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US4543389A
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Copolymerization catalyst and process for polymerizing impact resistant ethylene-propylene polymers
Assignee: Union Carbide Chemicals and Plastics Technology LLC
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Filing: 1984-04-10
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Granted: 1985-09-24
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Expires: 2004-04-10
Abstract
Abstract A process for the preparation of ethylene-propylene impact copolymers at improved catalyst productivity rates involving the formation of a propylene prepolymer by polymerization of propylene in liquid phase in the presence of a catalyst system containing titanium halide supported on magnesium halide and aluminum alkyl complexed with an electron donor. Ethylene and propylene are block polymerized onto the prepolymer in a vapor phase reaction zone in the presence of a second catalyst system comprising a solution of a C5-C9 polyalpha-monoolefin/catalyst/diluent.
Inventors
- 👤 Israel G. Burstain
- 👤 Brian L. Goodall
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 23:07
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/06; C08F297/08; Y; Y10; Y10S; Y10S526/00; Y10S526/903; Y10S526/904
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
323 words
In the process for preparing impact resistant ethylene-propylene polymers having high impact properties combined with high stiffness, which process comprises: (a) preparing a propylene prepolymer by polymerizing propylene in a first liquid phase reaction zone in the presence of a first catalyst system comprising: (i) a highly active solid catalyst component comprising titanium tetrachloride, magnesium chloride, and an electron donor, (ii) as cocatalyst a compound AlR 3 where R represents an alkyl group of from 2 to 8 carbon atoms, and (iii) a selectivity control agent which may be partly or totally complexed with the co-catalyst; (b) separating the propylene prepolymer from volatile constituents; and (c) introducing said separated propylene prepolymer, ethylene monomer and propylene monomer into at least one vapor phase reaction zone; the improvement wherein a second catalyst system is introduced into said vapor phase reaction zone, said second catalyst system comprising the solution prepared by: (i) polymerizing a C 5 -C 9 alpha-monoolefin in a second liquid phase reaction zone in the presence of a second catalyst system selected from the group consisting of: (i) a MgCl 2 supported-type catalyst system comprising a highly active solid catalyst component comprising titanium tetrachloride, magnesium chloride, and an electron donor, and as cocatalyst a compound AlR 1 3 where R 1 represents an alkyl group of from 2 to 8 carbon atoms; and (ii) a Ziegler/Natta-type catalyst system comprising an active TiCl 3 catalyst component and an organo-aluminum compound of the formula AlR 2 n X 3-n where R 2 is an alkyl group of 2 to 12 carbon atoms, X is hydrogen or halogen and n has a value of from 0.1 to 3; and a diluent, wherein said diluent is selected such that the resulting polymer is soluble therein and wherein the amount of C 5 -C 9 alpha-monoolefin polymerized therein is about 0.05 to about 100 grams per gram of second catalyst system; and (ii) recovering the resultant catalyst-diluent-polymer mass.
Claim 2
Dependent Claim
323 words
In the process for preparing impact resistant ethylene-propylene polymers having high impact properties combined with high stiffness, which process comprises: (a) preparing a propylene prepolymer by polymerizing propylene in a first liquid phase reaction zone in the presence of a first catalyst system comprising: (i) a highly active solid catalyst component comprising titanium tetrachloride, magnesium chloride, and an electron donor, (ii) as cocatalyst a compound AlR 3 where R represents an alkyl group of from 2 to 8 carbon atoms, and (iii) a selectivity control agent which may be partly or totally complexed with the co-catalyst; (b) separating the propylene prepolymer from volatile constituents; and (c) introducing said separated propylene prepolymer, ethylene monomer and propylene monomer into at least one vapor phase reaction zone; the improvement wherein a second catalyst system is introduced into said vapor phase reaction zone, said second catalyst system comprising the solution prepared by: (i) polymerizing a C 5 -C 9 alpha-monoolefin in a second liquid phase reaction zone in the presence of a second catalyst system selected from the group consisting of: (i) a MgCl 2 supported-type catalyst system comprising a highly active solid catalyst component comprising titanium tetrachloride, magnesium chloride, and an electron donor, and as cocatalyst a compound AlR 1 3 where R 1 represents an alkyl group of from 2 to 8 carbon atoms; and (ii) a Ziegler/Natta-type catalyst system comprising an active TiCl 3 catalyst component and an organo-aluminum compound of the formula AlR 2 n X 3-n where R 2 is an alkyl group of 2 to 12 carbon atoms, X is hydrogen or halogen and n has a value of from 0.1 to 3; and a diluent, wherein said diluent is selected such that the resulting polymer is soluble therein and wherein the amount of C 5 -C 9 alpha-monoolefin polymerized therein is about 0.05 to about 100 grams per gram of second catalyst system; and (ii) recovering the resultant catalyst-diluent-polymer mass.
Claim 3
Dependent Claim
11 words
The process of claim 1 wherein said cocatalyst is triethyl aluminum.
Claim 4
Dependent Claim
13 words
The process of claim 1 wherein said electron donor is an aromatic ester.
Claim 5
Dependent Claim
22 words
The process of claim 3 wherein said electron donor is selected from the group consisting of ethyl benzoate, p-ethyl toluate and ethyl-p-methoxybenzoate.
Claim 6
Dependent Claim
50 words
The process of claim 1 wherein said solid catalyst component has the general formula TiMg.sub.x Cl.sub.y (OR').sub.z.aED wherein R' is an alkyl group of 2-8 carbon atoms or an aryl, alkaryl, or aralkyl group of 6 to 20 carbon atoms, ED is an aromatic ester; x=5-40; y=10-100; z=0.02-1.0; and a=0.5-10.
Claim 7
Dependent Claim
26 words
The process of claim 1 wherein said diluent employed in said second catalyst system is an aliphatic, cycloaliphatic or aromatic hydrocarbon with a carbon number ≧6.
Claim 8
Dependent Claim
19 words
The process of claim 1 wherein said C 5 -C 9 alpha-monoolefin is pentene-1 and said diluent is isooctane.
Claim 9
Dependent Claim
18 words
The process of claim 1 wherein propylene and ethylene are copolymerized in said first liquid phase reaction zone.
Claim 10
Dependent Claim
27 words
The process of claim 8 wheren said propylene prepolymer comprises about 90 to about 99 weight percent propylene and about 10 to about 1 weight percent ethylene.
Claim 11
Dependent Claim
17 words
The process of claim 1 wherein said second catalyst system is a MgCl 2 supported-type catalyst system.
Claim 12
Dependent Claim
28 words
The process of claim 10 wherein said MgCl 2 supported-type catalyst system also contains a selectivity control agent which may be partly or totally complexed with the co-catalyst.
Claim 13
Dependent Claim
33 words
The process of claim 11 wherein said C 5 -C 9 alpha-monoolefin is pentene-1, said diluent is isooctane, and said co-catalyst used in said first and said second catalyst systems is triethyl aluminum.
Claim 14
Dependent Claim
27 words
The process of claim 1 wherein the molar ratio of ethylene to propylene monomer introduced to the vapor phase reaction zone is about 0.5:1 to about 2:1.
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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) | 1988-09-23 | 1989-03-25 | 1989-09-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-09-23 | 1993-03-25 | 1993-09-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-09-23 | 1997-03-25 | 1997-09-24 | $7700.00 | Window Closed / Lapsed |