Cyclic conjugated diene polymer and method of producing same

• US 5,792,824 A
• Filed: 12/08/1995
• Issued: 08/11/1998
• Est. Priority Date: 05/21/1993
• Status: Expired due to Term

• Current Assignee: Asahi Kasei Kogyo Kabushiki Kaisha (Asahi Kasei Corporation)
• Original Assignee: Asahi Kasei Kogyo Kabushiki Kaisha (Asahi Kasei Corporation)
• Inventors: Natori, Itaru
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US08/569,482
• Time in Patent Office: 977 Days
• Field of Search: 526/180, 526/181, 526/308, 526/309, 526/329.1, 526/347, 525/272, 525/297, 525/314, 525/299
• US Class Current: 526/266
• CPC Class Codes: C08F 132/06 having two or more carbon-to-carbon double bonds
• CPC Class Codes: C08F 2800/20 as weight or mass percentages
• CPC Class Codes: C08F 297/023 using a coupling agent
• CPC Class Codes: C08F 297/04 polymerising vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: C08F 8/04 Reduction, e.g. hydrogenation
• CPC Class Codes: C08F 8/18 Introducing halogen atoms or halogen-containing groups

Abstract

Disclosed is a cyclic conjugated diene polymer comprising a main chain represented by the formula (I): ##STR1## wherein A to E are monomer units constituting the main chain in which A to E are arranged in any order, and l to p are, respectively, weight percentages of A to E, based on the total weight of A to E; A is selected from cyclic conjugated diene monomer units, B is selected from chain conjugated diene monomer units, C is selected from vinyl aromatic monomer units, D is selected from polar monomer units, and E is selected from an ethylene monomer unit and α-olefin monomer units; and l to p satisfy the following requirements: 0.5≦l≦100, 0≦m, n, o, p<100, wherein when l=100 and the A monomer units are comprised of monomer units which are the same, the polymer has a number average molecular weight Mn of from 40,000 to 5,000,000, wherein when l=100 and the A monomer units are comprised of monomer units which are different, the polymer has an Mn of from 25,000 to 5,000,000, and wherein when 0.5≦l<100, the polymer has an Mn of from 500 to 5,000,000. The cyclic conjugated diene polymer has excellent thermal and mechanical properties. The polymer can be advantageously produced using a catalyst comprised of a complex of an organometallic compound containing a Group IA metal with a complexing agent, especially an amine.

Claims

1. A cyclic conjugated diene polymer comprising a main chain represented by the following formula (I):

##STR12## wherein A to E are monomer units constituting said main chain in which monomer units A to E are arranged in any order, and l to p are, respectively, weight percentages of monomer units A to E, based on the total weight of monomer units A to E;

wherein;

A is selected from the class consisting of cyclic conjugated diene monomer units each being independently represented by the following formula (III);

##STR13## wherein each R² independently represents a hydrogen atom, a halogen atom, a C₁ -C₂₀ alkyl group, a C₂ -C₂₀ unsaturated aliphatic hydrocarbon group, a C₅ -C₂₀ aryl group, a C₃ -C₂₀ cycloalkyl group, a C₄ -C₂₀ cyclodienyl group or a 5 to 10-membered heterocyclic group having at least one nitrogen, oxygen or sulfur atom as a heteroatom,

B is selected from the class consisting of chain conjugated diene monomer units,

C is selected from the class consisting of vinyl aromatic monomer units,

D is selected from the class consisting of polar monomer units, and

E is selected from the class consisting of an ethylene monomer unit and α

-olefin monomer units; and

wherein;

l to p satisfy the following requirements;

space="preserve" listing-type="equation">l+m+n+o+p=100,

3. The cyclic conjugated diene polymer according to claim 1, wherein l=100, and wherein said A monomer units are comprised of cyclic conjugated diene monomer units which are the same or different.

4. The cyclic conjugated diene polymer according to claim 1, wherein 0.5≦

l<

100, and wherein said A monomer units are comprised of cyclic conjugated diene monomer units which are the same or different.

5. The cyclic conjugated diene polymer according to claim 1, which is an at least-tri-block copolymer.

6. The cyclic conjugated diene polymer according to claim 1, which is a block copolymer further containing at least two polymer blocks each containing at least one A monomer unit.

7. The cyclic conjugated diene polymer according to claim 1, which is a block copolymer having at least two polymer blocks each consisting of at least two A monomer units.

8. The cyclic conjugated diene polymer according to claim 1, which is an at least-di-block copolymer comprising at least one polymer block consisting of at least two A monomer units, and at least one polymer block consisting of monomer units of at least one type selected from the group consisting of said B to said E.

9. The cyclic conjugated diene polymer according to claim 1, which is an at least-di-block copolymer comprising at least one α

polymer block consisting of at least two A monomer units, and at least one β

polymer block comprised mainly of monomer units of at least one type selected from said B and said E, wherein the weight ratio of said α

block to said β

block is from 1/99 to 99/1.

10. The cyclic conjugated diene polymer according to claim 1, which is an at least-tri-block copolymer comprising at least two Y blocks each consisting of at least two A monomer units, and at least one Z block comprised mainly of monomer units of at least one type selected from said B, said C and said E, wherein the weight ratio of said at least two Y blocks to said at least one Z block is from 1/99 to 99/1.

11. The cyclic conjugated diene polymer according to claim 1, which is a triblock copolymer comprising two Y blocks each consisting of at least two A monomer units, and one Z block comprised mainly of monomer units of at least one type selected from said B, said C and said E.

