Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers

• US 5,008,356 A
• Filed: 05/31/1989
• Issued: 04/16/1991
• Est. Priority Date: 03/02/1987
• Status: Expired due to Term

• Current Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Original Assignee: Mitsui Petrochemical Industries, Ltd. (Mitsui Chemicals)
• Inventors: Tsutsui, Toshiyuki, Kashiwa, Norio, Toyota, Akinori, Ishimaru, Naoshi
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Walker, Alex H.
• Application Number:
  US07/359,131
• Time in Patent Office: 685 Days
• Field of Search: 526/281, 526/160, 502/154
• US Class Current: 526/281
• CPC Class Codes: C08F 210/00 Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 232/00 Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
• CPC Class Codes: C08F 2500/25 Cycloolefine
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

A cyclo-olefinic random copolymer composed of an alpha-olefin component having 3 to 20 carbon atoms and a cyclo-olefin component,

(i) said copolymer containing 5 to 99 mole % of recurring units derived from said alpha-olefin component having 3 to 20 carbon atoms and 1 to 95 mole % of recurring units derived from said cyclo-olefin component, and

(ii) said copolymer having an intrinsic viscosity [η], measured in decalin at 135° C., of from 0.01 to 10 dl/g; and an olefinic random copolymer composed of (A) an olefin component having 3 to 20 carbon atoms and (B) a cyclic polyene component and as required, (C) a cyclo-olefin component,

(i) said copolymer containing 5 to 99 mole % of recurring units derived from said alpha-olefin component (A) having 3 to 20 carbon atoms and 1 to 95 mole % of recurring units derived from said cyclic polyene component (B) and 0 to 90 mole % of recurring units derived from said cyclo-olefin component (C), and

(ii) said copolymer having an intrinsic viscosity [η], measured in decalin at 135° C., of from 0.01 to 10 dl/g; and a process for production thereof. Also provided is a process for producing a cyclo-olefinic random copolymer, which comprises copolymerizing an alpha-olefin and a cyclo-olefin in the presence of a catalyst formed from

(A) a compound of a transition metal of Group IVB of the periodic table having as a ligand a multidentate coordination compound in which at least two conjugated cycloalkadienyl groups or substituted products thereof are bonded via a lower alkylene group, and

(B) an aluminoxane.

Claims

1. A process for producing a cyclo-olefinic random copolymer, which comprises copolymerizing an alpha-olefin and a cyclo-olefin in the presence of a catalyst formed from

(A) a compound of a transition metal of Group IVB of the periodic table having as a ligand a multidentate coordination compound in which at least two conjugated cycloalkadienyl groups or substituted products thereof are bonded via a lower alkylene group, and

(B) an aluminoxane.

2. The process of claim 1 wherein the transition metal compound is a zirconium compound containing as a ligand at least two indenyl groups or substituted indenyl groups or partially hydrogenated groups thereof which are bonded via an alkylene group.

3. The process of claim 2 wherein the aluminoxane is an organoaluminum compound represented by the general formula ##STR48## wherein R represents a hydrocarbon group, and m represents an integer of at least 2.

4. The process of claim 3 wherein R is a methyl, ethyl or isobutyl group, and m is an integer of at least 5.

5. The process of claim 3 wherein R is a methyl group and m is an integer of 5 to 50.

6. The process of claim 2 wherein the transition metal compound is ethylenebis(indenyl)zirconium dichloride.

7. The process of claim 3 wherein the alpha-olefin is selected from ethylene, propylene and 4-methyl-1-pentene, and the cyclo-olefin is selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 5-methyl-2-norbornene, norbornene and 5-ethylidene-2-norbornene.

8. The process of claim 4 wherein the alpha-olefin is selected from ethylene, propylene and 4-methyl-1-pentene, and the cyclo-olefin is selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 5-methyl-2-norbornene, norbornene and 5-ethylidene-2-norbornene.

9. The process of claim 6 wherein the alpha-olefin is selected from ethylene, propylene and 4-methyl-1-pentene, and the cyclo-olefin is selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 5-methyl-2-norbornene, norbornene and 5-ethylidene-2-norbornene.