JPH08225614A - Improved cyclic conjugated diene-based polymer and its production - Google Patents

Abstract

PURPOSE: To obtain a cyclic conjugated diene-based polymer having a narrow molecular weight distribution and improved thermal and mechanical properties by polymerizing a cyclic conjugated diene-based monomer with another monomer in the presence of a specified catalyst. CONSTITUTION: The process for producing the cyclic conjugated diene-based polymer having a main chain represented by the formula, which comprises polymerizing a cyclic conjugated diene-based monomer or copolymerizing a cyclic conjugated diene-based monomer with another comonomer in the presence of a catalyst comprising the mixture of complex of an organometallic compound containing a group 1A metal in the periodic table with a first complexing agent with a second complexing agent. In the formula, A is a unit derived from the cyclic conjugated diene monomer; B is a unit derived from a linear conjugated diene monomer; C is a unit derived from a vinylaromatic monomer; D is a unit derived from a polar monomer; E is a unit derived from ethylene or an α-olefinic monomer; a+b+c+d+e=100; 0.1<=a<=100; 0<=b<100; 0<=d<100; and 0<=e<100.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an improved cyclic conjugated diene polymer and a method for producing the same. More specifically, the present invention provides that the polymer main chain comprises at least one cyclic conjugated diene monomer unit, or at least one cyclic conjugated diene monomer unit and another copolymerizable therewith. Consists of at least one monomer unit, and the cyclic conjugated diene monomer unit is 1,2-bond and 1,4-
The relatively high 1,2-
The present invention relates to a cyclic conjugated diene polymer having a bond / 1,4-bond molar ratio, a relatively narrow molecular weight distribution, and improved thermal and mechanical properties. The present invention also relates to an industrially advantageous method for producing such an excellent cyclic conjugated diene-based polymer using a unique catalyst.

[0002]

2. Description of the Related Art In recent years, polymer chemistry has made progress through several innovations in order to meet the demands of diversifying markets. In particular, in the research of polymer materials intended for industrial materials, enormous research has been carried out to develop better thermal and mechanical properties, and various and diverse materials have been proposed and developed. For example, conjugated diene-based polymers such as polybutadiene and polyisoprene have been proposed many times in the past because of the large degree of freedom in designing polymer chains and the relative ease of controlling material properties. Is widely used as an important industrial material.

However, with the recent advances in industrial technology, the market demand for polymer materials has become more and more sophisticated, and even higher thermal characteristics (melting point, glass transition temperature, heat distortion temperature, etc.) and machinery There has been a strong demand for the development of polymeric materials having specific properties (tensile elastic modulus, bending elastic modulus, etc.).

As one of the most effective means for solving this problem, not only a monomer having a relatively small steric hindrance such as butadiene and isoprene, but also a monomer having a large steric hindrance, that is, a cyclic conjugated diene-based monomer is used. Active research activities have been carried out to obtain polymer materials with high thermal and mechanical properties by homopolymerizing or copolymerizing polymers and improving the structure of polymer chains of conjugated diene polymers. I'm starting to be seen. However, in the prior art, although a catalyst system showing a certain satisfactory polymerization activity for a monomer having a relatively small steric hindrance such as butadiene and isoprene, a monomer having a large steric hindrance, that is, a cyclic conjugated diene is proposed. A catalyst system having a sufficiently satisfactory polymerization activity has not yet been found for the system monomer.

That is, according to the prior art, it is difficult to homopolymerize the cyclic conjugated diene-based monomer, and it is not possible to obtain a sufficient high molecular weight polymer. In addition, the cyclic conjugated diene-based monomer has various thermal and mechanical properties in order to meet various market demands. Even when copolymerization with other monomers was attempted for the purpose of optimizing, it was possible to obtain only a low molecular weight substance such as an oligomer. That is,
A method for producing an excellent cyclic conjugated diene polymer, which is sufficiently satisfactory as an industrial material, has not yet been known, and this solution has been strongly desired.

J. Am. Chem. Soc., 81, 448 (1959), cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene, which is a cyclic conjugated diene-based monomer, using a composite catalyst composed of titanium tetrachloride and triisobutylaluminum. And this polymerization method is disclosed.
The polymerization method described here requires not only a large amount of polymerization catalyst and a long reaction time, but also the obtained polymer has an extremely low molecular weight, and thus has no industrial value.

J. Polym. Sci., Pt. A, 2, 3277 (196
4) includes 1,3-cyclohexadiene as a radical,
A method for polymerizing a cyclohexadiene homopolymer polymerized by various methods such as cation, anion and coordination polymerization is disclosed. In any of the polymerization methods described herein, the molecular weight of the obtained polymer is extremely low and is not industrially valuable.

British Patent Application No. 1,042,625 discloses a method for polymerizing a cyclohexadiene homopolymer by polymerizing 1,3-cyclohexadiene using a large amount of an organolithium compound as a catalyst. In the polymerization method disclosed herein, it is necessary to use 1 to 2% by weight of a catalyst with respect to a monomer, which is not only economically disadvantageous, but also the obtained polymer has a very low molecular weight. Will be. Furthermore, there is no suggestion or teaching about the possibility of obtaining copolymers. On the other hand, it is difficult to remove a large amount of catalyst residue remaining in the polymer by this polymerization method, and the polymer obtained by this polymerization method has no commercial value.

J. Polym. Sci., Pt. A, 3, 1553 (196
5) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using an organolithium compound as a catalyst. The number average molecular weight of the polymer obtained here was 20,000 even though the polymerization reaction was continued for 5 weeks.

Polym. Prepr. (Amer. Chem. Soc., Di
v. Polym. Chem.) 12,402 (1971) includes 1,3-
When cyclohexadiene is polymerized using an organolithium compound as a catalyst, it is disclosed that the limit of the number average molecular weight of cyclohexadiene homopolymer is 10,000 to 15,000. It is taught that the transfer reaction accompanied by the extraction of lithium cation and the elimination reaction of lithium hydride occur simultaneously.

Die Makromolekulare Chemie., 163, 13
(1973) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using a large amount of an organolithium compound as a catalyst. The oligomeric polymer obtained here has a number average molecular weight of 6,5.
It's just 00.

European Polymer J., 9, 895 (1973)
Includes a π-allyl nickel compound as a polymerization catalyst,
Copolymers of 1,3-cyclohexadiene with butadiene and isoprene are described. However, it has been reported that the polymer obtained here is an oligomer having an extremely low molecular weight and has a single glass transition temperature suggesting a random copolymer.

Polymer Collection, Vol. 34, No. 5,333 (19
77) describes a copolymer of 1,3-cyclohexadiene and acrylonitrile using zinc chloride as a polymerization catalyst. The alternating copolymer obtained here is an extremely low molecular weight oligomer.

J. Polym. Sci., Polym. Chem. Ed., 20,
901 (1982) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using an organic sodium compound as a catalyst. The organic sodium compound used here is sodium naphthalene, and the dianion formed from radical anions serves as the polymerization initiation point in practice. That is, although the number average molecular weight of the cyclohexadiene homopolymer reported here is apparently 38,700, the molecular chain of the number average molecular weight 19,350 practically grows in only two directions from the polymerization initiation point. Absent. Further, the polymerization method disclosed herein is a reaction at an extremely low temperature and has no industrial value.

Makromol. Chem., 191, 2743 (1990) discloses 1,3-polystyryllithium as a polymerization initiator.
A method of polymerizing cyclohexadiene is described. In the polymerization method described here, it is taught that transfer reaction accompanied by abstraction of lithium cation and elimination reaction of lithium hydride occur at the same time as the polymerization reaction, and the polymerization reaction is started using polystyryllithium as an initiator. Despite the fact that it was carried out, it was reported that at room temperature, a styrene-cyclohexadiene block copolymer was not obtained, and only a cyclohexadiene homopolymer was obtained.

Similarly, when polystyryllithium was used as an initiator and blocking was carried out at -10 ° C., a block copolymer of styrene-cyclohexadiene having a molecular weight of about 20,000 was obtained with a cyclohexadiene homopolymer in an extremely low yield. Has been done. However, the copolymer obtained here not only has a very small content of cyclohexadiene block, but also block copolymerization with a chain conjugated diene monomer, multiblock of triblock or more, and radial. There is no suggestion or teaching about blocks.

On the other hand, in the prior art, 1,3-cyclohexadiene is linked to the polymer chain substantially only by 1,4-bonds, and therefore the reported glass transition temperature (Tg) is It is no higher than 89 ° C.

[0018]

As described above,
In the prior art, there is no known production method that can be industrially advantageously carried out for a cyclic conjugated diene polymer, and an excellent cyclic conjugated diene polymer that is sufficiently satisfactory as an industrial material has not yet been obtained. There wasn't. Therefore, an object of the present invention is to improve the molecular weight distribution in a narrow range and to have excellent thermal properties (melting point, glass transition temperature, heat deformation temperature, etc.) and mechanical properties (tensile modulus, flexural modulus, etc.). The present invention provides a cyclic conjugated diene polymer.

Another object of the present invention is to be able to polymerize a cyclic conjugated diene-based monomer, which has been difficult to polymerize due to a large steric hindrance, and has a high cyclic conjugated diene-based monomer. It is an object of the present invention to provide a method for industrially producing the above-mentioned excellent cyclic conjugated diene polymer, which is effective in connecting to the main chain of the polymer at a 1,2-bond ratio.

[0020]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors have derived a part or all of a polymer main chain from a cyclic conjugated diene monomer. By using a specific catalyst, the monomer unit is anionically polymerized, preferably living anionically polymerized, in an arbitrary ratio and form under industrially advantageous production conditions, and at that time, a cyclic conjugated diene-based monomer is used. The present invention has been completed by establishing a technique for linking and introducing a monomer unit derived from a monomer into the main chain through 1,2-bonds and 1,4-bonds.

More specifically, a complex obtained by reacting an organometallic compound containing a Group IA metal with a complexing agent (first complexing agent) to polymerize the cyclic conjugated diene-based monomer, and If a mixture of a complexing agent (second complexing agent) (the first complexing agent and the second complexing agent may be the same or different) is used as a polymerization catalyst, it cannot be solved by the conventional technique. Transferring Reaction and IA by Extraction of Group IA Metal Cation at the End of Polymer by the Cyclic Conjugated Diene Monomer
Not only the elimination reaction of the group metal hydride is suppressed, but the polymerization catalyst exhibits excellent polymerization activity even under high temperature conditions of about 40 ° C. to about 70 ° C., and the cyclic conjugated diene-based monomer is , 2-bond and 1,4-bond-bonded (and at a relatively high 1,2-bond ratio) a cyclic conjugated diene polymer can be industrially advantageously produced, and the obtained polymer is further obtained. Has a narrow molecular weight distribution and has excellent thermal and mechanical properties, and has completed the present invention.

Generally, in the field of organometallic chemistry,
An organometallic compound containing a Group IA metal and an amine compound,
It is well known that complexing agents such as ether compounds and metal alkoxides form highly reactive complexes, and are used as effective reaction reagents in organic synthetic reactions of monomers. However, in the field of conventional polymer chemistry, a complex of an organometallic compound containing a Group IA metal has been described as I
It has been considered to be unfavorable for the polymerization reaction because the reactivity increases due to the dissociation of charges of the organometallic compound containing a Group A metal and causes side reactions such as metallation.

However, as described above, the present inventors have
When a mixture of a Group IA metal-containing material and a second complexing agent is used as a polymerization catalyst, the catalyst does not cause side reactions such as metallation and maintains a thermally stable complex state. Discovered the amazing fact that you can. Surprisingly, the polymerization reaction of the cyclic conjugated diene-based monomer is performed by using the mixture of the complex (organic metal compound containing a group IA metal and the first complexing agent) and the second complexing agent as a polymerization catalyst. When carried out, not only the living anion polymerization reaction of the cyclic conjugated diene-based monomer proceeds even under high temperature conditions,
The obtained polymer has a narrow molecular weight distribution, and the cyclic conjugated diene-based monomer is linked to the polymer main chain by a high 1,2-bond ratio, so that the thermal characteristics (glass transition temperature, heat distortion temperature The present invention has been completed by discovering the industrially most preferable fact that an excellent cyclic conjugated diene-based polymer of (3) etc. can be obtained.

That is, the present invention is a polymer having a polymer main chain represented by the following formula (I), in which the monomer unit A has 1,2-bonds and 1,4-bonds. They are linked in a chain and have a 1,2-bond / 1,4-bond molar ratio of 40.
It provides a cyclic conjugated diene polymer characterized by being in the range of / 60 to 90/10 and having a number average molecular weight of the above polymer in the range of 500 to 5,000,000.

[0025]

[Chemical 6] [In the formula (1), A to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order. a to e represent the respective wt% of the monomer units A to E with respect to the total weight of the monomer units A to E. A: One or more monomer units selected from cyclic conjugated diene monomer units. B: One or more monomer units selected from chain conjugated diene monomer units. C: One or more monomer units selected from vinyl aromatic monomer units. D: One or more monomer units selected from polar monomer units. E: One or more monomer units selected from ethylene and α-olefin monomer units. a to e satisfy the following relationships. a + b + c + d + e = 100, 0.1 ≦ a ≦ 100, 0
≦ b <100, 0 ≦ c <100, 0 ≦ d <100, and 0 ≦ e <100].

The present invention also provides a method for producing a cyclic conjugated diene polymer having a polymer main chain represented by the following formula (I):

[0027]

[Chemical 7] [In the formula (I), A to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order. a to e represent the respective wt% of the monomer units A to E with respect to the total weight of the monomer units A to E. A: One or more monomer units selected from cyclic conjugated diene monomer units. B: One or more monomer units selected from chain conjugated diene monomer units. C: One or more monomer units selected from vinyl aromatic monomer units. D: One or more monomer units selected from polar monomer units. E: One or more monomer units selected from ethylene and α-olefin monomer units. A to E satisfy the following relationships. a + b + c + d + e = 100, 0.1 ≦ a ≦ 100, 0
≦ b <100, 0 ≦ c <100, 0 ≦ d <100, and 0 ≦ e <100. ] ,.

The number average molecular weight of the above polymer is from 500 to
5,000,000, and the above-mentioned production method provides: a complex of at least one organometallic compound containing a metal of Group A of the Periodic Table with at least one first complexing agent, and at least one Cyclic conjugated diene monomer, or at least one cyclic conjugated diene monomer and at least one other monomer copolymerizable therewith (chain conjugated diene monomer, vinyl aromatic monomer A monomer selected from the group consisting of monomers, polar monomers, ethylene monomers, and α-olefin monomers), a catalyst comprising a mixture of the above complex and at least one second complexing agent. The present invention provides a production method characterized by polymerizing in the presence.

Next, in order to facilitate understanding of the present invention,
The basic features and aspects of the present invention are listed. 1. A polymer having a polymer main chain represented by the following formula (I), wherein the monomer unit A has 1,2-bonds and 1,4
-Bonded in the polymer main chain by a bond, 1,2-bond /
The 1,4-bond molar ratio is in the range of 40/60 to 90/10, and the number average molecular weight of the polymer is 500 to 5,000.
A cyclic conjugated diene polymer characterized by being in the range of 50,000.

[0030]

Embedded image [In the formula (1), A to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order. a to e represent the respective wt% of the monomer units A to E with respect to the total weight of the monomer units A to E. A: One or more monomer units selected from cyclic conjugated diene monomer units. B: One or more monomer units selected from chain conjugated diene monomer units. C: One or more monomer units selected from vinyl aromatic monomer units. D: One or more monomer units selected from polar monomer units. E: One or more monomer units selected from ethylene and α-olefin monomer units. a to e satisfy the following relationships. a + b + c + d + e = 100, 0.1 ≦ a ≦ 100, 0
≦ b <100, 0 ≦ c <100, 0 ≦ d <100, and 0 ≦ e <100. ].

2. The cyclic conjugated diene-based polymer as described in 1 above, which is a block copolymer. 3. The cyclic conjugated diene-based polymer as described in 1 or 2 above, which has a glass transition temperature (Tg) of 150 ° C. or higher. 4. The cyclic conjugated diene-based polymer as described in 2 above, which is a block copolymer having a block unit having a glass transition temperature (Tg) of 150 ° C. or higher. 5. 5. The cyclic conjugated diene polymer according to any one of items 2 to 4, which is at least a triblock block copolymer. 6. The cyclic conjugated diene-based polymer according to any one of items 2 to 5, which is a block copolymer having a block unit containing at least two or more monomer units A. 7. The above-mentioned items 2 to 5, which is a block copolymer having a block unit consisting of at least two or more monomer units A only.
5. The cyclic conjugated diene polymer according to any one of 1.

8. At least a diblock having at least one block unit consisting only of at least two or more monomer units A and at least one block unit consisting only of at least one monomer unit selected from monomer units B to E 5. The cyclic conjugated diene-based polymer as described in any one of the above items 2 to 4, which is the block copolymer. 9. One block unit X containing at least one monomer unit A, and one block unit Y mainly composed of at least one monomer unit selected from a monomer unit B and a monomer unit E. And the cyclic conjugated diene-based polymer according to the above 2 to 4, which is a block copolymer of a diblock having an X / Y weight ratio in the range of 1/99 to 99/1. 10. At least two block units X containing at least one monomer unit A, and at least one block mainly composed of at least one monomer unit selected from a monomer unit B and a monomer unit E 6. The cyclic conjugated diene-based polymer according to item 5, which is a block copolymer of at least a triblock having a unit Y and an X / Y weight ratio in the range of 1/99 to 99/1.