12. The cyclic conjugated diene polymer according to claim 9, wherein said at least-tri-block copolymer has a configuration represented by a formula selected from the group consisting of Y--(Z--Y)_q, (Y--Z)_r, Z--(Y--Z)_r, (Z--Y)_q .brket close-st._r, (Y--Z)_q .brket close-st._r, (Z--Y)_q --Z.brket close-st._r, and (Y--Z)_q --Y.brket close-st._r, in which Y and Z are as defined above, q is an integer of 1 or more, and r is an integer of 2 or more.

13. A cyclic conjugated diene polymer according to claim 1, wherein said A monomer unit is a 1,3-cyclohexadiene monomer unit or a derivative thereof.

14. The cyclic conjugated diene polymer according to claim 1, wherein said A monomer unit is a 1,3-cyclohexadiene monomer unit.

17. The method according to claim 14, wherein said metal belonging to Group IA of the Periodic Table is present in said complex in the form of an association of 2 metal atoms or more.

18. The method according to claim 14, wherein said metal belonging to Group IA of the Periodic Table is present in said complex in the form of an association of 4 metal atoms or more.

19. The method according to claim 14, wherein said at least one complexing agent comprises an amine.

20. The method according to claim 14, wherein said at least one complexing agent is an aliphatic amine.

21. The method according to claim 14, wherein said at least one complexing agent is a diamine.

22. The method according to claim 14, wherein said at least one complexing agent is an aliphatic diamine.

23. The method according to claim 14, wherein said at least one complexing agent is a tertiary amine.

24. The method according to claim 19, wherein said diamine is at least one member selected from the group consisting of tetramethylethylenediamine (TMEDA) and 1,4-diazabicyclo 2,2,2!-octane (DABCO).

25. The method according to claim 14, wherein said at least one organometallic compound containing a metal belonging to Group IA of the Periodic Table is an organolithium compound.

26. The method according to claim 14, wherein said at least one organometallic compound containing a metal belonging to Group IA of the Periodic Table is an organolithium compound selected from the group consisting of normal butyllithium (n-BuLi), secondary butyllithium (s-BuLi) and tertiary butyllithium (t-BuLi), and said at least one complexing agent is selected from the group consisting of tetramethylethylenediamine (TMEDA) and 1,4-diazabicyclo 2,2,2!-octane (DABCO).

27. The method according to claim 14, wherein said polymerization is a homopolymerization of one cyclic conjugated diene monomer, thereby producing a cyclic conjugated diene homopolymer.

28. The method according to claim 14, wherein said polymerization is a copolymerization of at least two cyclic conjugated diene monomers or a copolymerization of at least one cyclic conjugated diene monomer and at least one comonomer, thereby producing a cyclic conjugated diene copolymer.

29. The method according to claim 26, wherein said cyclic conjugated diene copolymer is a random copolymer.

30. The method according to claim 26, wherein cyclic conjugated diene copolymer is an alternating copolymer.

31. The method according to claim 26, wherein said cyclic conjugated diene copolymer is a block copolymer.

32. The method according to claim 26, wherein said cyclic conjugated diene copolymer is an at least-di-block copolymer.

33. The method according to claim 26, wherein said cyclic conjugated diene copolymer is an at least-tri-block copolymer.

34. The method according to claim 26, wherein said cyclic conjugated diene copolymer is a triblock copolymer.

35. The method according to claim 14, wherein said complex is formed prior to the polymerization of said at least one cyclic conjugated diene monomer.

2. 5≦

l≦

100,

space="preserve" listing-type="equation">0≦

m<

100,

space="preserve" listing-type="equation">0≦

n<

100,

space="preserve" listing-type="equation">0≦

o<

100,

and

space="preserve" listing-type="equation">0≦

p<

100,

with the proviso that when l=100 and said A monomer units are comprised of cyclic conjugated diene monomer units which are the same, said cyclic conjugated diene polymer has a number average molecular weight of from 40,000 to 5,000,000, that when l=100 and said A monomer units are comprised of cyclic conjugated diene monomer units which are different, said cyclic conjugated diene polymer has a number average molecular weight of from 25,000 to 5,000,000, and that when 0.5≦

l<

100, said cyclic conjugated diene polymer is a block copolymer which contains at least one polymer block consisting of at least two A monomer units, and has a number average molecular weight of from 500 to 5,000,000.

15. A method for producing a cyclic conjugated diene polymer comprising a main chain represented by the following formula (I):

##STR14## wherein A to E are monomer units constituting said main chain in which monomer units A to E are arranged in any order, and l to p are, respectively, weight percentages of monomer units A to E, based on the total weight of monomer units A to E;

wherein;

A is selected from the class consisting of cyclic conjugated diene monomer units,

B is selected from the class consisting of chain conjugated diene monomer units,

C is selected from the class consisting of vinyl aromatic monomer units,

D is selected from the class consisting of polar monomer units, and

E is selected from the class consisting of an ethylene monomer unit and α

-olefin monomer units; and

wherein;

l to p satisfy the following requirements;

space="preserve" listing-type="equation">l+m+n+o+p=100,

16. 5≦

l<

100,

space="preserve" listing-type="equation">0≦

m<

100,

space="preserve" listing-type="equation">0≦

n<

100

space="preserve" listing-type="equation">0≦

o<

100,

and

space="preserve" listing-type="equation">0≦

p<

100,

which comprises polymerizing at least one cyclic conjugated diene monomer, or at least one cyclic conjugated diene monomer and at least one comonomer copolymerizable therewith in the presence of a catalyst comprised of a complex of at least one organometallic compound containing a metal belonging to Group IA of the Periodic Table with at least one complexing agent, said at least one comonomer being selected from the class consisting of chain conjugated diene monomers, vinyl aromatic monomers, polar monomers, an ethylene monomer, and α

-olefin monomers.