Unsaturated copolymers, processes for preparing the same, and compositions containing the same

• US 6,310,164 B1
• Filed: 07/20/1998
• Issued: 10/30/2001
• Est. Priority Date: 07/18/1997
• Status: Expired due to Term

• Current Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Original Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Inventors: Yamaguchi, Masayoshi, Okada, Keiji, Morizono, Kenichi
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US09/118,901
• Time in Patent Office: 1,198 Days
• Field of Search: 526/339, 526/340, 526/347, 526/160, 526/161, 526/126, 526/127, 526/131, 526/132, 526/134, 526/153, 524/574, 524/575
• US Class Current: 526/339
• CPC Class Codes: C08F 210/00 Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/02 Ethene
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 210/18 with non-conjugated dienes, e.g. EPT rubbers
• CPC Class Codes: C08F 212/04 containing one ring
• CPC Class Codes: C08F 236/06 Butadiene
• CPC Class Codes: C08F 236/08 Isoprene
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

Unsaturated copolymer which is a copolymer of an αolefin of 2 to 12 carbon atoms and a conjugated diene monomer represented by the following formula (I-a) and has the properties: (a) in said copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I-a) form double bonds in the side chain of the copolymer, 1,4-addition units derived from the conjugated diene monomer (I-a) form double bonds in the main chain of the copolymer, and the quantity ratio of the double bonds of the side chain derived from the 1,2-addition units to the double bonds of the main chain derived from the 1,4-addition units (side chain double bonds derived from 1,2-addition units/main chain double bonds derived from 1,4-addition units) is in the range of 10/90 to 99/1 (b) five-membered rings are present in the main chain of said copolymer; and (c) the quantity ratio of the double bonds from all of the addition units to the five-membered rings (total of double bonds from all addition units/five-membered rings) is in the range of 20/80 to 90/10;

wherein R² is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms or an aryl group.

Claims

1. An unsaturated copolymer which is a copolymer of an α

-olefin of 2 to 12 carbon atoms and a conjugated diene monomer represented by the following formula (I-a);

wherein

R² is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms or an aryl group,

said unsaturated copolymer having the following properties;

(a) in said copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I-a) form double bonds in the side chain of the copolymer, 1,4-addition units derived from the conjugated diene monomer (I-a) form double bonds in the main chain of the copolymer, and, the quantity ratio of the double bonds of the side chain derived from the 1,2-addition units to the double bonds of the main chain derived from the 1,4-addition units (side chain double bonds derived from the 1,2-addition units/main chain double bonds derived from 1,4-addition units) is in the range of 10/90 to 99/1,

(b) five-membered rings are present in the main chain of said copolymer, and

(c) the quantity ratio of the double bonds from all of the addition units to the five-membered rings (total of double bonds from all addition units/five-membered rings) is in the range of 20/80 to 90/10.

2. The unsaturated copolymer as claimed in claim 1, wherein the conjugated diene monomer is 1,3-butadiene.

3. The unsaturated copolymer as claimed in claim 1, wherein the α

-olefin is ethylene or a combination of ethylene and an α

-olefin of 3 to 12 carbon atoms, and in the case of said combination, the molar ratio of ethylene to the α

-olefin of 3 to 12 carbon atoms is in the range of 99/1 to 40/60.

4. The unsaturated copolymer as claimed in claim 1, wherein the constituent units derived from the conjugated diene monomer are contained in the copolymer in the total amount of 0.01 to 30% by mol.

5. The unsaturated copolymer as claimed in claim 1, which has an iodine value of 1 to 50 g/100 g, an intrinsic viscosity (η

), as measured in decahydronaphthalene at 135°

C., of 0.01 to 10 dl/g and a glass transition temperature Tg of not higher than 25°

C.

6. An unsaturated copolymer-containing elastomer composition comprising:

(a) the copolymer as claimed in claim 1, and

(b) a crosslinking agent and/or a filler.

7. A process for preparing the unsaturated copolymer as claimed in claim 1, said process comprising:

copolymerizing an α

-olefin of 2 to 12 carbon atoms and at least one conjugated diene monomer represented by the following formula (I-a);

wherein

R² is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms or an aryl group,

in the presence of a catalyst;

said catalyst being at least one catalyst system comprising the following component (a);

(a) a transition metal complex represented by the following formula (II) or (III);

wherein

M is Ti, Zr, Hf, Nd, Sm or Ru;

Cp1 and Cp2 are each a cyclopentadienyl group, an indenyl group, a fluorenyl group or any of their derivatives, that is π

-bonded to M;

X¹ and X² are each an anionic ligand or a neutral Lewis base ligand;

Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a Sulfur atom; and

Z is C, O, B, S, Ge, Si, Sn or a group containing any of these atoms,

and at least one compound selected from the following components (b), (c) and (d);

(b) a compound which reacts with the transition metal M in the component (a) to form an ionic complex,

(c) an organoaluminum compound, and

(d) aluminoxane.