11. Two block units X containing at least one monomer unit A and mainly monomer units B
And one block unit Y composed of at least one monomer unit selected from the monomer unit E, and X
The cyclic conjugated diene-based polymer according to the above 5, which is a triblock block copolymer having a weight ratio of / Y in the range of 1/99 to 99/1. 12. The structure of the block copolymer of at least the above triblock,

[0034]

[Chemical 9] [However, p is an integer of 1 or more and q is an integer of 2 or more. X and Y have the same meaning as defined above. ] The cyclic | annular conjugated diene-type polymer of the preceding clause 10 represented by these.

13. The cyclic conjugate according to any one of the above items 1 to 12, wherein the monomer unit A is at least one cyclic conjugated diene monomer unit selected from the monomer units represented by the following formula (II). Diene polymer.

[0036]

[Chemical 10] [M represents an integer of 1 to 4. Each R ¹ is independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, or a C ₂ to
A C ₂₀ unsaturated aliphatic hydrocarbon group, a C _{5 to} C ₂₀ aryl group, a C _{3 to} C ₂₀ cycloalkyl group, a C _{4 to} C ₂₀ cyclodienyl group, or a 5- to 10-membered ring and at least one Is a heterocyclic group containing nitrogen, oxygen or sulfur as a hetero atom, each R ² is independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, a C _{2 to} C ₂₀ unsaturated aliphatic carbon group. hydrogen group, an aryl group of _{C 5 ~C 20, C 3 ~C} 20
A cycloalkyl group of C ₄ -C ₂₀ cyclodienyl group,
Or a heterocyclic group having a 5- to 10-membered ring and containing at least one nitrogen, oxygen or sulfur as a hetero atom, or each R ² independently represents two R ^2- (CR ³
₂ ) _n- (R ³ has the same meaning as R ^1, and n is 1 to 10
, Which is an integer of). ].

14. 14. The cyclic conjugated diene-based polymer as described in 13 above, wherein the monomer unit A is at least one cyclic conjugated diene-based monomer unit selected from the monomer units represented by the following formula (III).

[0038]

[Chemical 11] [Each R ² has the same meaning as defined in formula (II). ].

15. The monomer unit A is at least one selected from a 1,3-cyclopentadiene monomer unit, a 1,3-cyclohexadiene monomer unit, a 1,3-cyclooctadiene monomer unit and derivatives thereof. 14. The cyclic conjugated diene-based polymer as described in 13 above, which is characterized by being present. 16. 1. The monomer unit A is a 1,3-cyclohexadiene monomer unit or a derivative thereof, as described in 1 above.
4. The cyclic conjugated diene polymer according to item 4.

17. 15. The cyclic conjugated diene-based polymer as described in 14 above, wherein the monomer unit A is a 1,3-cyclohexadiene monomer unit.

18. At least one reaction selected from hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation is performed on the cyclic conjugated diene polymer according to any one of the items 1 to 17 above. Polymer obtained by things. 19. A method for producing a cyclic conjugated diene polymer having a polymer main chain represented by the following formula (I),

[0042]

[Chemical 12] [In the formula (1), A to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order. a to e represent the respective wt% of the monomer units A to E with respect to the total weight of the monomer units A to E. A: One or more monomer units selected from cyclic conjugated diene monomer units. B: One or more monomer units selected from chain conjugated diene monomer units. C: One or more monomer units selected from vinyl aromatic monomer units. D: One or more monomer units selected from polar monomer units. E: One or more monomer units selected from ethylene and α-olefin monomer units. A to E satisfy the following relationships. a + b + c + d + e = 100, 0.1 ≦ a ≦ 100, 0
≦ b <100, 0 ≦ c <100, 0 ≦ d <100, and 0 ≦ e <100. ] ,.

The number average molecular weight of the above polymer is from 500 to
5,000,000, and the above-mentioned production method provides: a complex of at least one organometallic compound containing a metal of Group A of the Periodic Table and at least one first complexing agent, and at least one Cyclic conjugated diene monomer, or at least one cyclic conjugated diene monomer and at least one other monomer copolymerizable therewith (chain conjugated diene monomer, vinyl aromatic monomer A monomer selected from the group consisting of monomers, polar monomers, ethylene monomers, and α-olefin monomers), a catalyst comprising a mixture of the above complex and at least one second complexing agent. A method for producing, characterized in that the polymerization is carried out in the presence.

20. Each of said at least one first complexing agent and at least one second complexing agent independently
20. The production method according to item 19, which is an organic compound containing at least one element selected from the group consisting of oxygen (O), nitrogen (N), sulfur (S) and phosphorus (P). 21. Each of the at least one first complexing agent and the at least one second complexing agent is independently an organic compound selected from the group consisting of an ether compound, a metal alkoxide, an amine compound and a thioether compound. 20. The manufacturing method according to item 19 above. 22. 20. The method according to item 19, wherein each of the at least one first complexing agent and the at least one second complexing agent is independently an ether compound or an amine compound.

23. Each of said at least one first complexing agent and at least one second complexing agent independently
20. The method according to item 19 above, which is an amine compound. 24. 20. The production method according to the above item 19, wherein each of the at least one first complexing agent and the at least one second complexing agent is independently a diamine compound. 25. 20. The production method according to the above item 19, wherein each of the at least one first complexing agent and the at least one second complexing agent is independently an aliphatic diamine compound.

26. Each of said at least one first complexing agent and at least one second complexing agent independently
20. The method according to item 19 above, which is a tertiary amine compound. 27. The above diamine compounds are tetramethylethylenediamine (TMEDA) and diazabicyclo [2,2,2].
[2] The manufacturing method according to the above [24], which is selected from octane (DABCO). 28. 28. The method according to any one of items 19 to 27 above, wherein the at least one organometallic compound containing a metal of Group IA of the periodic table is an organolithium compound.

29. The at least one organometallic compound containing a metal of Group IA of the Periodic Table consists of normal butyl lithium (n-BuLi), secondary butyl lithium (s-BuLi) and tertiary butyl lithium (t-BuLi). An organolithium compound selected from the group wherein each of the at least one first complexing agent and the at least one second complexing agent is independently
20. The production method according to the above item 19, which is selected from tetramethylethylenediamine (TMEDA) and diazabicyclo [2,2,2] octane (DABCO). 30. The above complex is prepared by reacting at least one organometallic compound containing a metal of Group IA of the periodic table with at least one first complexing agent at a molar ratio shown by the following formula. 30. The manufacturing method according to any one of items 19 to 29 above. A ₁ / B ₁ = 200/1 to 1/100 (where A ₁ represents the molar amount of the group IA metal atom in at least _one organometallic compound used, and B ₁ is at least one first complexing agent used) The molar amount of.

31. The above complex comprises at least one organometallic compound containing a metal of Group IA of the periodic table and at least one first complexing agent in a molar ratio represented by the following formula:
30. The manufacturing method according to any one of items 19 to 29 above, which is configured. A ₂ / B ₂ = 1 / 0.25 to 1/1 (where A ₂ represents the molar amount of the group IA metal atom in at least one organometallic compound in the complex, and B ₂ represents at least one in the complex) The molar amount of the first complexing agent is shown).

32. In the above catalyst, at least one of the above organometallic compounds and at least one of the above first
The complexing agent and the at least one second complexing agent described above are present in a molar ratio represented by the following formula:
29. The manufacturing method according to any one of 29. A ₃ / B ₃ = 100/1 to 1/200 (where A ₃ is the molar amount of Group IA metal atom in at least one organometallic compound in the catalyst, B ₃ is at least one first complex in the catalyst) Total molar amount of the agent and the at least one second complexing agent).

In the present invention, each monomer unit constituting the polymer is named according to the name of the monomer from which the monomer unit is derived. Therefore, for example, "cyclic conjugated diene-based monomer unit" means a structural unit of a polymer that is produced as a result of polymerizing a cyclic conjugated diene-based monomer that is a monomer, and its structure is a cyclic This is a molecular structure in which two carbon atoms of the cycloolefin corresponding to the conjugated diene-based monomer are binding sites. Further, for example, the “cyclic olefin-based monomer unit” means a constitutional unit of a polymer produced as a result of polymerizing a cyclic olefin which is a monomer, and its structure is such that two carbons of a cycloalkane are bonded to each other. This is the molecular structure of the site.

The cyclic conjugated diene-based polymer in the present invention means a monomer unit in which some or all of a plurality of monomer units constituting a polymer chain are derived from a cyclic conjugated diene-based monomer. And / or a polymer comprising a derivative of the monomer unit.

As a typical cyclic conjugated diene polymer of the present invention, a polymer whose main chain contains a monomer unit derived from only a cyclic conjugated diene monomer, or a cyclic conjugated diene polymer Examples of the polymer include a monomer and a monomer unit derived from at least one other monomer copolymerizable therewith.

More specifically, a homopolymer of a cyclic conjugated diene monomer, a copolymer of two or more cyclic conjugated diene monomers, a cyclic conjugated diene monomer, and a copolymerizable therewith Examples thereof include copolymers with at least one other monomer. As the most preferable cyclic conjugated diene-based polymer, a monomer unit derived from the cyclic conjugated diene-based monomer contained in the polymer chain is a polymer which is a monomer unit containing a cyclohexene ring. You can do it.

According to yet another aspect of the present invention, the cyclic conjugated diene polymer of the present invention is hydrogenated, halogenated, hydrohalogenated, alkylated, arylated, ring-opened and dehydrogenated. There is provided a polymer obtained by carrying out at least one reaction selected from Particularly, when high thermal and mechanical performance is required, it is preferable to carry out the hydrogenation reaction.

The cyclic conjugated diene-based monomer in the present invention is a cyclic conjugated diene having a 5-membered ring or more and composed of carbon-carbon bonds. A preferred cyclic conjugated diene-based monomer is a 5- to 8-membered cyclic conjugated diene composed of carbon-carbon bonds. A particularly preferred cyclic conjugated diene-based monomer is a 6-membered cyclic conjugated diene composed of carbon-carbon bonds. Specifically, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene and derivatives thereof can be exemplified.
Examples of preferable cyclic conjugated diene-based monomers include 1,3-cyclohexadiene and 1,3-cyclohexadiene derivatives. The most preferred cyclic conjugated diene-based monomer is 1,3-cyclohexadiene.

In the present invention, as the other monomer copolymerizable with the cyclic conjugated diene-based monomer, a conventionally known monomer which can be polymerized by anionic polymerization can be exemplified.

For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-
Chain conjugated diene-based monomers such as pentadiene, 1,3-hexadiene, or derivatives thereof, styrene, α
-Methylstyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene,
Vinyl anthracene, 1,1-diphenylethylene, m
-Vinyl aromatic monomers such as diisoprenyl benzene, vinyl pyridine, or their derivatives, polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, and methyl α-cyanoacrylate Body or ethylene oxide, propylene oxide, cyclohexene oxide, cyclic lactone,
Examples thereof include polar monomers such as cyclic lactams and cyclic siloxanes, or ethylene and α-olefin monomers. These monomers may be used alone or in combination of two or more, if necessary.

Further, the mode of the copolymer obtained by the production method of the present invention can be variously selected according to need. For example, diblock, triblock, tetrablock, multiblock, radial block, asymmetric radial block, graft block, star block, block copolymers such as comb blocks, graft copolymer,
Examples thereof include taper copolymers, random copolymers, alternating copolymers, and the like.

In the cyclic conjugated diene polymer of the present invention, the monomer unit derived from another copolymerizable monomer may be hydrogenated, halogenated, alkylated, arylated or the like after completion of the polymerization reaction. It is not particularly limited that the monomer unit is derived. The content of the monomer unit derived from the cyclic conjugated diene-based monomer in the cyclic conjugated diene-based polymer of the present invention is not particularly limited because it is variously set depending on its intended use, but in general, The range is 0.1 to 100 wt% with respect to the total weight of the polymer chain, preferably 0.5 to 100 wt%, and particularly preferably 1 to 100 wt%.

When the cyclic conjugated diene-based polymer of the present invention is used in applications and fields requiring high thermal and mechanical properties, a monomer derived from the cyclic conjugated diene-based monomer is used. The content of the unit is 5 to 10 relative to the total weight of the polymer chain.
It is preferably in the range of 0 wt%, and 10 to 100 wt
% Is particularly preferable, 15 to 100 wt%
Most preferably, it is within the range.

According to the production method of the present invention, a cyclic conjugated diene polymer can be produced by living anion polymerization, so that its molecular weight can be set arbitrarily, and its range is particularly limited. Not a thing. In the case of industrial production, the number average molecular weight of the polymer chain is usually preferably in the range of 500 to 5,000,000, and may be appropriately selected and set according to the application and purpose.
For example, when used as a functional material, it is generally 5
The range is from 00 to 2,000,000, and from 1,000 to
It is preferably in the range of 1,000,000, and 2,0
It is particularly preferable that the range is from 00 to 800,000,
Most preferably, it is in the range of 3,000 to 500,000.

On the other hand, when used as a structural material, the number average molecular weight of the polymer chain is generally 20,000 to
5,000,000 range, 30,000 to 4,
It is preferably in the range of, 000,000, and 40,000.
The range of 0 to 3,000,000 is more preferable, the range of 40,000 to 2,000,000 is particularly preferable, and the range of 40,000 to 1,000,000 is most preferable. preferable.

The cyclic conjugated diene polymer of the present invention has a polymer terminal with a conventionally known bifunctional or higher functional coupling agent (for example, for the purpose of controlling the molecular weight or obtaining a star-shaped polymer, if necessary). Dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, It is not particularly limited to bond with an ester or the like).

The number average molecular weight (Mn) in the present invention means G. P. It is the number average molecular weight in terms of standard polystyrene measured by C (gel permeation chromatography) method. The value of Mw / Mn, which is the standard of the molecular weight distribution of the cyclic diene polymer of the present invention, is 1.01 to 1
The range is 0, preferably 1.03 to 7.0, and particularly preferably 1.05 to 5.0.

In the cyclic diene polymer of the present invention,
It has a structure in which the monomer units A are linked in the polymer main chain by 1,2-bonds and 1,4-bonds. In the present invention, the ratio of 1,2-bonds measured by ¹ H-NMR is in the range of 40 mol% to 90 mol% with respect to the total of 1,2-bonds and 1,4-bonds. is necessary. When the ratio of 1,2-bonds is within the above range, a cyclic conjugated diene polymer having a high glass transition temperature (Tg) and improved thermal characteristics can be obtained. When the ratio of 1,2-bonds is low, sufficient thermal properties cannot be expressed because of low Tg, and when the ratio of 1,2-conjunction is too high, Tg remarkably increases. For this reason, the molding / processing temperature and the decomposition temperature are close to each other, which causes undesirable results.

When the productivity of the polymer and the molding and processability are taken into consideration, the ratio of 1,2-bonds is 40 to 85 mol.
% Is preferred, 40-80 mol% is more preferred, and 40-70 mol% is most preferred.
In the present invention, the ratio of 1,2-bonds is 40-9.
A cyclic conjugated diene-based polymer having a glass transition temperature of 150 ° C. or higher, particularly a homopolymer or a block copolymer, in the range of 0 mol% is most preferable in terms of thermal and mechanical properties.

When the cyclic conjugated diene-based polymer obtained by the production method of the present invention is a cyclic conjugated diene-based block copolymer having a block unit in the polymer chain, the (polymer) block unit is a cyclic conjugated diene-based polymer. A block unit composed of a monomer unit derived from a diene monomer, a cyclic conjugated diene monomer and a monomer unit derived from another monomer copolymerizable therewith Block unit, and further a block unit composed of a monomer unit derived from another monomer copolymerizable with the cyclic conjugated diene-based monomer can be designed, and various blocks can be designed as necessary. By designing and polymerizing units and binding them, a cyclic conjugated diene block copolymer can be obtained according to the purpose.

When the block unit of the present invention contains a monomer unit derived from a cyclic conjugated diene monomer in a part or all of the block unit, at least one molecule of the cyclic conjugated diene monomer is contained in the block unit. It is necessary to contain a monomer unit derived from a monomer, and at least two molecules of a monomer unit derived from a cyclic conjugated diene monomer are continuously bonded. It is preferable that 5 or more monomer units are continuously bonded, and it is more preferable that 10 or more monomer units are continuously bonded to improve thermal and mechanical properties. Therefore, it is particularly preferable.

The method for producing the cyclic conjugated diene-based block copolymer of the present invention includes a block unit composed of monomer units derived from one or more cyclic conjugated diene-based monomers, one or A block unit composed of two or more cyclic conjugated diene monomers and a monomer unit derived from one or more other monomers copolymerizable therewith, and further a cyclic conjugated diene system A block unit composed of a monomer unit derived from one or more other monomers copolymerizable with the monomer is polymerized / bonded according to the purpose, and further hydrogenated if necessary. Examples thereof include a method of performing at least one reaction selected from halogenation, halogenated hydrogenation, alkylation, arylation, ring opening and dehydrogenation.

The following methods can be enumerated as specific embodiments of the production method of the present invention. A block unit containing a monomer unit derived from a cyclic conjugated diene monomer or a block unit consisting of a monomer unit derived from a cyclic conjugated diene monomer is preliminarily polymerized, and its weight is From one end or both ends of the polymer, one or more other monomers that can be copolymerized with it are polymerized, and further hydrogenation, halogenation, hydrohalogenation, alkylation, arylation is further carried out as required. , A method of performing at least one reaction selected from ring opening and dehydrogenation.

