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

• US 5,003,019 A
• Filed: 02/29/1988
• Issued: 03/26/1991
• 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:
  US07/162,200
• Time in Patent Office: 1,121 Days
• Field of Search: 526/281, 526/160
• 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 cyclo-olefinic random copolymer composed of an alpha-olefin component having 3 to 20 carbon atoms and a cyclo-olefin component,

(i) said copolymer consisting essentially of 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.

2. The cyclo-olefinic random copolymer of claim 1 which contains 15 to 95 mole % of units derived from said alpha-olefin component and 5 to 85 mole % of units derived from said cyclo-olefin.

3. The cyclo-olefinic random copolymer of claim 1 which contains 30 to 90 mole % of units derived from said alpha-olefin component and 10 to 70 mole % of units derived from said cyclo-olefin.

4. The cyclo-olefinic random copolymer of claim 1 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.05 to 7 dl/g.

5. The cyclo-olefinic random copolymer of claim 2 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.05 to 7 dl/g.

6. The cyclo-olefinic random copolymer of claim 3 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.05 to 7 dl/g.

7. The cyclo-olefinic random copolymer of claim 1 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.5 to 5 dl/g.

8. The cyclo-olefinic random copolymer of claim 2 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.5 to 5 dl/g.

9. The cyclo-olefinic random copolymer of claim 3 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.5 to 5 dl/g.

10. The cyclo-olefinic random copolymer of claim 7 wherein the alpha-olefin component is a component selected from propylene and 4-methyl-1-pentene components, and the cyclo-olefin component is a component selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, norbornene and 5-methyl-2-norbornene components.

11. The cyclo-olefinic random copolymer of claim 8 wherein the alpha-olefin component is a component selected from propylene and 4-methyl-1-pentene components, and the cyclo-olefin component is a component selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, norbornene and 5-methyl-2-norbornene components.

12. The cyclo-olefinic random copolymer of claim 9 wherein the alpha-olefin component is a component selected from propylene and 4-methyl-1-pentene components, and the cyclo-olefin component is a component selected from tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, norbornene and 5-methyl-2-norbornene components.

25. The cyclo-olefinic random copolymer of claim 1 wherein the recurring units derived from said cyclo-olefin component are represented by the formula (IV), (V) or (VI) ##STR48## wherein a and b are each an integer of 0 or more, c and d are each an integer of 3 or more, and each of R₁ to R₁₀ represent a hydrogen atom, a halogen atom, or a hydrocarbon group.

26. The cyclo-olefinic random copolymer of claim 1 which has a molecular-weight distribution (Mw/Mn) of not more than 3.

27. The cyclo-olefinic random copolymer of claim 1 having a glass transition temperature (Tg) of from 20°

to 200°

C.

13. An olefinic random copolymer 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 consisting essentially of 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.

14. The olefinic random copolymer of claim 13 which contains 15 to 95 mole % of units derived from the alpha-olefin component (A), 5 to 85 mole % of units derived from the cyclic polyene component, and 2 to 80 mole % of the cyclo-olefin component.

15. The olefinic random copolymer of claim 13 which contains 30 to 90 mole % of units derived from the alpha-olefin component (A), 10 to 70 mole % of units derived from the cyclic polyene component, and 5 to 70 mole % of the cyclo-olefin component.

16. The olefinic random copolymer of claim 13 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.05 to 7 dl/g.

17. The olefinic random copolymer of claim 14 which has an intrinsic viscosity [η

], measured in decalin at

18. The olefinic random copolymer of claim 15 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.05 to 7 dl/g.

19. The olefinic random copolymer of claim 13 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.5 to 5 dl/g.

20. The olefinic random copolymer of claim 14 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.5 to 5 dl/g.

21. The olefinic random copolymer of claim 15 which has an intrinsic viscosity [η

], measured in decalin at 135°

C., of 0.5 to 5 dl/g.

22. The olefinic random copolymer of claim 19 wherein the alpha-olefin component (A) is a propylene component, the cyclic polyene component (B) is a component selected from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene components, and the cyclo-olefin component (C) is a component selected from tetracyclodecene and norbornene components.

23. The olefinic random copolymer of claim 20 wherein the alpha-olefin component (A) is a propylene component, the cyclic polyene component (B) is a component selected from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene components, and the cyclo-olefin component (C) is a component selected from tetracyclodecene and norbornene components.

24. The olefinic random copolymer of claim 21 wherein the alpha-olefin component (A) is a propylene component, the cyclic polyene component (B) is a component selected from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene components, and the cyclo-olefin component (C) is a component selected from tetracyclodecene and norbornene components.

28. The olefin random copolymer of claim 13 wherein said cyclic polyene component (B) is selected from the group consisting of 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, dicyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2norbornene, 5-isopropylidene-2-norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,5-norbornadiene;

and wherein the recurring units derived from said cyclo-olefinic component (C) are represented by the formula (IV), (V) or (VI);

##STR49## wherein a and b are each an integer of 0 or more, c and d are each an integer of 3 or more, and each of R₁ to R₁₀ represent a hydrogen atom, a halogen atom, or a hydrocarbon group.

29. The olefinic random copolymer of claim 13 having a molecular-weight distribution (Mw/Mn) of not more than 3.