Claims
- 1. A method for preparing copolymers of an .alpha.-olefin and an .alpha.,.omega. diene, comprising:
- charging to a polymerization reaction zone from 80 to 99.99 weight percent of an .alpha.-olefin selected from the group consisting of ethylene, propylene, and butene-1, from 0.01 to 20 weight percent of an .alpha.,.omega.-diene having from 7 to about 30 carbon atoms, and a solid heterogeneous coordination catalyst;
- maintaining the reaction zone essentially free of solvent and at a temperature at which the .alpha.-olefin is fluid but below the crystalline melting point of the copolymer effective to produce an essentially gel-free, copolymer having unsaturated side chains present in the range of from about 0.001 to about 5 mole percent of the copolymer; wherein said copolymer has greater than about 80 weight percent heptane insolubles; and
- wherein said copolymer has a branching index in the range of from about 0.2 to about 0.9.
- 2. The method of claim 1 wherein the .alpha.-olefin is propylene.
- 3. The method of claim 1, wherein the .alpha.,.omega.-diene has up to 12 carbon atoms.
- 4. The method of claim 1, wherein the catalyst is a Ziegler catalyst.
- 5. The method of claim 1, wherein up to 10 mole percent hydrogen is charged to said reaction zone to control molecular weight of said copolymer.
- 6. The method of claim 1, wherein the copolymer has from about 0.1 to about 1 mole percent unsaturated side chains, and wherein said copolymer has a branching index in the range of from about 0.6 to about 0.8.
- 7. A method for preparing a copolymer of an .alpha.-olefin and an .alpha.,.omega. diene, comprising:
- charging from 95 to 99.99 mole percent of an .alpha.-olefin selected from the group consisting of ethylene, propylene, and butene-1 to a reaction zone with from 0.01 to 5 mole percent of an .alpha.,.omega. diene of from 7 to 12 carbon atoms, up to 10 mole percent hydrogen, and a solid, heterogeneous Ziegler catalyst;
- maintaining the reaction zone essentially free of solvent and at a temperature at which the .alpha.-olefin is fluid but substantially below the crystalline melting point of the copolymer; and
- recovering an essentially gel-free copolymer from the reaction zone, wherein the copolymer has from about 0.1 to about 1 mole percent unsaturated side chains; wherein said copolymer has greater than about 80 weight percent heptane insolubles and wherein said copolymer has a branching index in the range of from about 0.2 to about 0.9.
- 8. The method of claim 7 wherein the .alpha.-olefin is propylene.
- 9. The method of claims 1 or 7 wherein the .alpha.,.omega. diene is 1,9-decadiene.
- 10. The method of claim 7, wherein the catalyst is a solid-supported catalyst.
- 11. The method of claim 7, wherein the catalyst is obtained by (1) contacting TiCl.sub.4 with an organoaluminum compound at a temperature between about -50.degree. and 30.degree. C. to produce a TiCl.sub.3 reduced solid product, (2) contacting the reduced solid TiCl.sub.3 product with a minor amount of an .alpha.-olefin having at least 3 carbon atoms under polymerization conditions to obtain a reduced TiCl.sub.3 solid product containing between about 1 and 1000 weight percent of prepolymerized .omega.-olefin based on the weight of TiCl.sub.3, and (3) treating said prepolymerized reduced solid with one of (a) a chlorinated hydrocarbon having at least 2 carbon atoms and a Lewis base complexing agent, or (b) titanium tetrachloride and a Lewis base complexing agent to convert the prepolymerized TiCl.sub.3 reduced solid to a substantially non-friable highly active, crystalline prepolymerized TiCl.sub.3 composition.
- 12. The method of claim 11, wherein the catalyst further comprises an organometallic cocatalyst.
- 13. A method of preparing an essentially gel-free copolymer of propylene and an .alpha.,.omega. diene comprising:
- charging from 99.95 to 98 mole percent propylene, from 0.05 to 2 mole percent 1,9-decadiene, from 0.01 to 5 mole percent hydrogen, and a solid heterogeneous Ziegler catalyst to a reaction zone;
- maintaining the reaction zone essentially free of solvent and at a temperature below about 150.degree. C. effective to randomly copolymerize said propylene and said diene; and recovering an essentially gel-free isotactic copolymer;
- wherein said copolymer has a branching index in the range of from about 0.2 to about 0.9, wherein said copolymer has greater than about 80 weight percent heptane insolubles wherein said copolymer has about and of from about 0.1 to about 1 mole percent unsaturated side chains.
- 14. The method of claim 13, wherein a minor proportion of ethylene is charged to said reaction zone.
- 15. The method of claim 13, further comprising using said copolymer as a feed with ethylene and propylene in a subsequent polymerization reactor.
- 16. The method of claim 15, wherein said catalyst is obtained by (1) contacting TiCl.sub.4 with an organoaluminum compound at a temperature between about -50.degree. and 30.degree. C. to produce a TiCl.sub.3 reduced solid product, (2) contacting the reduced solid TiCl.sub.3 product with a minor amount of an .alpha.-olefin having at least 3 carbon atoms under polymerization conditions to obtain a reduced TiCl.sub.3 solid product containing between about 1 and 1000 weight percent of prepolymerized .alpha.-olefin based on the weight of TiCl.sub.3, and (3) treating said prepolymerized reduced solid with one of (a) a chlorinated hydrocarbon having at least 2 carbon atoms and a Lewis base complexing agent or (b) TiCl.sub.4 and a Lewis base complexing agent, to convert the prepolymerized TiCl.sub.3 reduced solid to a substantially non-friable highly active, crystalline prepolymerized TiCl.sub.3 composition.
- 17. The method of claim 16, wherein the catalyst includes an organometallic cocatalyst.
- 18. The method of claim 16 wherein said copolymer has a branching index in the range of from about 0.6 about 0.8.
Parent Case Info
The present application is a Rule 60 divisional of U.S. Ser. No. 07/519,616, filed May 7, 1990 now abandoned.
US Referenced Citations (12)
Non-Patent Literature Citations (1)
Entry |
Briston, Plastic Films, J. Wiley and Sons, N. Y., 103-105 (1974). |
Divisions (1)
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Number |
Date |
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519616 |
May 1990 |
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