One kind or two or more kinds of other monomers copolymerizable with the cyclic conjugated diene monomer are preliminarily polymerized, and the cyclic conjugated diene monomer is added from one end or both ends of the polymer. And, if necessary, polymerizing one or more other monomers copolymerizable with the cyclic conjugated diene-based monomer, and further hydrogenating, halogenating, hydrohalogenating, alkylating as necessary. , At least one reaction selected from arylation, ring opening and dehydrogenation.

A block unit containing a monomer unit derived from a cyclic conjugated diene monomer or a block unit consisting of a monomer unit derived from a cyclic conjugated diene monomer is polymerized and then Block unit or cyclic conjugated diene-based monomer containing a monomer unit derived from a cyclic conjugated diene-based monomer, which is obtained by polymerizing one or two or more other monomers copolymerizable with Block units consisting of monomer units derived from are sequentially polymerized and, if necessary, further selected from hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation. A method of performing at least one reaction.

One or more other monomers copolymerizable with the cyclic conjugated diene monomer are preliminarily polymerized to contain a monomer unit derived from the cyclic conjugated diene monomer. Block unit or a block unit consisting of a monomer unit derived from a cyclic conjugated diene-based monomer is polymerized, and is further copolymerizable with the cyclic conjugated diene-based monomer. A method in which the monomers are sequentially polymerized and, if necessary, at least one reaction selected from hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation is further performed.

A cyclic conjugated diene-based monomer and one or more other monomers having different polymerization rates and different from each other and capable of copolymerization are simultaneously polymerized to form a tapered block copolymer. A method of carrying out at least one reaction selected from hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation.

A block unit containing a monomer unit derived from a cyclic conjugated diene type monomer or a block unit derived from a cyclic conjugated diene type monomer is polymerized and then copolymerized with this. Alternatively, two or more kinds of other monomers are polymerized, and a polymer terminal is conventionally known as a bifunctional or higher functional coupling agent (for example, dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride). , Methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, esters, etc.) and hydrogenation, etc., if necessary.

A cyclic conjugated diene-based monomer and one or more other monomers copolymerizable with the cyclic conjugated diene-based monomer are charged in different composition ratios, polymerized at the same time, and further hydrogenated if necessary,
A method of carrying out at least one reaction selected from halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation.

The cyclic conjugated diene-based monomer is first polymerized, and at any conversion rate, one or two or more other copolymerizable monomers having different polymerization rates and different copolymerization rates are added and polymerized, and then left. Block copolymer by polymerizing the cyclic conjugated diene-based monomer, which may be further hydrogenated, halogenated, hydrohalogenated, alkylated, arylated, ring-opened and dehydrogenated. A method of carrying out at least one reaction selected can be exemplified, and various block copolymers can be prepared depending on the needs and purposes.

A block unit containing a monomer unit derived from one or more kinds of cyclic conjugated diene-based monomers or consisting of a cyclic conjugated diene-based monomer unit can be copolymerized with this. It is not particularly limited to contain a monomer unit derived from one kind or two or more kinds of other monomers. Furthermore, the block unit consisting of a monomer unit derived from one or two or more other monomers copolymerizable with one or two or more cyclic conjugated diene-based monomers is one or two or more. The inclusion of a monomer unit derived from the cyclic conjugated diene monomer is also not particularly limited.

The most preferred monomer unit or block unit derived from one or more cyclic conjugated diene-based monomers in the present invention is a cyclohexene ring-containing monomer unit or a constitutional unit thereof. The block unit is a monomer unit obtained by further performing a hydrogenation reaction, an elimination reaction, a ring-opening reaction, or the like, or a block unit containing or consisting of the same.

In the cyclic conjugated diene-based polymer obtained by the production method of the present invention, a preferred monomer derived from the cyclic conjugated diene-based monomer introduced into part or all of the polymer main chain by the polymerization reaction. The unit is a monomer unit represented by the following formula (II), and the most preferred monomer unit is a monomer unit represented by the following formula (III).

[0081]

[Chemical 13] [M represents an integer of 1 to 4. R ¹ is each independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, C ₂ -C
₂₀ unsaturated aliphatic hydrocarbon radical, C ₅ -C ₂₀ aryl group, C ₃ -C ₂₀ cycloalkyl group, at least one a cyclodienyl group, or a 5-10 membered ring, a C ₄ -C ₂₀ Is a heterocyclic group containing nitrogen, oxygen or sulfur as a hetero atom, R ² is each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, or a C _{2 to} C ₂₀ unsaturated aliphatic hydrocarbon. A group, a C _{5 to} C ₂₀ aryl group, a C _{3 to} C ₂₀ cycloalkyl group, a C _{4 to} C ₂₀ cyclodienyl group, or a 5 to 10 membered ring with at least one nitrogen, oxygen or sulfur hetero group. Is a heterocyclic group containing as an atom,
Alternatively, each R ² is independently two R ² — (CR ³ ₂ )
_n − (R ³ has the same meaning as R ¹ and n is an integer of 1 to 10) represents a bonding group or a group. ]

[0082]

Embedded image [Each R ² has the same meaning as defined in formula (II). ] The preferable carbon number of the said alkyl group is 2-10. The unsaturated aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms.
Is. The preferred carbon of the aryl group is 5-10. The cycloalkyl group preferably has 5 to 10 carbon atoms.
Is. The cyclodienyl group preferably has 5 to 5 carbon atoms.
It is 10. The preferred carbon number of the heterocyclic group is a 5- to 8-membered ring.

Specific examples of R ¹ and R ² of the above substituents include methyl group, ethyl group, n-propyl group, is
o-propyl group, n-butyl group, sec-butyl group, t
ert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, vinyl group, phenyl group,
Examples thereof include a tolyl group, a naphthyl group, a cyclopentadienyl group, an indenyl group, a pyridyl group and a piperidyl group.

When the cyclic conjugated diene block copolymer of the present invention is required to have elastomeric properties (rubber elasticity), at least two or more (polymer) block units having a Tg (glass transition temperature) higher than room temperature are used. It is necessary to have at least one (polymeric) block unit (rubber phase or soft segment) having a Tg lower than room temperature (having a constrained phase or hard segment) and forming a micro phase-separated structure with it.

The block copolymer having such a polymer chain structure can exhibit elastomeric properties (rubber elasticity) because the constrained phase acts as a physical crosslinking point when the constrained phase is less than Tg. On the other hand, since the polymer chains flow above Tg of the constrained phase, melt molding (injection molding, blow molding, extrusion molding, etc.) and solvent cast molding (film molding, etc.) are possible. Of course, the cyclic conjugated diene-based block copolymer of the present invention can exhibit elastomeric properties (rubber elasticity) by crosslinking the polymer chains.

Next, preferred embodiments when the cyclic conjugated diene polymer of the present invention is a block copolymer will be listed. (1) A cyclic conjugated diene block copolymer having a glass transition temperature (Tg) of 150 ° C. or higher. (2) A cyclic conjugated diene-based block copolymer having a block unit having a glass transition temperature (Tg) of 150 ° C. or higher.

(3) At least a triblock cyclic conjugated diene block copolymer. (4) A cyclic conjugated diene-based block copolymer having a block unit containing at least two or more monomer units A. (5) A cyclic conjugated diene-based block copolymer having a block unit consisting of at least two or more monomer units A. (6) At least one block unit consisting only of at least two or more monomer units A and at least one block unit consisting only of at least one monomer unit selected from monomer units B to E At least a diblock cyclic conjugated diene block copolymer.

(7) One block unit X containing at least one monomer unit A, and mainly monomer unit B
And one block unit Y composed of at least one monomer unit selected from the monomer unit E, and X
A cyclic conjugated diene block copolymer of a diblock having a weight ratio of / Y in the range of 1/99 to 99/1. (8) At least composed of at least two block units X containing at least one monomer unit A and at least one monomer unit selected from a monomer unit B and a monomer unit E An at least triblock cyclic conjugated diene-based block copolymer having one block unit Y and having an X / Y weight ratio in the range of 1/99 to 99/1.

(9) Two block units X containing at least one monomer unit A, and mainly monomer unit B
And one block unit Y composed of at least one monomer unit selected from the monomer unit E, and X
A triblock cyclic conjugated diene-based block copolymer having a weight ratio of / Y in the range of 1/99 to 99/1. (10) The structure is

[0090]

[Chemical 15] [However, p is an integer of 1 or more and q is an integer of 2 or more. X and Y have the same meaning as defined above. ] The cyclic | annular conjugated diene type block copolymer which is represented by this at least is a triblock.

The cyclic conjugated diene-based block copolymer of the present invention is mainly composed of a cyclic conjugated diene-based monomer unit (50 wt% or more of the block unit) or the same in order to develop elastomeric properties (rubber elasticity). At least two block units (X blocks) composed of a derivative or a cyclic conjugated diene monomer unit and a vinyl aromatic monomer unit, mainly (50 w of block unit).
It is preferable that the polymer main chain structure has at least one block unit (Y block) composed of a chain conjugated diene monomer unit or a derivative thereof (t% or more).

A block unit (X block) composed of a cyclic conjugated diene monomer unit or a derivative thereof.
It is more preferable that the polymer main chain structure has at least two and at least one block unit (Y block) mainly composed of a chain conjugated diene monomer unit or a derivative thereof. At least two block units (X blocks) composed of a monomer unit or a derivative thereof, or composed of a cyclic conjugated diene monomer unit and a vinyl aromatic monomer unit, mainly chain-conjugated It is particularly preferable that the polymer main chain structure is obtained by hydrogenating a polymer having at least one block unit (Y block) composed of a diene monomer unit or a derivative thereof. Furthermore, at least two block units (X blocks) composed of a cyclic conjugated diene monomer unit or its derivative, and a block unit composed mainly of a chain conjugated diene monomer or its derivative (Y Most preferably, the polymer main chain structure is obtained by hydrogenating a polymer having at least one block).

As an industrial material, 1,3-cyclohexadiene or 1,3-cyclohexadiene and styrene, or a monomer derived from α-methylstyrene as a monomer unit constituting the above X block is used. A unit is preferred, and as the monomer unit constituting the Y block,
Monomer units (including hydrogenated structures) derived from 1,3-butadiene and / or isoprene are preferred.

When the Y block is formed by polymerizing 1,3-butadiene and / or isoprene,
The amount of vinyl bonds in the Y block can be set arbitrarily and its range is not particularly limited, but when low temperature characteristics are required, it is relative to the total amount of cis and trans 1,4-bonds and vinyl bonds. , Vinyl bond is 10 ~ 90mol%
Is preferable, and the range of 20-80 mol% is the most preferable.

In the cyclic conjugated diene block polymer obtained by the production method of the present invention, a line represented by the following formula (IV) is a general formula of a preferable polymer main chain structure which exhibits elastomeric properties (rubber elasticity). The block copolymer and the radial block copolymer represented by the following formula (V) can be exemplified. (Y-X) _q , X- (Y-
X) _p , Y- (X-Y) _q (IV) [wherein p is an integer of 1 or more and q is an integer of 2 or more. ]

[0096]

Embedded image [P is an integer of 1 or more, and q is an integer of 2 or more.
Z is, for example, a residue of a polyfunctional coupling agent such as dimethyldichlorosilane, methylene chloride, silicon tetrachloride, tin tetrachloride, epoxidized soybean oil or an initiator such as a polyfunctional organic group A metal compound. Represent ].

As the cyclic conjugated diene block copolymer having a typical thermoplastic elastomer characteristic of the present invention,
10 to 60 wt% of X block, preferably 15 to 50
wt%, Y block 90-40 wt%, preferably 8
5 to 50 wt% and the number average molecular weight is 100
A triblock cyclic conjugated diene-based block copolymer represented by the following formula, XYX, which is 0 to 200,000, can be exemplified.

On the other hand, when the cyclic conjugated diene polymer of the present invention is adopted as a tough plastic, the X block content is 40 to 90 wt%, preferably 45 to 90 wt%.
85 wt%, Y block 60 to 10 wt%, preferably 55 to 15 wt%, and a number average molecular weight of 1,
A triblock cyclic conjugated diene-based block copolymer represented by the following formula, X-Y-X, which is 000 to 200,000 can be exemplified.

The cyclic conjugated diene polymer having the above-mentioned elastomer properties (rubber elasticity) is hydrogenated, halogenated,
It may be a polymer obtained by carrying out at least one reaction selected from hydrogenation, alkylation, arylation, ring opening and dehydrogenation. When the above polymer is required to have high thermal / mechanical / chemical performance, it is preferable to carry out the hydrogenation reaction subsequent to the polymerization reaction.

The method for producing the improved cyclic conjugated diene polymer according to the present invention will be described below, but the production method is not limited to the following. For example, in the present invention, a complex compound obtained by reacting at least one organometallic compound containing a metal of Group IA of the periodic table with at least one complexing agent (first complexing agent) and at least one complex compound The cyclic conjugated diene polymer can be obtained by carrying out a polymerization reaction using a stabilized polymerization catalyst composed of a mixture with a further complexing agent (second complexing agent).

The catalyst used in the method of the present invention is thermally stable and does not cause side reactions such as metallation. Using this catalyst, at least one cyclic conjugated diene monomer, or At least one cyclic conjugated diene monomer and at least one other monomer copolymerizable therewith (chain conjugated diene monomers, vinyl aromatic monomers, polar monomers, Ethylene monomer, and selected from the group consisting of α- olefin monomers),
Even under industrially advantageous high temperature conditions, not only the anionic polymerization of the cyclic conjugated diene-based monomer, particularly the living anion polymerization reaction proceeds, but also the obtained polymer has a narrow molecular weight distribution and the cyclic conjugated diene-based monomer The quantity is high 1,2
-A cyclic conjugated diene-based polymer having excellent heat resistance can be obtained because the polymer is linked in the polymer main chain depending on the bonding ratio.

In the production method of the present invention, a metal of Group IA of the Periodic Table which can be used as a polymerization catalyst (hereinafter often referred to as
Lithium, as an example of simply "Group IA metal")
Mention may be made of sodium, potassium, rubidium, cesium, and francium. Preferred is lithium, sodium or potassium, and particularly preferred is
Lithium or sodium, most preferably lithium.

The organometallic compound containing a Group IA metal of the present invention is an organometallic compound containing the above Group IA metals lithium, sodium, potassium, rubidium, cesium and francium. Examples of the preferable organic metal compound containing a Group IA metal include organic metal compounds containing lithium, sodium and potassium. As the particularly preferable organic metal compound containing a Group IA metal, an organic metal compound containing lithium and sodium can be exemplified, and as the most preferable organic metal compound containing a Group IA metal, an organic metal compound containing lithium is used. It can be illustrated.

That is, as the preferable organic metal compound in the present invention, an organic lithium compound, an organic sodium compound, and an organic potassium compound can be exemplified.
Particularly preferred are organic lithium compounds and organic sodium compounds, and most preferred are organic lithium compounds.

In the production method of the present invention, the organolithium compound most preferably used as the polymerization catalyst in the polymerization reaction means one or two organic lithium compounds bonded to an organic molecule or organic polymer containing at least one carbon atom. It is an organic compound or organic polymer compound containing the above lithium atom (including lithium ion).

Here, the organic molecule means a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon group, a C ₅ -C
₂₀ aryl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₄
To C ₂₀ cyclodienyl group can be exemplified. Examples of the organic polymer include polybutadiene, polyisoprene, polystyrene, poly-α-methylstyrene, polyethylene and the like.

Specific examples of the organolithium compound used in the production method of the present invention include methyllithium, ethyllithium, n-propyllithium, iso-propyllithium, n-butyllithium, sec-butyllithium and tert-butyl. Lithium, pentyl lithium, hexyl lithium, allyl lithium, cyclohexyl lithium, phenyl lithium, hexamethylene dilithium,
Cyclopentadienyl lithium, indenyl lithium,
9-fluorenyllithium, 9-anthrylmethyllithium, 1,1-diphenyl-n-hexyllithium,
1,1-diphenyl-3-methylpentyllithium, lithium naphthalene, butadienyldilithium, isoprenyldilithium, etc., or polybutadienyllithium, polybutadienyldilithium, polyisoprenyllithium, polyisoprenyldilithium Illustrative examples include known oligomeric or polymeric organic lithium containing a lithium atom in a part of a polymer chain such as lithium, polystyryllithium, polystyryldilithium, and poly-α-methyldilithium.

The type of the preferred organolithium compound is not particularly limited as long as it forms a stable complex, but typical organolithium compounds include methyllithium, ethyllithium, n-propyllithium and is.
o-propyllithium, n-butyllithium, sec-
Butyl lithium, tert-butyl lithium, and cyclohexyl lithium can be illustrated.

A preferred organolithium compound that can be industrially adopted is n-butyllithium (n-BuLi), se.
c-Butyllithium (s-BuLi) and tert-butyllithium (t-BuLi), and the most preferable organolithium compound is n-butyllithium (n-BuL).
i).

IA adopted in the production method of the present invention
The organometallic compound containing a group metal may be one kind or a mixture of two or more kinds as necessary. As described above, the polymerization catalyst in the production method of the present invention is IA
It is a mixture of a complex obtained by reacting at least one organometallic compound containing a group metal with at least one first complexing agent, and at least one second complexing agent. The types of the first complexing agent and the second complexing agent may be the same or different.