8. An unsaturated copolymer of an α

-olefin of 2 to 12 carbon atoms and conjugated diene monomer represented by the following formula (I-b);

wherein

R1 is an alkyl group of 1 to 8 carbon atoms or an aryl group,

wherein the constituent units derived from the conjugated diene monomer are contained in the copolymer in the total amount of 0.01 to 30% by mol, and

said unsaturated copolymer having the following properties;

(a) in said copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I-b) form double bonds in the side chain of the copolymer, 1,4-addition units derived from the conjugated diene monomer (I-b) form double bonds in the main chain of the copolymer, and the quantity ratio of the double bonds of the side chain derived from the 1,2-addition units to the double bonds of the main chain derived from the 1,4-addition units (side chain double bonds derived from 1,2-addition units/main chain double bonds derived from 1,4-addition units) is in the range of 5/95 to 99/1.

10. A process for preparing the unsaturated copolymer as claimed in claim 8, said process comprising

copolymerizing an α -olefin of 2 to 12 carbon atoms and at least one conjugated diene monomer represented by the following formula (I-b);

wherein

R¹ is an alkyl group of 1 to 8 carbon atoms or an aryl group, in the presence of a catalyst;

said catalyst being at least one catalyst system comprising the following component (a);

(a) a transition metal complex represented by the following formula (II) or (III);

wherein

M is Ti, Zr, Hf, Nd, Sm or Ru;

Cp1 and Cp2 are each a cyclopentadienyl group, an indenyl group, a fluorenyl group or any of their derivatives, that is π

-bonded to M;

X¹ and X² are each an anionic ligand or a neutral Lewis base ligand;

Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom; and

Z is C, O, B, S, Ge, Si, Sn or a group containing any of these atoms, and at least one compound selected from the following components (b), (c) and (d);

(b) a compound which reacts with the transition metal M in the component (a) to form an ionic complex,

(c) an organoaluminum compound, and

(d) aluminoxane.

9. An unsaturated copolymer of an α

-olefin of 2 to 12 carbon atoms and a conjugated diene monomer represented by the following formula (I-b);

wherein

R1 is an alkyl group of 1 to 8 carbon atoms or an aryl group, said unsaturated copolymer having the following properties;

(a) in said copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I-b) form double bonds in the side chain of the copolymer, 1,4-addition units derived from the conjugated diene monomer (I-b) form double bonds in the main chain of the copolymer, and the quantity ratio of the double bonds of the side chain derived from the 1,2-addition units to the double bonds of the main chain derived from the 1,4-addition units (side chain double bonds derived from 1,2-addition units/main chain double bonds derived from 1,4-addition units) is in the range of 5/95 to 99/1,

(b) five-membered rings are present in the main chain of said copolymer, and

(c) the quantity ratio of the double bonds from all of the addition units to the five-membered rings (total of double bonds from all addition units/five-membered rings) is in the range of 20/80 to 90/10.

22. The unsaturated copolymer as claimed in claim 9, wherein the conjugated diene monomer is isoprene.

23. The unsaturated copolymer as claimed in claim 9, wherein the α

-olefin is ethylene or a combination of ethylene and an α

-olefin of 3 to 12 carbon atoms, and in the case of said combination, the molar ratio of ethylene to the α

-olefin of 3 to 12 carbon atoms is in the range of 99/1 to 40/60.

24. The unsaturated copolymer as claimed in claim 9, wherein the constituent units derived from the conjugated diene monomer are contained in the copolymer in the total amount of 0.01 to 30% by mol.

25. The unsaturated copolymer as claimed in claim 9, which has an iodine value of 1 to 50 g/100 g, an intrinsic viscosity (η

), as measured in decahydronaphthalene at 135°

C., of 0.01 dl/g and a glass transition temperature Tg, as measured by DSC, of not higher than 25°

C.

26. An unsaturated copolymer-containing elastomer composition comprising:

(a) the copolymer as claimed in claim 9, and

(b) a crosslinking agent and/or a filler.

27. A process for preparing the unsaturated copolymer as claimed in claim 9, said process comprising

copolymerizing an α

-olefin of 2 to 12 carbon atoms and at least one conjugated diene monomer represented by the following formula (I-b);

wherein

R1 is an alkyl group of 1 to 8 carbon atoms or an aryl group, in the presence of a catalyst;

said catalyst being at least one catalyst system comprising the following component (a);

(a) a transition metal complex represented by the following formula (II) or (III);

M is Ti, Zr, Hf, Nd, Sm or Ru;

Cp1 and Cp2 are each a cyclopentadienyl group, an indenyl group, a fluorenyl group or any of their derivatives, that is π

-bonded to M;

X¹ and X² are each an anionic ligand or a neutral Lewis base ligand;

Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom; and

Z is C, O, B, S, Ge;

Si, Sn or a group containing any of these atoms, and at least one compound selected from the following components (b), (c) and (d);

(b) a compound which reacts with the transition metal M in the component (a) to form an ionic complex,

(c) an organoaluminum compound, and

(d) aluminoxane.

