; said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of said polymeric substance.
Claim 13
Dependent Claim
19 words
The process of claim 10 wherein said alkylaluminum compound is a dialkylaluminum chloride and said additive is a trihydrocarbylphosphite.
Claim 14
Dependent Claim
26 words
The process of claim 10 wherein said alkylaluminum compound is a dialkylaluminum chloride and said additive is a sterically hindered, lower alkyl substituted, cyclic, tertiary amine.
Claim 15
Dependent Claim
26 words
The process of claim 10 wherein said alkylaluminum compound is a dialkylaluminum chloride and said additive is a sterically hindered, lower alkyl substituted, cyclic, amine oxide.
Claim 16
Dependent Claim
13 words
The process of claim 11 wherein said additive is a lower alkyl, trialkylphosphite.
Claim 17
Dependent Claim
20 words
The process of claim 12 wherein said additive is a sterically hindered, di- or tri-lower alkyl substituted, cyclic, tertiary amine.
Claim 18
Dependent Claim
10 words
The process of claim 13 wherein said additive is 2,6-lutidine-N-oxide.
Claim 19
Dependent Claim
10 words
The process of claim 14 wherein said additive is tributylphosphite.
Claim 20
Dependent Claim
10 words
The process of claim 15 wherein said additive is 2,4,6-collidine.
Claim 21
Dependent Claim
179 words
A process for the polymerization of propylene or a mixture of propylene and ethylene or propylene and another C 4 to C 8 alpha-olefin to form a highly crystalline polymeric substance, said process involving contacting under polymerizing conditions said propylene or said mixture with a catalyst comprising: (a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide, said alkylaluminum compound having been treated with an effective amount, up to about 10 mol percent based on the amount of said alkylaluminum compound, of hydrogen sulfide; (b) an activated titanium trichloride; and (c) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines, and sterically hindered, lower alkyl substituted, cyclic, amine oxides; said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of said polymeric substance.
Claim 22
Dependent Claim
179 words
A process for the polymerization of propylene or a mixture of propylene and ethylene or propylene and another C 4 to C 8 alpha-olefin to form a highly crystalline polymeric substance, said process involving contacting under polymerizing conditions said propylene or said mixture with a catalyst comprising: (a) an alkylaluminum compound selected from the group consisting of a trialkyl aluminum, a mixture of a trialkyl aluminum and an alkylaluminum dichloride or dibromide, a mixture of a trialkyl aluminum and a dialkylaluminum chloride or bromide and a dialkylaluminum chloride or bromide, said alkylaluminum compound having been treated with an effective amount, up to about 10 mol percent based on the amount of said alkylaluminum compound, of hydrogen sulfide; (b) an activated titanium trichloride; and (c) an effective amount of an additive which is selected from the group consisting of trihydrocarbylphosphites, sterically hindered, lower alkyl substituted, cyclic, tertiary amines, and sterically hindered, lower alkyl substituted, cyclic, amine oxides; said amounts effective to result in a substantial reduction of alkane solubles while not seriously affecting the total yield of said polymeric substance.
Claim 23
Dependent Claim
18 words
The process of claim 19 wherein said alkylaluminum compound is a dialkylaluminum chloride and said additive is 2,6-lutidine-N-oxide.
Claim 24
Dependent Claim
28 words
The process of claim 19 wherein said alkyaluminum compound is a dialkylaluminum chloride and said additive is a sterically hindered, di- or tri-lower alkyl substituted, cyclic, tertiary amine.
Claim 25
Dependent Claim
10 words
The process of claim 21 wherein said additive is 2,4,6-collidine.
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) | 1981-02-06 | 1981-08-08 | 1982-02-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-02-06 | 1985-08-08 | 1986-02-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-02-06 | 1989-08-08 | 1990-02-07 | $7700.00 | Window Closed / Lapsed |