The types of the first complexing agent and the second complexing agent are not particularly limited, but each of the above-mentioned at least one first complexing agent and at least one second complexing agent (Hereinafter, often referred to simply as “complexing agent”) is independently capable of coordinating with the metal atom (or metal ion) contained in the organometallic compound containing a Group IA metal, A compound containing an element having an unshared electron pair, for example, an organic compound containing at least one element selected from the group consisting of oxygen (O), nitrogen (N), sulfur (S) and phosphorus (P). Is preferred. Among these organic compounds, ether compounds, metal alkoxides, amine compounds and thioether compounds are preferable. As a particularly preferred organic compound, a cyclic ether compound (tetrahydrofuran, crown ether, etc.),
Mention may be made of metal alkoxide compounds and amine compounds, most preferably amine compounds.

More specifically, a polar group R ¹ R ² N-group (which has an unshared electron pair and is capable of forming a complex by being coordinated with an organometallic compound containing a Group IA metal). R ¹ and R ^{2 each} represent an alkyl group, an aryl group, or a hydrogen atom, which may be the same or different.) Are organic amine compounds or organic polymer amine compounds containing one or more. You can do it. Among these amine compounds, particularly preferred amine compounds are
It is a tertiary (tertiary) amine compound and the most preferred tertiary (tertiary) amine compound is a tertiary (tertiary) diamine compound.

Specific examples of the complexing agent in the present invention include:
Diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 18-crown-
6, dibenzo-18-crown-6, 15-crown-
5, dibenzo-24-crown-8, cryptand, lithium-t-butoxide, potassium-t-butoxide,
Di-t-butoxybarium, porphyrin, 1,2-dipiperazinoethane, trimethylamine, triethylamine, tri-n-butylamine, quinuclidine, pyridine, 2-methylpyridine, 2,6-dimethylpyridine,
Dimethylaniline, diethylaniline, tetramethyldiaminomethane ,. Tetramethylethylenediamine, tetramethyl-1,3-propanediamine, tetramethyl-
2-butene-1,4-diamine, tetramethyl-1,4
-Butanediamine, tetramethyl-1,6-hexanediamine, tetramethyl-1,4-phenylenediamine,
Tetramethyl-1,8-naphthalenediamine, tetramethylbenzidine, tetraethylethylenediamine, tetraethyl-1,3-propanediamine, tetramethyldiethylenetriamine, tetraethyldiethylenetriamine ,.

Pentamethyldiethylenetriamine, pentaethyldiethylenetriamine, diazabicyclo [2,2]
2,2] octane, 1,5-diazabicyclo [4,3,
0] -5-nonene, 1,8-diazabicyclo [5,4,4]
0] -7-undecene, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, tetrakis (dimethylamino) ethylene, tetraethyl-2-butene-1,4-diamine, (-)-2,3
-Dimethoxy-1,4-bis (dimethylamino) butane (DBB), (+)-1- (2-pyrrolidinylmethyl)
Pyrrolidine, 2,2'-bipyridyl, 4,4'-bipyridyl, 1,10-phenanthroline, hexamethylphosphoramide (HMPA), hexamethylphosphorus triamide (HMPT) and the like can be exemplified.

The tertiary (tertiary) amine compound which is a preferable complexing agent in the present invention includes trimethylamine, triethylamine, tri-n-butylamine, quinuclidine, pyridine, 2-methylpyridine, 2,6-dimethylpyridine and dimethyl. Aniline, diethylaniline, tetramethyldiaminomethane (tetramethylmethylenediamine), tetramethylethylenediamine, tetramethyl-
1,3-propanediamine (tetramethylpropylenediamine), tetramethyl-2-butene-1,4-diamine, tetramethyl-1,4-butanediamine (tetramethylbutylenediamine), tetramethyl-1,6-hexane Diamine (tetramethylhexanediamine), tetramethyl-1,4-phenylenediamine, tetramethyl-1,8-naphthalenediamine, tetramethylbenzidine, tetraethylethylenediamine, tetraethyl-
1,3-propanediamine, tetramethyldiethylenetriamine, tetraethyldiethylenetriamine, pentamethyldiethylenetriamine ,.

Pentaethyldiethylenetriamine, 1,
4-diazabicyclo [2,2,2] octane, 1,5-
Diazabicyclo [4,3,0] -5-nonene, 1,8-
Diazabicyclo [5,4,0] -7-undecene, 1,
4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane, tetrakis (dimethylamino) ethylene, tetraethyl-2-butene-1,4-diamine, (-)-2,3-dimethoxy -1,4-bis (dimethylamino) butane (DBB), (+)-1-
(2-pyrrolidinylmethyl) pyrrolidine, 2,2'-bipyridyl, 4,4'-bipyridyl, 1,10-phenanthroline, hexamethylphosphoramide (HMPA),
Hexamethylphosphorus triamide (HMPT) and the like can be exemplified.

In the present invention, the particularly preferable complexing agent is an aliphatic amine compound, and the most preferable amine compound is an aliphatic diamine compound.

The most preferable aliphatic diamine compound is tetramethylmethylenediamine (TMMDA), tetraethylmethylenediamine (TEMDA), tetramethylethylenediamine (TMEDA), tetraethylethylenediamine (TEEDA), tetramethylpropylenediamine (TMPDA), tetraethylpropylene. Diamine (TEPDA), Tetramethyl butylene diamine (TMBDA), Tetra ethyl butylene diamine (TE
BDA), tetramethylpentanediamine, tetraethylpentanediamine, tetramethylhexanediamine (TMHDA), tetraethylhexanediamine (TE
HDA) and 1,4-diazabicyclo [2,2,2] octane (DABCO) can be exemplified.

The most preferable aliphatic diamine compound which can be industrially adopted is an aliphatic diamine represented by the following formula (IV) which reacts with an organolithium compound to form a stable complex compound and has a nitrogen-nitrogen atom Those having 1 to 6 carbon atoms are preferable, those having 1 to 3 carbon atoms are particularly preferable, and aliphatic diamine having 2 carbon atoms is most preferable. R ¹ R ² N (CH ₂ ) _n NR ³ R ⁴ (VI) [R ^{1 to} R ⁴ each independently represent a C _{1 to} C ₂₀ alkyl group. These may be the same or different. n
Is an integer of 1 to 20. ].

As a particularly preferable complexing agent in the present invention, tetramethylethylenediamine (TMEDA),
1,4-diazabicyclo [2,2,2] octane (DA
BCO) can be exemplified and the most preferable. As the complexing agent, tetramethylethylenediamine (TMEDA) can be exemplified. The above-mentioned complexing agent, preferably the amine compound, can be one kind or a mixture of two or more kinds, if necessary.

In the polymerization reaction in the production method of the present invention, the industrially preferable combination of the organometallic compound containing a Group IA metal and the complexing agent for synthesizing the complex compound as the polymerization catalyst is methyllithium (MeLi ), Ethyl lithium (EtLi), n-propyl lithium (n
-PrLi), iso-propyllithium (i-PrL)
i), n-butyllithium (n-BuLi), sec-
Butyllithium (s-BuLi), tert-butyllithium (t-BuLi), and an organic metal compound containing at least one Group IA metal selected from cyclohexyllithium (particularly an organic lithium compound), tetramethylmethylenediamine (TMMDA), Tetramethylethylenediamine (TMEDA), tetramethylpropylenediamine (TMPDA), tetramethylhexanediamine (TMHDA) and 1,4-diazabicyclo [2,2]
It is a combination composed of at least one complexing agent (especially amine compound) selected from 2,2] octane (DABCO).

The most preferred combination is n-butyllithium (n-BuLi), sec-butyllithium (s).
-BuLi) and tert-butyllithium (t-Bu
At least one organolithium compound selected from Li) and tetramethylethylenediamine (TMED
A) and a combination composed of at least one amine compound selected from 1,4-diazabicyclo [2,2,2] octane (DABCO).

The method of reacting an organometallic compound containing a Group IA metal with a first complexing agent to synthesize a complex is not particularly limited, and conventionally known techniques may be applied as necessary. it can. For example, a method in which an organometallic compound is dissolved in an organic solvent in a dry inert gas atmosphere and a solution of a complexing agent is added to synthesize a basic complex, or a complex is formed in a dry inert gas atmosphere. A method in which the agent is dissolved in an organic solvent and a solution of an organometallic compound is added to this to synthesize a basic complex can be exemplified, and the method is appropriately selected as necessary.

The above organic solvent is preferably selected according to the kind and amount of the organic metal and the kind and amount of the first complexing agent, and is preferably used after being sufficiently deaerated and dried.

The temperature condition for reacting the organometallic compound with the first complexing agent can also be appropriately selected generally in the range of -100 to 100 ° C. Industrially room temperature to 8
It is preferable to carry out in the range of 0 ° C, and most preferably in the range of room temperature to 60 ° C. The dry inert gas is preferably helium, nitrogen or argon, and industrially nitrogen or argon is preferably used. The above-mentioned basic complex is a complex formed by reacting the following organometallic compound containing a Group IA metal with a first complexing agent, and the organometallic compound containing a Group IA metal is 2 It is considered to have a state in which molecules or more, preferably 3 or more, and particularly preferably 4 or more molecules are associated.

The above complex is prepared by reacting at least one organometallic compound containing a metal of Group IA of the Periodic Table with at least one first complexing agent in a molar ratio shown by the following formula. . Generally, A ₁ / B ₁ = 200/1 to 1/100, preferably A ₁ / B ₁ = 100/1 to 1/80, more preferably A ₁ / B ₁ = 80/1 1/50, more preferably A ₁ / B ₁ = 50/1 to 1/20, particularly preferably A ₁ / B ₁ = 20/1 to 1/10, most preferably A ₁ / B ₁ = 1 /0.2～1/1.2 (however, the molar amount of a ₁ uses at least one of indicates the molar amount of group IA metal atom of the organometallic compound, which B ₁ represents at least one of the first complexing agent is used Indicates).

In the method of the present invention, the polymerization reaction is carried out by allowing a complex obtained by reacting an organometallic compound containing a Group IA metal with a first complexing agent and a second complexing agent to coexist in the form of a mixture. The following method can be given as a specific method for carrying out the method. (1) A method in which the second complexing agent is added in advance to the polymerization solvent, and then the complex is added, and then the polymerization reaction is carried out. (2) A method in which the complex is added to the polymerization solvent and then the second complexing agent is added to carry out the polymerization reaction. (3) A method of forming a complex in a polymerization solvent, adding a second complexing agent without isolating the complex, and conducting a polymerization reaction. (4) After the complex is formed in the polymerization solvent by using a large amount of the first complexing agent, the unreacted first complexing agent remaining without forming the complex is used as the second complexing agent to carry out the polymerization reaction. Method.

The above-mentioned various methods can be appropriately selected according to need. However, when the polymerization reaction is carried out at a high temperature, particularly at a temperature of 60 ° C. or higher, the above-mentioned methods (1) to (3) can be used. As shown, a method of polymerizing through a two-step process of forming a complex and mixing the complex and a second complexing agent is preferable. The amount of the second complexing agent that is allowed to coexist with the complex in the form of a mixture is not particularly limited. At least one organometallic compound,
It is preferable that the at least one first complexing agent and the at least one second complexing agent are present in a molar ratio represented by the following formula.

Generally, A ₃ / B ₃ = 100/1 to 1/200, preferably A ₃ / B ₃ = 80/1 to 1/100, more preferably A ₃ / B ₃ = 50 / 1 to 1/80, particularly preferably A ₃ / B ₃ = 20/1 to 1/50, most preferably A ₃ / B ₃ = 10/1 to 1/20 (where A ₃ is in the catalyst) Of the Group IA metal atom in the at least one organometallic compound, and B3 represents the total molar amount of the at least one first complexing agent and the at least one second complexing agent in the catalyst).

When the cyclic conjugated diene polymer obtained by the production method of the present invention requires particularly high thermal performance, that is, high 1,2-bond content in the monomer unit A, A ₃ / B ₃ = 2/1 to 1/10 is preferable, and A ₃ / B ₃ = 1.25 / 1 to 1/5 is the most preferable industrial production condition (A ₃ and B ₃ is as defined above).

The most preferable polymerization method in the present invention is
At least one organometallic compound containing a metal of Group IA of the Periodic Table and at least one first complexing agent are formed into a complex having a molar ratio represented by the following formula, and the complex and In this method, a polymerization catalyst obtained by mixing with a complexing agent is used to carry out a polymerization reaction. A ₂ / B ₂ = 1 / 0.25 to 1/1 (where A ₂ represents the molar amount of the group IA metal atom in at least one organometallic compound in the complex, and B ₂ represents at least one in the complex) The molar amount of the first complexing agent is shown).

As a typical polymerization method in the present invention,
N-Butyllithium (n-BuLi), sec-butyllithium (s-BuLi), and tert-butyllithium (t-), which are organometallic compounds containing a Group IA metal.
BuLi) and at least one organolithium compound (A ₂ mol) selected from tetramethylethylenediamine (TMEDA) and 1,4-diazabicyclo [2,2,2] octane (DABCO) as the first complexing agent. At least one amine compound (B ₂ mo
l) and the following molar ratio A ₂ / B ₂ = 1 / 0.25 to 1/1 (A ₂ and B ₂ are as defined above) to form a complex compound, and Set to range,
A method of carrying out the polymerization reaction under the condition that the second complexing agent coexists can be exemplified.

As the basic complex used in the production method of the present invention, a complex compound represented by the following formula (VII) can be exemplified as a preferable complex structure. [(X) _x · (Y) _y ] _k (VIII) [X represents one or more kinds of an organometallic compound containing a Group A metal. Y represents the first complexing agent. x, y,
k is an integer of 1 or more. ].

The complex synthesized by the above method is in a thermally unstable state and is considered to be stabilized by the second complexing agent. It is possible to carry out living anionic polymerization of a cyclic conjugated diene monomer even under a temperature condition of 60 ° C. or higher. Further, it becomes possible to produce a cyclic conjugated diene polymer having a narrow molecular weight distribution even under a temperature condition of room temperature or higher.

Furthermore, according to the above method, undesirable side reactions such as metallization are unlikely to occur even in the presence of a large amount of complexing agent, so that 1,2 having excellent heat resistance is obtained.
-It is possible to efficiently introduce a cyclic conjugated diene-based monomer unit containing a large number of bond structures into the polymer main chain. In addition,
The second complexing agent coexisting with the basic complex can be set variously according to the purpose, and therefore the kind thereof is not particularly limited, and it is the same as the complexing agent used for the synthesis of the basic complex. It may be different or different, but preferably the same is economically advantageous.

The polymerization mode in the production method of the present invention is not particularly limited, and gas phase polymerization, bulk polymerization (bulk polymerization), solution polymerization or the like can be appropriately selected and employed. As the polymerization reaction process, for example, batch type,
It is possible to select and use semi-batch type, continuous type, etc. as needed. The polymerization reactor may be appropriately selected according to the purpose and requirements, and examples thereof include an autoclave, a coil reactor, a tube reactor, a kneader and an extruder.

In the case where the polymerization reaction in the production method of the present invention is a solution polymerization, butane, n-pentane, n-hexane, n-heptane and n- are preferably used as a polymerization solvent.
Aliphatic hydrocarbon solvents such as octane, iso-octane, n-nonane, n-decane, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, norbornane Examples thereof include alicyclic hydrocarbon solvents, benzene, toluene, xylene, ethylbenzene, aromatic hydrocarbon solvents such as cumene, diethyl ether, tetrahydrofuran, ether solvents such as tetrahydropyran, and the like. It can be selected in a timely manner.

These polymerization solvents may be used singly or as a mixture of two or more if necessary. Examples of preferred polymerization solvents include aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents. The most preferred polymerization solvent is an aliphatic hydrocarbon solvent,
It is an alicyclic hydrocarbon solvent or a mixed solvent thereof. The most preferable polymerization solvent in the production method of the present invention is at least one polymerization solvent selected from n-hexane, cyclohexane and methylcyclohexane, or a mixed solvent of two or more thereof.

In the polymerization reaction in the production method of the present invention, the amount of the polymerization catalyst used may vary depending on the purpose, and therefore it is not particularly limited. As 1 × 10 ^-6 mol
To 5 × 10 ⁻¹ mol, preferably 5 × 10
^It can be carried out in the range of ^-6 mol to ¹ x 10 ^-1 mol.

The polymerization temperature in the polymerization reaction of the present invention is set to various values depending on the needs, but is generally -100 to 150 ° C, preferably -80 to 120 ° C, particularly preferably -30 to 110. ° C, most preferably 0 to 1
It can be carried out in the range of 00 ° C. Further, from an industrial viewpoint, it is preferable to carry out the polymerization reaction in the range of room temperature to 90 ° C, particularly preferably in the range of 30 to 85 ° C, and 40
The most preferred range is -80 ° C.

The time required for the polymerization reaction is not particularly limited because it varies depending on the purpose or the polymerization conditions, but it is usually within 48 hours, particularly preferably in the range of 0.5 to 24 hours. It is industrially most preferable to carry out for 1 to 10 hours.

The atmosphere of the reaction system in the polymerization reaction is preferably an inert gas such as helium, nitrogen or argon, which is sufficiently dry and has a high purity of an inert gas such as oxygen and carbon dioxide gas. Gas is particularly desirable.
From an industrial point of view, it is preferable to use sufficiently dry and highly pure nitrogen or argon, and it is most preferable to use nitrogen.