11. An unsaturated random copolymer of an α

-olefin of 2 to 12 carbon atoms, an aromatic vinyl compound and a conjugated diene monomer,

which conjugated diene monomer is represented by the following formula (I);

wherein

R¹ and R² are each independently a hydrogen atom, an alkyl group of 1 to 8 carbon atoms or an aryl group, and at least one of R¹ and R² is a hydrogen atom,

said unsaturated copolymer having the following properties;

(a) in said copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I) form double bonds in the side chain of the copolymer, 1,4-addition units derived from the conjugated diene monomer (I) form double bonds in the main chain of the copolymer, and the quantity ratio of the double bonds of the side chain derived from the 1,2-addition units to the double bonds of the main chain derived from the 1,4-addition units (side chain double bonds derived from 1,2-addition units/main chain double bonds derived from 1,4-addition units) is in the range of 10/90 to 99/1.

12. The unsaturated copolymer as claimed in claim 11, which is a copolymer of an α

-olefin of 2 to 12 carbon atoms, an aromatic vinyl compound and a conjugated diene monomer represented by the following formula (I)

wherein

R¹ and R² are each independently a hydrogen atom, an alkyl group of 1 to 8 carbon atoms or an aryl group, and at least one of R¹ and R² is a hydrogen atom,

said unsaturated copolymer having the following properties;

(a) in said copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I) form double bonds in the side chain of the copolymer, 1,4-addition units derived from the conjugated diene monomer (I) form double bonds in the main chain of the copolymer, and the quantity ratio of the double bonds of the side chain derived from the 1,2-addition units to the double bonds of the main chain derived from the 1,4-addition units (side chain double bonds derived from 1,2-addition units/main chain double bonds derived from 1,4-addition units) is in the range of 10/90 to 99/1,

(b) five-membered rings are present in the main chain of said copolymer,

(c) the quantity ratio of the double bonds from all of the addition units to the five-membered rings (total of double bonds from all addition units/five-membered rings) is in the range of 20/80 to 90/10, and

(d) the constituent units derived from the aromatic vinyl compound are contained in an amount of 0.1 to 60% by mol.

13. The unsaturated copolymer as claimed in claim 11, wherein the constituent units derived from the conjugated diene monomer are contained in the copolymer in the total amount of 0.01 to 30% by mol.

14. The unsaturated copolymer as claimed in claim 11, wherein the conjugated diene monomer is 1,3-butadiene.

15. The unsaturated copolymer as claimed in claim 11, wherein the conjugated diene monomer is isoprene.

16. The unsaturated copolymer as claimed in claim 11, wherein the α

-olefin is ethylene or a combination of ethylene and an α

-olefin of 3 to 12 carbon atoms, and in the case of said combination, the molar ratio of ethylene to the α

-olefin of 3 to 12 carbon atoms is in the range of 99/1 to 40/60.

17. The unsaturated copolymer as claimed in claim 11, wherein the aromatic vinyl compound is styrene.

18. The unsaturated copolymer as claimed in claim 11, which has an iodine value of 1 to 50 g/100 g, an intrinsic viscosity (η

), as measured in decahydronaphthalene at 135°

C., of 0.01 to 10 dl/g and a glass transition temperature Tg of not higher than 25°

C.

19. The unsaturated copolymer as claimed in claim 11, wherein the peak of a melting point (Tm) of the copolymer, as measured by DSC, is not higher than 120°

C.

20. An unsaturated copolymer-containing elastomer composition comprising:

(a) the unsaturated copolymer as claimed in claim 11, and

(b) a crosslinking agent and/or a filler.

21. A process for preparing the unsaturated copolymer as claimed in claim 11, said process comprising:

copolymerizing an α

-olefin of 2 to 12 carbon atoms, an aromatic vinyl compound and at least one conjugated diene monomer represented by the following formula (I);

wherein

R¹ and R² are each independently a hydrogen atom, an alkyl group of 1 to 8 carbon atoms or an aryl group, and at least one of R¹ and R² is a hydrogen atom,

in the presence of a catalyst;

said catalyst being at least one catalyst system comprising the following component (a);

(a) a transition metal complex represented by the following formula (II) or (III);

wherein

M is Ti, Zr, Hf, Nd, Sm or Ru;

Cp1 and Cp2 are each a cyclopentadienyl group, an indenyl group, a fluorenyl group or any of their derivatives, that is π

-bonded to M;

X¹ and X² are each an anionic ligand or a neutral Lewis base ligand;

Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a Sulfur atom; and

Z is C, O, B, S, Ge, Si, Sn or a group containing any of these atoms;

and at least one compound selected from the following components (b), (c) and (d);

(b) a compound which reacts with the transition metal M in the component (a) to form an ionic complex,

(c) an organoaluminum compound, and

(d) aluminoxane.