The pressure of the polymerization reaction system may be set within the above-mentioned polymerization temperature range within the pressure range necessary for maintaining each monomer and the polymerization solvent in the liquid phase, and is appropriately set as necessary. I can do things. In the polymerization reaction in the production method of the present invention, it is a predetermined condition that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the polymerization catalyst and the growing (active) terminal are kept in the polymerization system. To obtain the polymer of

In the production method of the present invention, in order to separate and recover the cyclic conjugated diene polymer from the polymer solution, it is usually used when recovering the polymer from a polymer solution (reaction solution) of a known polymer. It is possible to employ a conventionally known technique. For example, a steam coagulation method of directly contacting the reaction solution with steam, a reprecipitation method of adding a poor solvent for the polymer to the reaction solution to precipitate the polymer, a method of heating the reaction solution in a container to distill off the solvent, The method of contacting the reaction solution with a heating roll to distill off the solvent, the method of performing pelletization while distilling off the solvent with a vented extruder, after adding the polymer solution to warm water, the solvent and water with a vented extruder It is possible to exemplify a method of performing pelletization while distilling off, and an optimal method can be adopted depending on the properties of the cyclic conjugated diene polymer and the solvent used.

In the production method of the present invention, subsequent to the polymerization reaction, if necessary, at least one selected from hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation. It is also possible to carry out the reaction of. Each of the above reactions can be carried out without a catalyst if necessary, or in the presence of a conventionally known catalyst. For example, when the production method of the present invention comprises a step of carrying out a polymerization reaction and then a hydrogenation reaction, a polymerization reaction is carried out and a cyclic conjugated diene-based monomer unit is contained in the polymer main chain. A hydrogenated cyclic conjugated diene polymer obtained by synthesizing a polymer and then hydrogenating it in the presence of a hydrogenation catalyst to hydrogenate a part or all of the carbon-carbon unsaturated bonds contained in the polymer. Can be obtained.

As a concrete production method, the polymerization reaction of the polymer comprising a cyclic conjugated diene monomer unit or containing the same is stopped after the polymerization reaction reaches a predetermined (target) polymerization rate. Then, a method for producing a hydrogenated cyclic conjugated diene polymer can be exemplified by adding a hydrogenation catalyst into the reactor and introducing hydrogen gas, and subsequently carrying out a hydrogenation reaction. . More specifically, a method for producing a hydrogenated polymer batchwise by stopping the polymerization reaction by a conventional method, adding a hydrogenation catalyst in the same reactor in which the polymerization reaction was performed, and introducing hydrogen.

The polymerization reaction is stopped by a conventional method,
A method for producing a semi-batch hydrogenated polymer by transferring a polymer solution to a reactor separate from the polymerization reaction, adding a hydrogenation catalyst into the reactor, and introducing hydrogen. Alternatively,
A method of continuously producing a hydrogenated polymer by continuously carrying out a polymerization reaction and a hydrogenation reaction in a tube type reactor can be exemplified. These methods are
It can be appropriately selected and adopted as needed.

When the production method of the present invention includes a hydrogenation reaction, the hydrogenation reaction is carried out in the presence of a hydrogenated polymer and a hydrogenation catalyst in a hydrogen atmosphere. The method of the hydrogenation reaction in the production method of the present invention is generally carried out by maintaining the polymer solution at a predetermined temperature under hydrogen or an inert gas atmosphere, adding a hydrogenation catalyst with stirring or without stirring, and reacting. It is carried out by introducing hydrogen gas after maintaining the temperature and pressurizing it to a predetermined pressure. In addition, the hydrogenation reaction format is
Conventionally known techniques can be adopted. For example, any of a batch system, a semi-batch system, a continuous system, or a combination thereof can be adopted as necessary.

The hydrogenation catalyst which can be used in the hydrogenation reaction of the present invention is not particularly limited in kind and amount as long as it is a catalyst which can obtain a required hydrogenation rate, but it is practically a periodical method. Homogeneous hydrogenation catalyst (organometallic compound, organometallic complex) or heterogeneous hydrogenation catalyst (solid catalyst, supported catalyst) containing at least one metal selected from Group IVA to VIII metals or rare earth metals in the table ) Can be selected from.

The most preferred hydrogenation catalyst in the present invention is a homogeneous hydrogenation catalyst, that is, an organometallic compound or organometallic complex selected from IVA to VIII group metals or rare earth metals, or a group VIII metal supported catalyst (solid). Catalyst). These preferred homogeneous hydrogenation catalysts are organometallic compounds, organometallic complexes, silica, zeolite,
It is not particularly limited to be carried by an inorganic compound such as crosslinked polystyrene or an organic polymer compound.

Examples of particularly preferable metals contained in the hydrogenation catalyst used in the present invention include titanium, cobalt, nickel, ruthenium, rhodium and palladium. When these metals are homogeneous hydrogenation catalysts, ligands such as hydrogen, halogens, nitrogen compounds and organic compounds must be coordinated or bonded. These ligands may be used alone or in combination of two or more if necessary, but the combination of ligands is soluble in the solvent in which the polymer to be hydrogenated is dissolved. Is particularly preferable.

The hydrogenation catalysts may be used alone or in combination of two or more, if necessary, without any particular limitation.

Further, as the hydrogenation catalyst, at least one organic metal compound or organic metal complex selected from Group IVA to Group VIII metals or rare earth metals, and IA to IIA, IIIB such as alkyllithium, alkylmagnesium and alkylaluminum. The combination of at least one organometallic compound selected from the group metals is the most industrially preferable method.

On the other hand, when the hydrogenation catalyst is a solid catalyst,
Although it is possible to use the above metal as it is, it is generally preferable to use it in a state of being carried on a carrier such as carbon, alumina, silica, barium sulfate. Examples of preferred solid catalysts include supported catalysts containing at least one metal selected from rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum, and particularly preferably ruthenium, rhodium and A supported catalyst containing at least one metal selected from palladium can be exemplified. These catalysts are not particularly limited to be used alone or in combination of two or more kinds.

When the cyclic conjugated diene polymer obtained by the production method of the present invention is a hydrogenated polymer, the amount of the hydrogenation catalyst used in the hydrogenation reaction depends on the kind of the polymer to be hydrogenated (polymer main Chain structure, molecular weight, etc.) or hydrogenation conditions (solvent, temperature, concentration, solution viscosity, etc.). Generally, the metal atom concentration is 0.1 to 100, relative to the polymer to be hydrogenated. 000 ppm range, preferably 1-50,000 ppm range,
More preferably, it is in the range of 5 to 10,000 ppm,
It is particularly preferably used in the range of 10 to 10,000 ppm.

When the amount of the hydrogenation catalyst used is extremely small, a sufficient reaction rate cannot be obtained. On the other hand, when the amount of the hydrogenation catalyst used is large, the reaction rate increases but it is economically disadvantageous. The separation and recovery of the catalyst becomes difficult, and the adverse effect of the catalyst residue on the polymer is unavoidable, resulting in undesirable results.

In the production method of the present invention, the solvent which can be used in the hydrogenation reaction is preferably inert to the hydrogenation catalyst and has high solubility in the polymer to be hydrogenated.

Industrially, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent are preferable, and an aliphatic hydrocarbon solvent or an alicyclic hydrocarbon solvent, or a mixture thereof. Most preferred is a solvent. In the production method of the present invention, it is economically advantageous to carry out the hydrogenation reaction subsequent to the polymerization reaction from an industrial point of view, so the hydrogenation reaction is carried out in the same solvent as that used for the polymerization reaction. It is most preferable to do.

The concentration of the polymer solution during the hydrogenation reaction is not particularly limited, but is usually preferably 1 to 90 wt%, more preferably 2 to 60 wt%, particularly preferably 3 to 40 wt%. Is. When the concentration of the polymer solution is low, it is economically disadvantageous because the operation efficiency for the hydrogenation reaction is low, and when the concentration is high, the viscosity of the polymer solution increases and the reaction rate decreases. This results in unfavorable results.

The temperature of the hydrogenation reaction may be appropriately set as necessary, but is generally in the range of -78 to 500 ° C, preferably -10 to 300 ° C, particularly preferably 20 to It is 250 degreeC. If the reaction temperature is too low, a sufficient reaction rate cannot be obtained. On the other hand, if the reaction temperature is too high, the deactivation of the hydrogenation catalyst or the deterioration of the polymer may result in unfavorable results. become.

[0161] The pressure of the hydrogenation reaction in the production process of the present invention is in the range of 0.1~500kg / cm ² G, preferably in the range of 1~400kg / cm ² G, particularly preferably 2~300kg / Cm ² G range. When the pressure of hydrogen is low, a sufficient reaction rate cannot be obtained,
On the other hand, if the pressure is set too high, the reaction rate increases, but it is not economical because an expensive pressure resistant reaction device is required as the device. It also leads to undesirable results such as hydrogenolysis of the polymer.

The time required for the hydrogenation reaction depends on the amount and type of hydrogenation catalyst, the concentration of the polymer solution, the temperature of the reaction system,
Since it is also related to pressure, it is not possible to limit it in particular,
It can be carried out for usually 5 minutes to 240 hours, preferably 10 minutes to 100 hours, particularly preferably 30 minutes to 48 hours. After the completion of the hydrogenation reaction, the hydrogenation catalyst may be adsorbed by an adsorbent, separated by sedimentation, separated by filtration, separated by filtration, if necessary
It can be separated and recovered from the reaction solution by a conventionally known means such as a washing removal method with water or a lower alcohol in the presence of an organic acid and / or an inorganic acid.

In the production method of the present invention, in order to separate and recover the hydrogenated cyclic conjugated diene polymer from the polymer solution, it is generally carried out when recovering the polymer from the polymer solution of a known polymer. It is possible to adopt the conventionally known technology. For example, a steam coagulation method of directly contacting the reaction solution with steam, a reprecipitation method of adding a poor solvent for the polymer to the reaction solution to precipitate the polymer, a method of heating the reaction solution in a container to distill off the solvent, The method of contacting the reaction solution with a heating roll to distill off the solvent, the method of performing pelletization while distilling off the solvent with a vented extruder, after adding the polymer solution to warm water, the solvent and water with a vented extruder It is possible to exemplify a method of performing pelletization while distilling off, and an optimal method can be adopted depending on the properties of the cyclic conjugated diene polymer and the solvent used.

1, obtained by the polymerization method of the present invention,
A polymer obtained by hydrogenating the monomer unit A of a cyclic conjugated diene polymer having a high content of the monomer unit A having a 2-bond is an industrial polymer having particularly high thermal and mechanical properties. Is the most preferable material. As described above, in the production method of the present invention, subsequent to the polymerization reaction, if necessary, further selected from hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation. It is also possible to carry out at least one reaction.

That is, after the polymerization reaction, if necessary, the hydrogenation reaction and / or other addition reaction, or the reaction selected from the elimination reaction and the ring opening reaction can be appropriately selected and carried out. It is preferable to carry out an optimal reaction depending on the purpose. Each of the above reactions can be carried out without a catalyst if necessary, or in the presence of a conventionally known catalyst.

In the production method of the present invention, a dehydrogenation reaction can be exemplified as a more specific and suitable elimination reaction for a polymer, which can be carried out by directly adopting a conventionally known technique. it can. More specifically, by the polymerization reaction according to the production method of the present invention, a cyclic conjugated diene polymer serving as a precursor is polymerized, and continuously or after the cyclic conjugated diene polymer is separated and recovered, the polymer is subsequently polymerized. It is a reaction for converting a part or all of the monomer unit A contained therein to an aromatic ring.

For the dehydrogenation reaction of the present invention, a conventionally known technique can be adopted as it is and is not particularly limited, but preferably, a part or all of the monomer unit A in the polymer chain is an aromatic ring, It is desirable that it can be converted into a benzene ring. The dehydrogenation reaction in the present invention may be a catalytic reaction or a stoichiometric reaction, and in general, the precursor cyclic conjugated diene polymer as it is, if necessary, the polymer as a solvent, preferably Is diluted with an organic solvent, a dehydration catalyst, a dehydrogenation reagent and the like are added as necessary, and the reaction is carried out under predetermined conditions.

The dehydrogenation reaction of the present invention is carried out by directly extracting a hydrogen atom or molecule from a monomer unit in a polymer chain, or in a state of being bonded to another compound such as hydrogen halide or hydrogen sulfonate. A conventionally known reaction form such as a drawing method or a drawing method by a disproportionation reaction,
Can be adopted as needed. A simple dehydrogenation reaction using commonly available reagents is quinone (qu
Inone) can be used as a dehydrogenation reagent.

Typical quinones are 1,4-benzoquinone (quinone), tetrachloro-1,2-benzoquinone (o-chloranil), tetrachloro-1,4-benzoquinone (p-chloranyl) and tetrabromo-1. , 2-benzoquinone (o-bromanyl), tetrabromo-1,4
-Benzoquinone (p-bromanyl), tetrafluoro-
1,2-benzoquinone, tetrafluoro-1,4-benzoquinone, tetraiodo-1,2-benzoquinone, tetraiodo-1,4-benzoquinone, tetrahydroxy-
1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-p-benzoquinone, 1,2-naphthoquinone,
1,4-naphthoquinone, anthraquinone, 1-chloroanthraquinone, 1-bromoanthraquinone, 1-fluoroanthraquinone, 1-iodoanthraquinone, 2,6
Examples thereof include dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone, 1,4,4a, 9a-tetrahydroanthraquinone, and phenanthrenequinone.

Among these quinones, 1,4-benzoquinone (quinone), tetrachloro-1,2-benzoquinone (o-chloranil) and tetrachloro are used for industrially carrying out the dehydrogenation reaction. -1,4-benzoquinone (p
-Chloranil), tetrabromo-1,2-benzoquinone (o-bromanyl), tetrabromo-1,4-benzoquinone (p-bromanyl) is preferably used, and tetrachloro-1,4-benzoquinone (p-chloranyl) is used. It is most preferable to do.

In the dehydrogenation reaction of the present invention, when the cyclic conjugated diene polymer is dissolved in an organic solvent to carry out the dehydrogenation reaction, the cyclic conjugated diene polymer as a precursor is sufficiently dissolved as the organic solvent. The kind and amount thereof are not particularly limited as long as they are provided, and may be appropriately selected depending on the solubility of the cyclic conjugated diene polymer.

Examples of these organic solvents include butane,
Aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, n-octane, iso-octane, n-nonane, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethyl Alicyclic hydrocarbon solvents such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, cumene, diethyl ether, tetrahydrofuran, tetrahydropyran, etc. Ether solvents, chloroform, methylene chloride,
Examples thereof include halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene.

The reaction temperature in the dehydrogenation reaction is set to be different depending on the need, but it is generally 0 to 3
50 ° C, preferably 0-300 ° C, particularly preferably 0-
It can be carried out at 250 ° C, most preferably in the range of 0 to 200 ° C. From an industrial point of view, room temperature to 200
It is advantageous to carry out in the range of ° C.

The time required for the dehydrogenation reaction varies depending on the purpose or the reaction conditions and is not particularly limited, but is usually 48 hours or less, and particularly preferably 1 to 24 hours. Be implemented. The atmosphere in the dehydrogenation reaction system is preferably an inert gas such as nitrogen, argon or helium, particularly a sufficiently dry inert gas having a high purity in order to suppress side reactions.

The pressure of the reaction system is not particularly limited as long as it is within the above reaction temperature range and is sufficient to maintain the catalyst, the reagent, the solvent and the like in the liquid phase. In addition, impurities such as water, oxygen, carbon dioxide gas that inactivate the dehydrogenation catalyst and dehydrogenation reagent, or cause crosslinking and decomposition of the precursor cyclic conjugated diene polymer in the reaction system. It is preferable to carry out the dehydrogenation reaction while paying attention not to mix such substances.

In order to separate and recover the polymer from the polymer solution after completion of the dehydrogenation reaction, a conventionally known technique which is usually used when recovering a polymer from a polymer solution of a known polymer is adopted. You can do it. For example, a steam coagulation method of directly contacting the reaction solution with steam, a reprecipitation method of adding a poor solvent for the polymer to the reaction solution to precipitate the polymer, a method of heating the reaction solution in a container to distill off the solvent, The method of contacting the reaction solution with a heating roll to distill off the solvent, the method of performing pelletization while distilling off the solvent with a vented extruder, after adding the polymer solution to warm water, the solvent and water with a vented extruder It is possible to exemplify a method of performing pelletization while distilling off, and an optimal method can be adopted depending on the properties of the cyclic conjugated diene polymer and the solvent used. Furthermore,
Examples of the ring-opening reaction in the production method of the present invention include ozone oxidation reaction and nitric acid oxidation reaction.

The cyclic conjugated diene polymer obtained by the production method of the present invention comprises a stabilizer such as a heat stabilizer, an antioxidant and an ultraviolet absorber, a lubricant, a nucleating agent, a plasticizer, depending on the purpose and use thereof. Dye, pigment, cross-linking agent, foaming agent, antistatic agent, anti-slip agent, anti-blocking agent, release agent,
It is not particularly limited to contain additives, reinforcing agents, etc., which are added or blended with general polymer materials, such as other polymer materials and inorganic reinforcing materials (glass filler, mineral fiber, inorganic filler, etc.). Absent.

As a stabilizer such as a heat stabilizer, an antioxidant and an ultraviolet absorber, a conventionally known stabilizer can be directly used. For example, it is possible to employ various heat stabilizers such as phenol-based, organic phosphate-based, organic phosphite-based, organic amine-based, and organic sulfur-based heat stabilizers, antioxidants, and ultraviolet absorbers. The stabilizers such as heat stabilizers, antioxidants, and ultraviolet absorbers are generally added in an amount of 0.001 to 10 wt% with respect to the cyclic conjugated diene polymer.

The cyclic conjugated diene-based polymer obtained by the production method of the present invention may be used as a single material depending on its purpose and application, or may be another polymer material (including a cyclic conjugated diene-based polymer) or an inorganic reinforced material. -It can also be used as a composite material with an organic reinforcing material. When the cyclic conjugated diene polymer obtained by the production method of the present invention is used as a composite material (resin composition), other polymer materials to be blended may be selected from conventionally known organic polymers as necessary. It is possible to select, and the kind and amount are not particularly limited.

The cyclic conjugated diene polymer obtained by the production method of the present invention is used as an excellent industrial material (structural material or functional material) as a high performance plastic, general-purpose plastic, special elastomer, thermoplastic elastomer, elastic fiber, Sheet, film, tube, hose, optical material, coating agent, insulating agent, lubricant, plasticizer, separation membrane,
Permselective membrane, microporous membrane, functional membrane, functional film (conductive film, photosensitive film, etc.), functional beads (molecular sieve, polymer catalyst, polymer catalyst substrate, etc.), automobile parts, electrical parts, aviation・ Space parts, railway parts, marine parts,
Electronic parts, battery parts, electronics related parts, multimedia related parts, plastic materials for batteries, solar cell parts, functional fibers, functional sheets, machine parts, medical device parts, pharmaceutical packaging materials, sustained release packaging materials, Pharmaceutical substance support substrate, printed circuit board material, food container, general packaging material, clothing, sports / leisure goods, general miscellaneous goods, tires,
Not only used as a modifier for belts and other resins, but also as a curable resin such as thermosetting resin, UV curable resin, electron beam curable resin, wet curable resin, etc. by adding a cross-linking agent as required. It can also be used as.

[0181]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples and is not construed. The chemicals used in this invention were of the highest purity available.
General solvents are degassed according to the usual method, under an inert gas atmosphere,
What was refluxed and dehydrated on an active metal, and then distilled and purified was used.

The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer were measured by using a liquid chromatograph (HLC-8082) manufactured by Tosoh Corporation of Japan, and Showa Denko (Japan). Co., Ltd. column (Showdex: K
805 + K804 + K802), and G. P. C
The values in terms of standard polystyrene measured by the (gel permeation chromatography) method are shown.

Polymer chain structure analysis was carried out using an NMR measuring device (JEOL α-400) manufactured by JEOL, Japan. Measurement frequency, 400MHz ⁽¹ H), 100M
Hz ( ¹³ C). O-Dichlorobenzene-d ₄ was used as the solvent at the time of measurement, and the sample concentration was 10 wt%, 1
The measurement was performed at 35 ° C. At the time of measurement, the peak of cyclohexane was referred to as 1.4 ppm.

Ratio of 1,2-bonds and 1,4-bonds of polycyclohexadiene (molar ratio of 1,2-bonded monomer units and 1,4-bonded monomer units) Was calculated by the following method. 1,2-bonded CHD monomer unit (1,2-CHD) and 1,4-bonded CH
In the D monomer unit (1,4-CHD), the number of protons (Ha) adjacent to the olefin is different (FIG. 1).

In the case of 1,2-CHD, Ha / (Ha +
Hb) = 1/2, and in the case of 1,4-CHD, Ha
/ (Ha + Hb) = 1/3. That is, if the proportion of protons (H) that correlates with olefins is calculated,
The composition ratio of 1,2-bond and 1,4-bond is obtained.

When a peak correlated with an olefin was measured by the H-H COZY method, H (5.5 to 5.8 ppm) derived from the olefin and 1.85 to 2.35 p were obtained.
A cross peak was observed at H of pm (FIGS. 2 and 3). For the H-H COZY method, for example, "NMR of Polymer / Biomolecule" p. 31-41 (edited by Riichiro Nakajo, edited by Isao Ando and Yoshio Inoue, Tokyo Kagaku Dojin, 1992)
Year) can be referred to. Therefore, 1.85-2.
It was confirmed that 35 ppm of H was H (Ha) next to the olefin.

Here, the ratio of 1,2-CHD is α, and the ratio of 1.
The ratio of the peak area of H of 85 to 2.35 ppm (Ha /
If Ha + Hb) is β, the following equation becomes 1/2 × α + 1/3 (1-α) = β, and by calculating α from this, 1,2-CH
The ratio of D was calculated.

The chemical shift of the polymerization catalyst (complex) is measured by the NMR measuring device (JEOL α-4, manufactured by JEOL, Japan).
00). Measurement frequency is 400MHz
( ¹ H), 100 MHz ( ¹³ C), 155 MHz ( ⁷ L
i), measured at 58.7 ( ⁶ Li). ⁷ Li, ⁶ Li
Chemical shift of 1M-LiCl (inD ₂ O) =
It was measured as 0 ppm.

The glass transition temperature (Tg) of the polymer was a value measured by the DSC method using DSC200 manufactured by Seiko Denshi Kogyo KK of Japan. The conversion rate (mol%) of the monomer in the polymerization reaction system is a gas chromatograph (GC14A) manufactured by Shimadzu Corporation, Japan.
The value calculated by measuring the absolute amount of the monomer remaining in the reaction system (by the internal standard method) is shown. Ethylbenzene was used as the internal standard substance.

The mechanical and thermal practical properties of the polymer can be measured by
The procedure was as follows. Tensile test (1/8 inch) Tested according to ASTM D638. Tensile Strength (TS), Tensile Elongation (TE) Bending Test (1/8 inch) Tests were performed according to ASTM D790. Flexural Strength (FS), Flexural Modulus (FM) Izod Impact Test A test was conducted according to ASTM D256 (normal temperature). Heat distortion temperature (HDT: ° C) High load 1.82 MPa according to ASTM D648,
The test was conducted under the condition of a low load of 0.46 MPa. 1 MPa = 10.20 kg · f / cm ² 1 J / m = 0.102 kg · cm / cm.

In the following examples and comparative examples, for example, polycyclohexadiene-polyisoprene diblock copolymer is simply referred to as "CHD-Ip diblock copolymer". The same applies to other block copolymers.

[0192]

【Example】

Example 1 <Synthesis of Complex Formed from Organometallic Compound Containing Group IA Metal and First Complexing Agent> Under dry argon atmosphere, known amount of N, N, N ′, N′-tetramethylethylenediamine (TMEDA) ) (First complexing agent) was dissolved in cyclohexane to prepare a 1.0 M cyclohexane solution of TMEDA. Then, the solution is cooled and kept at -10 ° C,
Under a dry argon atmosphere, n-butyl lithium (n-B
A predetermined amount of n-BuLi n-hexane solution was slowly added so that uLi) / TMEDA = 4/2 (mol ratio).

When the n-BuLi solution was dropped into the TMEDA solution, TMEDA and n-BuLi rapidly reacted,
A white crystalline complex was formed. After heating and dissolving the reaction solution to 70 ° C., the reaction solution was gradually cooled to −78 ° C. to precipitate a white (plate-like) crystal complex. Then, the obtained complex was filtered under a dry argon atmosphere and washed with cyclohexane repeatedly to purify the complex of white (plate-like) crystals. When ¹ H-NMR of this complex was measured, the n-BuLi / TMEDA ratio in the complex was 4/2.

<Polymerization reaction> Sufficiently dried according to a conventional method 1
The inside of the 00 ml Schlenk tube was replaced with dry argon. 27.0 g of cyclohexane was injected into the Schlenk tube, and the temperature of the solution was kept at room temperature. Furthermore, the above n-B
A complex of uLi / TMEDA = 4/2 (molar ratio) was added and dissolved in an amount of 0.3 mmol in terms of lithium atom, and the temperature of the solution was raised to and maintained at 70 ° C.

To this solution, a 1.0 M solution of TMEDA (second complexing agent) in cyclohexane was added so that TMEDA (second complexing agent) was 0.225 mmol, and the mixture of the complex and TMEDA was added. A cyclohexane solution was obtained.
At this point, Li / TMEDA was 4/5 (molar ratio). Furthermore, 1,3-cyclohexadiene (1,3) was added to a cyclohexane solution of the mixture of the obtained complex and TMEDA.
3-CHD) (3.0 g) was added, and the polymerization reaction was performed at 70 ° C. for 1 hour in a dry argon atmosphere.

After completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of methanol / hydrochloric acid mixed solvent. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer with a yield of 100 wt%. The resulting cyclohexadiene (C
The number average molecular weight (Mn) of HD) homopolymer is 9,70.
And the molecular weight distribution (Mw / Mn) was 1.28. 1,2-of the cyclic conjugated diene-based monomer units in the polymer
The bond / 1,4-bond ratio is 56/44 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method.
Was 154 ° C.

Example 2 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at 40 ° C. An n-hexane solution of n-BuLi (1.6 M) was converted into a lithium atom and converted to 0.3 mmo.
1 and added and stirred for 10 minutes. Then, a 1.0 M cyclohexane solution of TMEDA (first complexing agent) was prepared. This solution was added to n-BuLi / TMEDA = 4/2 (m
ol ratio) and reacted at 40 ° C. for 10 minutes, and the resulting complex solution was heated to and maintained at 70 ° C.

To this solution, a 1.0 M solution of TMEDA (second complexing agent) in cyclohexane was additionally added so that TMEDA (second complexing agent) was 0.225 mmol, and a mixture of the complex and TMEDA was added. A cyclohexane solution was obtained.
At this point, Li / TMEDA was 4/5 (molar ratio). Furthermore, 3.0 g of 1,3-CHD was added to a cyclohexane solution of the mixture of the obtained complex and TMEDA,
The polymerization reaction was carried out at 70 ° C. for 1 hour in a dry argon atmosphere.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further added with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer with a yield of 100 wt%. The number average molecular weight (Mn) of the obtained CHD homopolymer was 9,300, and the molecular weight distribution (Mw / Mn) was 1.36. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 51/49 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method is It was 152 ° C.

Comparative Example 1 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. An n-hexane solution (1.6M) of n-BuLi is 0.30 mm in terms of lithium atom.
and added for 10 minutes. Furthermore, 1,3-CHD
3.0 g was added, and a polymerization reaction was carried out at room temperature for 6 hours in a dry argon atmosphere. The anion color disappeared immediately after the reaction started.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further added with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and dried in vacuum at 80 ° C. Yield is 23 wt%
It was nothing more than The number average molecular weight (Mn) of the obtained CHD homopolymer was 3,200, and the molecular weight distribution (Mw)
/ Mn) was 2.89. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer unit in the polymer is 5
/ 95 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method was only 88 ° C.

Comparative Example 2 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at 40 ° C. An n-hexane solution (1.6M) of n-BuLi is 0.30 mm in terms of lithium atom.
and added for 10 minutes. Furthermore, 1,3-CHD
3.0 g was added and the mixture was dried at 40 ° C. under a dry argon atmosphere for 6 minutes.
The polymerization reaction was carried out for a time. The anion color disappeared immediately after the reaction started.

After completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and a large amount of a mixed solvent of methanol / hydrochloric acid was added to the polymer. Was separated, washed with methanol, and dried in vacuum at 80 ° C. Yield is 20wt%
It was nothing more than The number average molecular weight (Mn) of the obtained CHD homopolymer was 2,920, and the molecular weight distribution (Mw)
/ Mn) was 2.92. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer unit in the polymer is 2
/ 98 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method was only 87 ° C.

Examples 3 to 6 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. Furthermore, a complex of n-BuLi / TMEDA = 4/2 (mol ratio) obtained in the same manner as in Example 1 was added and dissolved in an amount of 0.15 mmol in terms of lithium atom, and the temperature of the obtained complex solution was adjusted. The temperature was raised to and maintained at 40 ° C.

To this solution, a 1.0 M solution of TMEDA in cyclohexane was added to the solution of TMEDA (second complexing agent) in an amount of 0.2
0375, 0.0750, 0.1125, 0.150m
The cyclohexane solution of the mixture of the complex and TMEDA was obtained by additionally adding so as to become mol. Li / TM at this point
EDA = 4/3, 4/4, 4/5, 4/6 (mol ratio)
Met.

Further, 3.0 g of 1,3-CHD was added to a cyclohexane solution of the obtained mixture of the complex and TMEDA, and a polymerization reaction was carried out at 40 ° C. for 4 hours in a dry argon atmosphere. After completion of the polymerization reaction, BHT [2,6-bis (t
-Butyl) -4-methylphenol] 10 wt% methanol solution was added to stop the reaction, and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid, washed with methanol, and vacuum dried at 80 ° C. All yields are 100 wt
%Met. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 48/52, 5 and 5, respectively.
It was 1/49, 52/48, 54/46 (mol ratio).

Comparative Examples 3 to 6 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. Further, an n-BuLi solution of n-BuLi (1.6 M) was added in an amount of 0.15 m in terms of lithium atom.
mol was added, and the temperature of the solution was raised to and maintained at 40 ° C. To this solution, a 1.0 M solution of TMEDA in cyclohexane was added, and TMEDA contained 0.0047 and 0.009, respectively.
4, 0.0188, and 0.0375 mmol were added, and the mixture was stirred for 10 minutes. At this point Li / TMED
A = 4 / 0.125, 4 / 0.25, 4 / 0.5, 4 /
It was 1 (mol ratio).

Furthermore, 3.0 g of 1,3-CHD was added,
The polymerization reaction was carried out at 40 ° C. for 4 hours under a dry argon atmosphere. After completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and a large amount of methanol /
The polymer was separated with a hydrochloric acid mixed solvent, washed with methanol, and dried in vacuum at 80 ° C. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the obtained polymer was 6/94, 9/91, 21/79, 29/71, respectively.
(Mol ratio).

Example 7 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. Furthermore, an n-BuLi solution of n-BuLi (1.6 M) was converted to a lithium atom content of 0.30 m.
mol was added and stirred for 10 minutes. Then N, N,
N ', N',-tetramethylpropylenediamine (TM
PDA) (first complexing agent) is dissolved in cyclohexane and T
A 1.0 M cyclohexane solution of MPDA was prepared.
This solution was added to n-BuLi / TMPDA = 4/2 (mol
Ratio) and reacted at room temperature for 10 minutes, and the resulting complex solution was heated to 40 ° C. and held.

To this solution, a 1.0 M solution of TMPDA (second complexing agent) in cyclohexane was added so that the amount of TMPDA (second complexing agent) was 0.225 mmol, and the mixture of the complex and TMPDA was added. A cyclohexane solution was obtained.
At this point, Li / TMPDA was 4/5 (molar ratio).

Further, 3.0 g of 1,3-CHD was added to a cyclohexane solution of the mixture of the obtained complex and TMPDA, and a polymerization reaction was carried out at 40 ° C. for 4 hours in a dry argon atmosphere. After completion of the polymerization reaction, BHT [2,6-bis (t
-Butyl) -4-methylphenol] 10 wt% methanol solution was added to stop the reaction, and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid, washed with methanol, and vacuum dried at 80 ° C. The yield was 100 wt%. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer units in the obtained polymer was 47/53 (m
ol ratio).

Examples 8 to 12 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 20.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. Further, 0.07 mmol of a complex composed of n-BuLi / TMEDA = 4/2 (mol ratio) synthesized in the same manner as in Example 1 was added and dissolved in terms of lithium atom, and the temperature of the obtained complex solution was set to 60. The temperature was raised to and maintained at ℃.

To this solution, a 1.0 M solution of TMEDA (second complexing agent) in cyclohexane was added additionally while changing the amount of TMEDA (second complexing agent) to be added.
A cyclohexane solution of the mixture of A was obtained. Furthermore, in a cyclohexane solution of the mixture of the obtained complex and TMEDA,
3.0 g of 1,3-CHD was added, and a polymerization reaction was carried out at 60 ° C. for 4 hours in a dry argon atmosphere.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of methanol / hydrochloric acid mixed solvent. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the obtained polymer was 44/56, 5 respectively.
2/48, 54/46, 56/44, 60/40 (mo
1 ratio). The results are shown in Table 1.

[0215]

[Table 1] .

Comparative Example 7 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. Further, an n-BuLi solution of n-BuLi (1.6 M) was added in an amount of 0.15 m in terms of lithium atom.
mol is added, and the temperature of the solution is raised to 60 ° C. and maintained,
Stir for 10 minutes. Add 1,3-CHD 3.0g,
The polymerization reaction was carried out at 60 ° C. for 4 hours under a dry argon atmosphere. In this polymerization method, the color of the cyclohexadienyl anion disappeared immediately after the initiation of the polymerization, and the polymer was not recovered.

Example 13 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. An n-hexane solution of n-BuLi (1.6M) was used as a lithium atom and was 0.15 mm.
and added for 10 minutes. Then TMEDA
A 1.0 M cyclohexane solution of (first complexing agent) was prepared. This solution was added to n-BuLi / TMEDA = 4/2.
(Mol ratio), and the mixture was reacted at room temperature for 10 minutes, and the obtained complex solution was heated to and maintained at 40 ° C.

To this solution, a 1.0 M solution of TMEDA (second complexing agent) in cyclohexane was added so that TMEDA (second complexing agent) was 0.1125 mmol.
A cyclohexane solution of the complex and TMEDA mixture was obtained. At this point, Li / TMEDA = 4/5 (molar ratio)
Met. Further, 3.0 g of 1,3-CHD was added to a cyclohexane solution of the obtained mixture of the complex and TMEDA, and a polymerization reaction was carried out at 40 ° C. for 4 hours under a dry argon atmosphere.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer with a yield of 100 wt%. The number average molecular weight (Mn) of the obtained CHD homopolymer was 19,750, and the molecular weight distribution (Mw / Mn) was 1.09. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 50/50 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method is It was 156 ° C.

Example 14 A polymerization reaction was performed in the same manner as in Example 13 except that the reaction temperature of n-BuLi and TMEDA was 60 ° C. The number average molecular weight (Mn) of the obtained CHD homopolymer was 2
0,800 and the molecular weight distribution (Mw / Mn) is 1.2.
It was 6. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 52/48 (mol
Ratio), and the glass transition temperature (Tg) measured by the DSC method was 155 ° C.

Example 15 A polymerization reaction was performed in the same manner as in Example 13 except that the reaction temperature of n-BuLi and TMEDA was 40 ° C. The number average molecular weight (Mn) of the obtained CHD homopolymer was 2
It is 0.060, and the molecular weight distribution (Mw / Mn) is 1.1.
It was 4. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer was 54/46 (mol
Ratio), and the glass transition temperature (Tg) measured by the DSC method was 159 ° C.

Comparative Example 8 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. An n-hexane solution of n-BuLi (1.6M) was used as a lithium atom and was 0.15 mm.
and added for 10 minutes. Furthermore, 1,3-CHD
3.0 g was added, and a polymerization reaction was carried out at room temperature for 6 hours in a dry argon atmosphere. The anion color disappeared immediately after the reaction started.

After completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and dried in vacuum at 80 ° C. The yield was only 18 wt%. The number average molecular weight (Mn) of the obtained CHD homopolymer was 2,750, and the molecular weight distribution (Mw /
Mn) was 3.19. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 2 /
It was 98 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method was only 87 ° C.

Example 16 The inside of a 300 ml pressure-resistant glass bottle that had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 12
0.0 g was poured into a pressure resistant bottle, and the temperature of cyclohexane was kept at room temperature. An n-hexane solution of n-BuLi (1.6 M) was used as a lithium atom and converted to 3.0 mmo.
1 and added and stirred for 10 minutes. Then, a 1.0 M cyclohexane solution of TMEDA (first complexing agent) was prepared. This solution was added to n-BuLi / TMEDA = 4/2 (m
ol ratio) and reacted at room temperature for 10 minutes, and the resulting complex solution was heated to and maintained at 40 ° C.

To this solution, a 1.0 M solution of TMEDA (second complexing agent) in cyclohexane was added so that TMEDA (second complexing agent) was 2.25 mmol, and the mixture of the complex and TMEDA was added. A cyclohexane solution was obtained. At this point, Li / TMEDA was 4/5 (molar ratio). To this solution, 4.5 g of 1,3-CHD was added, and a polymerization reaction was carried out at 40 ° C. for 1 hour in a dry argon atmosphere.

Next, 21.0 g of isoprene (Ip) was added, and a CHD-Ip diblock copolymer was synthesized by carrying out a polymerization reaction at 40 ° C. for 1 hour in a dry argon atmosphere. Next, 4.5 g of 1,3-CHD was added and a CHD-Ip-CHD triblock copolymer was obtained by carrying out a polymerization reaction at 40 ° C. for 2 hours in a dry argon atmosphere.

After completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to terminate the reaction, and the polymer was further mixed with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and vacuum dried at 60 ° C. to obtain a viscous polymer with a yield of 100 wt%. The number average molecular weight (Mn) of the obtained CHD-Ip-CHD triblock copolymer was 9,8.
90, and the molecular weight distribution (Mw / Mn) was 1.04. The content of the cyclic conjugated diene monomer unit in the polymer measured by ¹ H-NMR was in agreement with the charged composition. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 43/57 (mol
Ratio).

Example 17 The inside of a 300 ml pressure-resistant glass bottle that had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 12
0.0 g was poured into a pressure resistant bottle, and the temperature of cyclohexane was kept at room temperature. A solution of s-BuLi in n-hexane (1.1 M) was converted into lithium atom to obtain 3.0 mmo.
1 and added and stirred for 10 minutes. Then, a 1.0 M cyclohexane solution of TMEDA (first complexing agent) was prepared. This solution was added to s-BuLi / TMEDA = 4/2 (m
ol ratio) and reacted at room temperature for 10 minutes, and the resulting complex solution was heated to and maintained at 40 ° C.

To this solution, a 1.0 M solution of TMEDA (second complexing agent) in cyclohexane was additionally added so that TMEDA (second complexing agent) was 2.25 mmol, and a mixture of the complex and TMEDA was added. A cyclohexane solution was obtained. At this point, Li / TMEDA was 4/5 (molar ratio).

A cyclohexane solution of the mixture of the obtained complex and TMEDA was added to m-diisopropenylbenzene (m
-DIPB) was added in an amount of 1.5 mmol, and after the reaction solution changed from blue (indicating the presence of radicals) to orange (indicating the disappearance of radicals), isoprene (Ip) 21.0
g was added and a polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 9.0 g of 1,3-CHD was added, and a polymerization reaction was performed at 40 ° C. for 2 hours in a dry argon atmosphere to obtain CHD-I.
A p-CHD triblock copolymer was synthesized.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of methanol / hydrochloric acid mixed solvent. Was separated, washed with methanol, and vacuum dried at 60 ° C. to obtain a polymer exhibiting rubber elasticity at a yield of 100 wt%. Obtained CHD-Ip-
Number average molecular weight (Mn) of CHD triblock mopolymer
Was 19,890 and the molecular weight distribution (Mw / Mn) was 1.34. The content of the cyclic conjugated diene monomer unit in the polymer measured by ¹ H-NMR was in agreement with the charged composition. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer unit in the polymer is 46/5.
It was 4 (mol ratio).

Example 18 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. An n-hexane solution (1.6M) of n-BuLi was converted into a lithium atom to be 0.07 mm.
and added for 10 minutes. Then TMEDA
A 1.0 M cyclohexane solution of (first complexing agent) was prepared. This solution was added to n-BuLi / TMEDA = 4/2.
(Mol ratio), and the mixture was reacted at room temperature for 10 minutes and then heated to 40 ° C. and maintained.

To this solution, a 1.0 M solution of TMEDA (second complexing agent) in cyclohexane was added so that TMEDA (second complexing agent) was 0.0525 mmol.
A cyclohexane solution of the complex and TMEDA mixture was obtained. At this point, Li / TMEDA = 4/5 (molar ratio)
Met. Furthermore, 3.0 g of 1,3-CHD was added to a cyclohexane solution of the obtained mixture of the complex and TMEDA, and a polymerization reaction was performed at 40 ° C. for 6 hours in a dry argon atmosphere.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of methanol / hydrochloric acid mixed solvent. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer with a yield of 100 wt%. The number average molecular weight (Mn) of the obtained CHD homopolymer was 44,800 and the molecular weight distribution (Mw / Mn) was 1.21. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 51/49 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method is It was 165 ° C.
The tensile modulus (TM) of this polymer is 4,612 MPa.
(1 MPa = 10.20 kg · f / cm ² ).

Example 19 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. 1 g of the polymer obtained in Example 18 and 50 ml of trichlorobenzene were placed in a Schlenk tube and heated to 150 ° C. under a dry argon atmosphere and stirred to dissolve.

To this polymer solution, tetrachloro-1,
4-Benzoquinone (p-chloranil) was added in an amount of 4 equivalents relative to the hexene unit, and a dehydrogenation reaction was carried out at 150 ° C. for 20 hours. After completion of the reaction, desolvation operation was performed according to a conventional method to obtain a pale yellow polymer. From the UV spectrum, it was confirmed that 72% of the cyclohexene unit was a cyclic conjugated diene polymer in which a benzene ring was converted.

Example 20 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2700 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TME was further added.
After adding 7.5 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes. After heating the autoclave to 60 ° C., 11.25 mmol of TMEDA (second complexing agent) was additionally added. 300 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 60 ° C. for 3 hours. G.
C. 1,3-CHD conversion after 3 hours by analysis is 9
It was 9.8 mol%.

After completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method) to dehydrate n-molar with Li atom.
The polymerization reaction was stopped by adding heptanol, and [Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. as a stabilizer was added to the polymer solution, followed by desolvation according to a conventional method to obtain a CHD homopolymer. It was The number average molecular weight (Mn) of the obtained polymer was 20,100, and the molecular weight distribution was (Mw / Mn) 1.27. 1,2-bond of cyclic conjugated diene monomer unit in polymer /
The 1,4-bond ratio is 48/52 (molar ratio), and D
Glass transition temperature (Tg) measured by SC method is 15
It was 1 ° C.

Example 21 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2700 g of cyclohexane was introduced into the autoclave and kept at 60 ° C under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and further TM
After adding 7.5 mmol of EDA (first complexing agent),
Stirred at 0 ° C. for 10 minutes. The autoclave was maintained at 60 ° C., and 11.25 mmol of TMEDA (second complexing agent) was additionally added. 300 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 60 ° C. for 3 hours. G.
C. 1,3-CHD conversion after 3 hours by analysis is 9
It was 9.2 mol%.

After the completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method) to dehydrate n-molar with Li atom.
The polymerization reaction was stopped by adding heptanol, and [Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. as a stabilizer was added to the polymer solution, followed by desolvation according to a conventional method to obtain a CHD homopolymer. It was The number average molecular weight (Mn) of the obtained polymer was 20,500 and the molecular weight distribution (Mw / Mn) was 1.29. 1,2-bond of cyclic conjugated diene monomer unit in polymer /
The 1,4-bond ratio is 50/50 (molar ratio), and D
Glass transition temperature (Tg) measured by SC method is 15
It was 2 ° C.

Example 22 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2700 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TME was further added.
After adding 7.5 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes. After raising the temperature of the autoclave to 40 ° C., 11.25 mmol of TMEDA (second complexing agent) was additionally added. 300 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 4 hours. G.
C. The 1,3-CHD conversion rate after 4 hours by analysis is 9
It was 9.6 mol%.

After completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atom was added to carry out the polymerization reaction. After stopping, a polymer solution, [Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd., was added to the polymer solution, and desolvation was carried out according to a conventional method to obtain a CHD homopolymer. The number average molecular weight (Mn) of the obtained polymer was 20,200 and the molecular weight distribution (Mw / Mn) was 1.23. 1,2-bonds / 1,4-bonds of cyclic conjugated diene-based monomer units in polymer
The binding ratio was 61/39 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method was 158 ° C.

Example 23 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1500 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 22 was introduced into an autoclave, and then titanocene dichloride (TC) and diisobutylaluminum hydride (DIBAL-H) were used as a hydrogenation catalyst, and TC / DIB was used.
A catalyst solution prepared by adding AL-H = 1/6 (molar ratio) to cyclohexane was added to the polymer so as to be 290 ppm in terms of Ti metal atom.

After substituting the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 35 kg / cm ² G
As a result, the hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction,
Desolvation was performed according to a conventional method to obtain a hydrogenated CHD homopolymer. The hydrogenation rate of the double bond contained in the polymer to be hydrogenated, which was calculated by ¹ H-NMR measurement, was 67 mo.
It was 1%. Number average molecular weight (Mn) of the obtained polymer
Is 21,400, and the molecular weight distribution (Mw / Mn) is 1.
It was 22. The glass transition temperature (Tg) measured by the DSC method was 201 ° C.

Example 24 The inside of a sufficiently dried 4 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1000 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1000 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 22 was introduced into an autoclave, and 10 g of a solid catalyst in which 5 wt% of palladium (Pd) was carried on barium sulfate (BaSO ₄ ) was added.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 55 kg / cm ² G
As a result, the hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction,
Desolvation was performed according to a conventional method to obtain a hydrogenated CHD homopolymer. The hydrogenation rate of double bonds contained in the polymer to be hydrogenated calculated by ¹ H-NMR measurement was 100 m.
It was ol%. The number average molecular weight (M
n) is 20,800, and molecular weight distribution (Mw / Mn)
It was 1.24. The glass transition temperature (Tg) measured by the DSC method was 233 ° C.

Example 25 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TME was further added.
After adding 7.5 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes. After raising the temperature of the autoclave to 40 ° C., 11.25 mmol of TMEDA (second complexing agent) was additionally added. 600 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 4 ° C. for 4 hours. G. C.
The 1,3-CHD conversion after 4 hours by analysis is 97.4.
It was mol%.

After completion of the polymerization reaction, 700 g of cyclohexane
Was introduced to dilute the reaction solution, and the temperature was raised to 80 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydration n-heptanol in an amount equal to that of Li atom was added to stop the polymerization reaction. The polymer solution was used as a stabilizer in Ciba-Geigy, Switzerland.
[IRGANOX B215 (0037HX)] manufactured by the company was added, and desolvation operation was performed according to a conventional method to obtain a CHD homopolymer. The number average molecular weight (Mn) of the obtained polymer was 4
3,800, molecular weight distribution (Mw / Mn) 1.28
Met.

The 1,2-bond / 1,4-bond ratio in the cyclic conjugated diene monomer unit in the polymer is 58/42 (mo.
and the glass transition temperature (Tg) measured by the DSC method was 167 ° C. The elastic modulus (TM) of this polymer is 4,710 MPa (1 MPa = 10.20 k).
It was g · f / cm ² ). Heat distortion temperature (HDT: 1.
82 MPa) was 131 ° C.

Example 26 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 900 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 7.5 mmol of n-BuLi in terms of lithium atom was added, and TMEDA was further added.
After adding 3.75 mmol (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
5.63 mmol of MEDA (second complexing agent) was added additionally. 600 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 6 hours. G. C. The 1,3-CHD conversion rate after 6 hours by analysis was 94.7 mol.
%Met.

After completion of the polymerization reaction, cyclohexane 2000
After introducing g, the reaction solution was diluted and heated to 80 ° C.,
The reaction solution was pressure-fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), dehydrated n-heptanol equivalent to Li atom was added to terminate the polymerization reaction, and the polymer solution was stabilized. As an agent, [IRGANOX B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. in Switzerland was added, and the solvent was removed according to a conventional method to obtain a CHD homopolymer. The number average molecular weight (Mn) of the obtained polymer was 81,800, and the molecular weight distribution (Mw / Mn) was 1.3.
It was 2.

The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 63/37 (mol
The glass transition temperature (Tg) measured by the DSC method was 171 ° C. The tensile modulus (TM) of this polymer was 4,815 MPa (1 MPa = 10.20 k).
It was g · f / cm ² ). Heat distortion temperature (HDT: 1.
82 MPa) was 135 ° C.

Example 27 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1500 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 25 was introduced into an autoclave, and then titanocene dichloride (TC) and diisobutylaluminum hydride (DIBAL-H) were used as hydrogenation catalysts in TC / DIB.
A catalyst solution prepared by adding AL-H = 1/6 (molar ratio) to cyclohexane was added to the polymer so as to be 290 ppm in terms of Ti metal atom.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 35 kg / cm ² G
As a result, the hydrogenation reaction was performed for 10 hours. After completion of the hydrogenation reaction, desolvation operation was performed according to a conventional method to obtain a hydrogenated CHD homopolymer. The hydrogenation rate of the double bond contained in the polymer to be hydrogenated calculated by ¹ H-NMR measurement was 87.
It was mol%.

The number average molecular weight (Mn) of the obtained polymer was 45,300, and the molecular weight distribution (Mw / Mn) was 1.2.
It was 7. The glass transition temperature (Tg) measured by the DSC method was 228 ° C. The flexural strength (FS) of this polymer was 37.80 MPa (1 MPa = 10.20 k).
g · f / cm ² ) and flexural modulus (FM) is 6,0
It was 49 MPa. Heat distortion temperature (HDT: 1.82M
Pa) was 188 ° C. Example 28 Example 2 except that the polymer obtained in Example 26 was used.
A hydrogenation reaction was carried out in the same manner as in 7. After completion of the hydrogenation reaction, desolvation operation was performed according to a conventional method to obtain a hydrogenated CHD homopolymer. The hydrogenation rate of the double bond contained in the polymer to be hydrogenated calculated by ¹ H-NMR measurement was 79.
It was mol%.

The number average molecular weight (Mn) of the obtained polymer was 83,600, and the molecular weight distribution (Mw / Mn) was 1.4.
It was 1. The glass transition temperature (Tg) measured by the DSC method was 223 ° C. The flexural strength (FS) of this polymer was 44.80 MPa (1 MPa = 10.20 k).
g · f / cm ² ), flexural modulus (FM) is 6,322M
It was Pa. Heat distortion temperature (HDT: 1.82 MPa)
Was 190 ° C.

Example 29 The interior of a sufficiently dried 4 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1000 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1000 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 25 was introduced into an autoclave, and 10 g of a solid catalyst in which 5 wt% of palladium (Pd) was carried on barium sulfate (BaSO ₄ ) was added.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 55 kg / cm ² G
As a result, the hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction,
Desolvation was performed according to a conventional method to obtain a hydrogenated CHD homopolymer. The hydrogenation rate of double bonds contained in the polymer to be hydrogenated calculated by ¹ H-NMR measurement was 100 m.
It was ol%.

The number average molecular weight (Mn) of the obtained polymer was 44,100, and the molecular weight distribution (Mw / Mn) was 1.2.
It was 3. The glass transition temperature (Tg) measured by the DSC method was 236 ° C. The flexural strength (FS) of this polymer was 45.54 MPa (1 MPa = 10.20 k).
g · f / cm ² ), flexural modulus (FM) is 6,764M
It was Pa.

The heat distortion temperature (HDT: 1.82 MPa) was 192 ° C.

Example 30 Example 2 except that the polymer obtained in Example 26 was used.
A hydrogenation reaction was carried out in the same manner as in 9. After completion of the hydrogenation reaction, desolvation operation was performed according to a conventional method to obtain a hydrogenated CHD homopolymer. The hydrogenation rate of the double bond contained in the polymer to be hydrogenated calculated by ¹ H-NMR measurement is 10
It was 0 mol%. The number average molecular weight (Mn) of the obtained polymer was 82,700, and the molecular weight distribution (Mw / M
n) was 1.25. The glass transition temperature (Tg) measured by the DSC method was 238 ° C. The flexural strength (FS) of this polymer was 48.64 MPa (1 MPa = 1
0.20 kg · f / cm ² ) and the flexural modulus (FM) was 7,664 MPa. Heat distortion temperature (HDT: 1.
82 MPa) was 198 ° C.

Example 31 A hydrogenation reaction was carried out in the same manner as in Example 29 except that the carrier of the hydrogenation catalyst was alumina (Al ₂ O ₃ ). After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to give hydrogenated C
An HD homopolymer was obtained. The hydrogenation rate of the double bond contained in the polymer to be hydrogenated, calculated by ¹ H-NMR measurement, was 100 mol%. The number average molecular weight (Mn) of the obtained polymer was 81,900, and the molecular weight distribution (Mw / Mn) was 1.29. The glass transition temperature (Tg) measured by the DSC method was 238 ° C.

Example 32 Except that the carrier of the hydrogenation catalyst was silica (SiO ₂ ),
A hydrogenation reaction was carried out in the same manner as in Example 29. After completion of the hydrogenation reaction, desolvation operation is performed according to a conventional method, and hydrogenated CHD
A homopolymer was obtained. The hydrogenation rate of the double bond contained in the polymer to be hydrogenated, calculated by ¹ H-NMR measurement, was 100 mol%. The number average molecular weight (Mn) of the obtained polymer was 82,100, and the molecular weight distribution (Mw
/ Mn) was 1.33. The glass transition temperature (Tg) measured by the DSC method was 238 ° C.

Example 33 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 12.0 mmol of n-BuLi in terms of lithium atom was added, and TME was added.
After adding 6.0 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes. After heating the autoclave to 40 ° C., 9.0 mmol of TMEDA (second complexing agent) was additionally added. 600 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 6 hours. G. C. The 1,3-CHD conversion rate after 4 hours by analysis is 98.4 m.
It was ol%.

After completion of the polymerization reaction, 700 g of cyclohexane
Was introduced to dilute the reaction solution, and the temperature was raised to 80 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. 1,2 of the cyclic conjugated diene monomer unit in the polymer
The −bonding / 1,4-bonding ratio is 60/40 (mol ratio), and the glass transition temperature (T) measured by the DSC method.
g) was 170 ° C.

C was added to this polymer solution as a hydrogenation catalyst.
o (acac) ₃ and TIBAL (triisobutylaluminum), Co (acac) ₃ / TIBAL = 1 /
The catalyst solution prepared by adding 6 (molar ratio) to cyclohexane was added so as to be 100 ppm with respect to the polymer. The inside of the autoclave was replaced with hydrogen, the temperature was raised to 185 ° C., and the hydrogen pressure was adjusted to 50 kg / cm ₂ G to carry out a hydrogenation reaction for 4 hours. After completion of the hydrogenation reaction, the autoclave was cooled to room temperature, the pressure was reduced to normal pressure, and then the inside was replaced with nitrogen. TIBAL was treated by adding methanol according to a conventional method.

As a stabilizer for the polymer solution, a product of Ciba-Geigy Co., Ltd. [Irganox B215 (0037H
X)] was added and the solvent was removed according to a conventional method to obtain a hydrogenated CHD homopolymer. ¹ H-N of the obtained polymer
The hydrogenation rate of the cyclohexene ring calculated by MR is 1
And the number average molecular weight (Mn) is 50,700,
The molecular weight distribution (Mw / Mn) was 1.21. DSC
Glass transition temperature (Tg) measured by the method is 235 ° C
Met.

The flexural strength (FS) of this polymer was 46.8.
4 MPa (1 MPa = 10.20 kg · f / cm ² ),
The flexural modulus (FM) was 6,974 MPa. The heat distortion temperature (HDT: 1.82 MPa) was 195 ° C.

Example 34 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2700 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, add 30.0 mmol of n-BuLi in terms of lithium atom, and further add TME.
After adding 15.0 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
22.5 mmol of MEDA (second complexing agent) was added additionally. 45 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 1 hour.

Next, 210 g of isoprene (Ip) was introduced into the autoclave and a polymerization reaction was carried out at 40 ° C. for 1 hour and 30 minutes to obtain a CHD-Ip diblock copolymer.
Furthermore, 45 g of 1,3-CHD was introduced into the autoclave and the polymerization reaction was carried out at 40 ° C. for 3 hours to obtain CHD-Ip-C.
An HD triblock copolymer was obtained. After completion of the polymerization reaction,
The reaction solution was pressure-fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 9,
It was 700 and the molecular weight distribution (Mw / Mn) was 1.14. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 48/52 (mol ratio)
Met.

Example 35 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2700 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen.

Next, 37.5 mmol of n-BuLi in terms of lithium atom was added, and 18.75 mmol of TMEDA (first complexing agent) was further added, followed by stirring at room temperature for 10 minutes. After heating the autoclave to 40 ° C, T
28.1 mmol of MEDA (second complexing agent) was additionally added. Ip15g was introduced into the autoclave, then 1,3-CHD30g was introduced into the autoclave, and
Polymerization reaction was performed at 0 ° C. for 1 hour and 30 minutes to obtain an Ip-CHD diblock copolymer. 210 g of isoprene (Ip)
Was introduced into an autoclave and a polymerization reaction was carried out at 40 ° C. for 1 hour and 30 minutes to obtain an Ip-CHD-Ip triblock copolymer.

Then, 30 g of 1,3-CHD was introduced into the autoclave, and the polymerization reaction was carried out at 40 ° C. for 2 hours.
A p-CHD-Ip-CHD tetrablock copolymer was obtained. Furthermore, Ip15g was introduced into the autoclave,
Polymerization reaction is carried out at 40 ° C. for 30 minutes and Ip-CHD-Ip-C
An HD-Ip pentablock copolymer was obtained.

After the completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atoms was added to carry out the polymerization reaction. I stopped. The number average molecular weight (Mn) of the obtained polymer was 8,200, and the molecular weight distribution (Mw / Mn) was 1.08. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer unit in the polymer was 43/57 (mol ratio).

Example 36 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2700 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, add 30.0 mmol of n-BuLi in terms of lithium atom, and further add TME.
After adding 15.0 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes. After heating the autoclave to 40 ° C., 22.5 mmol of TMEDA (second complexing agent) was added additionally. 15 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 1 hour.

Then, 270 g of isoprene (Ip) was introduced into the autoclave and a polymerization reaction was carried out at 40 ° C. for 2 hours to obtain a CHD-Ip diblock copolymer. Furthermore,
Introduce 15 g of 1,3-CHD into the autoclave, and
Polymerization reaction was performed at 0 ° C for 3 hours to obtain a CHD-Ip-CHD triblock copolymer.

After the completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (which was sufficiently dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atom was added to carry out the polymerization reaction. I stopped. The number average molecular weight (Mn) of the obtained polymer was 10,500, and the molecular weight distribution (Mw / Mn) was 1.04. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer unit in the polymer was 45/55 (mol ratio).

Example 37 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1500 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 36 was introduced into an autoclave, and then titanocene dichloride (TC) and diisobutylaluminum hydride (DIBAL-H) were used as a hydrogenation catalyst, and TC / DIB was used.
A catalyst solution prepared by adding AL = 1/6 (molar ratio) to cyclohexane was added to the polymer so as to be 100 ppm in terms of Ti metal atom.

The autoclave was replaced with hydrogen at 100 ° C.
The temperature was raised to, and the hydrogenation reaction was carried out for 1 hour at a hydrogen pressure of 8 kg / cm ² G. The hydrogenation rate of the isoprene (Ip) part calculated by ¹ H-NMR measurement is 100 mol.
%, And the CHD part was not hydrogenated.

Example 38 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TME was further added.
After adding 7.5 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
11.25 mmol of MEDA (second complexing agent) was additionally added. 300 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was performed at 40 ° C. for 20 minutes. G. C. The 1,3-CHD conversion rate after 20 minutes by analysis is 47.8 mo.
It was 1%. Next, 300 g of isoprene (Ip) was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 5 hours. When Ip is added during the polymerization of 1,3-CHD, Ip is preferentially polymerized, and when Ip is almost consumed, the polymerization of 1,3-CHD starts again. Was a CHD-Ip-CHD triblock copolymer.

After completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atom was added to carry out the polymerization reaction. I stopped. The number average molecular weight (Mn) of the obtained polymer was 41,500, and the molecular weight distribution (Mw / Mn) was 1.31. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer unit in the polymer is 49/51 (mol ratio), and the glass transition temperature of the CHD block measured by the DSC method ( Tg)
Was 152 ° C.

The tensile strength (TS) of this polymer was 26.2.
MPa (1 MPa = 10.20 kg · f / cm ² ), tensile elongation (TE) is 157%, flexural strength (FS) is 23.0 MPa, flexural modulus (FM) is 2,950 MP.
It was a. The Izod impact strength is N.
B. (Not broken).

Example 39 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1800 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 10.0 mmol of n-BuLi in terms of lithium atom is added, and further, TME is added.
After adding 5.0 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
7.5 mmol of MEDA (second complexing agent) was added additionally.
200 g of 1,3-CHD was introduced into the autoclave,
A polymerization reaction was carried out at 40 ° C. for 20 minutes. G. C. The 1,3-CHD conversion rate after 20 minutes by analysis is 49.5 mol%.
Met. Next, 400 g of isoprene (Ip) was introduced into the autoclave, and a polymerization reaction was carried out at 40 C for 6 hours. When Ip is added during the polymerization of 1,3-CHD,
The obtained polymer was a CHD-Ip-CHD triblock copolymer because Ip was preferentially polymerized and 1,3-CHD was polymerized again when Ip was almost consumed.

After completion of the polymerization reaction, cyclohexane 1000
5 g was added to dilute the reaction solution, the temperature was raised to 70 ° C., and then another (fully dried according to a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 62,
And the molecular weight distribution (Mw / Mn) was 1.44. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 48/52 (mol ratio)
The glass transition temperature (Tg) of the CHD block measured by the DSC method was 151 ° C. The tensile strength (TS) of this polymer was 19.5 MPa (1 MPa = 1
0.20 kgf / cm ² ) and tensile elongation (TE)
Was 695%.

Example 40 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TME was further added.
After adding 7.5 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After heating the autoclave to 40 ° C., T
11.25 mmol of MEDA (second complexing agent) was additionally added. 1,3-CHD300g and Ip300g are mixed,
It was introduced into the autoclave and a polymerization reaction was carried out at 40 ° C. for 6 hours. G. C. 1,3-CHD after 6 hours by analysis
The conversion rate was 98.3 mol%. When 1,3-CHD and Ip coexist, Ip is preferentially polymerized, and when Ip is almost consumed, the polymerization of 1,3-CHD starts again. Therefore, the obtained polymer is Ip-CHD. It was a diblock copolymer.

After the completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer-equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 40,
It was 100, and the molecular weight distribution (Mw / Mn) was 1.49. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 51/49 (mol ratio)
And the glass transition temperature (Tg) of the CHD block measured by the DSC method was 153 ° C. The tensile strength (TS) of this polymer was 12.5 MPa (1 MPa = 1
0.20 kgf / cm ² ) and tensile elongation (TE)
Was 28%, flexural strength (FS) was 18.7 MPa, and flexural modulus (FM) was 815 MPa. Izod (Iz
od) Impact strength is N. B. (Not broken).

Example 41 A polymerization reaction was carried out in the same manner as in Example 38 except that the mixed monomer of 480 g of 1,3-CHD and 120 g of Ip was changed. G. C. The 1,3-CHD conversion rate after 6 hours by analysis was 96.6 mol%. 1,3-CHD is I
Since a large amount of coexisted with p, polymerization of 1,3-CHD also started from the initial stage of the polymerization reaction, and the obtained polymer was a polymer containing an Ip-CHD random part.

After completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried according to a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 41,
It was 200, and the molecular weight distribution (Mw / Mn) was 1.41. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 52/48 (mol ratio)
And the glass transition temperature (Tg) of the CHD block measured by the DSC method was 154 ° C. The tensile strength (TS) of this polymer was 47.5 MPa (1 MPa = 1
0.20 kgf / cm ² ) and tensile elongation (TE)
Was 5%, flexural strength (FS) was 92.9 MPa, and flexural modulus (FM) was 3,210 MPa. Heat distortion temperature (HD
T: 1.82 MPa) was 128 ° C. The Izod impact strength was 78.2 J / m.

Example 42 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1500 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 38 was introduced into an autoclave, and then titanocene dichloride (TC) and diisobutylaluminum hydride (DIBAL-H) were used as a hydrogenation catalyst and TC / DIB.
A catalyst solution prepared by adding AL-H = 1/6 (molar ratio) to cyclohexane was added to the polymer so as to be 290 ppm in terms of Ti metal atom.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 35 kg / cm ² G
As a result, the hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction,
Desolvation is performed according to a conventional method, and hydrogenated CHD-Ip-C is used.
An HD triblock copolymer was obtained. The hydrogenation rate of the isoprene (Ip) part calculated by ¹ H-NMR measurement was 100%, and the hydrogenation rate of the CHD part was 96%.

The number average molecular weight (Mn) of the obtained polymer was 42,400, and the molecular weight distribution (Mw / Mn) was 1.2.
It was 8. The glass transition temperature (Tg) of the hydrogenated CHD block measured by the DSC method was 233 ° C.
The tensile strength (TS) of this polymer is 30.8 MPa (1M
Pa = 10.20 kg · f / cm ² ), the tensile elongation (TE) is 357%, and the bending strength (FS) is 29.0 MP.
a, the flexural modulus (FM) was 3,050 MPa.
The Izod impact strength is N. B. (Not broken).

Example 43 Example 4 except that the polymer obtained in Example 39 was used.
The hydrogenation reaction was carried out in the same manner as in 2.

After completion of the hydrogenation reaction, desolvation was carried out according to a conventional method to obtain a hydrogenated CHD-Ip-CHD triblock copolymer. The hydrogenation rate of the isoprene (Ip) part calculated by ¹ H-NMR measurement was 100%, and C
The hydrogenation rate of the HD portion was 92%. The number average molecular weight (Mn) of the obtained polymer was 62,700 and the molecular weight distribution (Mw / Mn) was 1.39. The glass transition temperature (Tg) of the hydrogenated CHD block measured by the DSC method was 232 ° C. The tensile strength (TS) of this polymer was 24.3 MPa (1 MPa = 10.20 kg).
F / cm ² ) and the tensile elongation (TE) was 706%.

Example 44 The interior of a sufficiently dried 4 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1000 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1000 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 38 was introduced into an autoclave, and 10 g of a solid catalyst in which 5 wt% of palladium (Pd) was carried on barium sulfate (BaSO ₄ ) was added.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 55 kg / cm ² G
As a result, the hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction,
Desolvation is performed according to a conventional method, and hydrogenated CHD-Ip-C is used.
An HD triblock copolymer was obtained. The hydrogenation rates of the isoprene (Ip) part and the CHD part were both 100%, which were calculated by ¹ H-NMR measurement.

The number average molecular weight (Mn) of the obtained polymer was 40,900, and the molecular weight distribution (Mw / Mn) was 1.
It was 33. Hydrogenated CHD measured by DSC method
The glass transition temperature (Tg) of the block was 232 ° C. The tensile strength (TS) of this polymer is 30.2 MPa.
(1 MPa = 10.20 kg · f / cm ² ), the tensile elongation (TE) is 320% and the bending strength (FS) is 28.
The flexural modulus (FM) was 2 MPa and 3,150 MPa. The Izod impact strength is N. B.
(Not broken).

Example 45 Example 4 except that the polymer obtained in Example 39 was used.
The hydrogenation reaction was carried out in the same manner as in 4. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated CHD-Ip.
A -CHD triblock copolymer was obtained. ¹ H-NMR
Isoprene (Ip) part, CH calculated by measurement
The hydrogenation rates of the D part were both 100%.

The number average molecular weight (Mn) of the obtained polymer was 61,900, and the molecular weight distribution (Mw / Mn) was 1.
It was 46. Hydrogenated CHD measured by DSC method
The glass transition temperature (Tg) of the block was 230 ° C. The tensile strength (TS) of this polymer is 25.9 MPa.
(1 MPa = 10.20 kg · f / cm ² ) and the tensile elongation (TE) was 650%.

Example 46 The inside of a sufficiently dried 5 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TME was further added.
After adding 7.5 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
11.25 mmol of MEDA (second complexing agent) was additionally added. 300 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was performed at 40 ° C. for 20 minutes. G. C. The 1,3-CHD conversion rate after 20 minutes by analysis is 50.1 mo.
It was 1%. Next, 300 g of styrene (St) was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 5 hours. When St is added during the polymerization of 1,3-CHD, St is preferentially polymerized, and when St is consumed, the polymerization of 1,3-CHD starts again, and thus the obtained polymer is , CHD-St-CHD triblock copolymer.

After the completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atom was added to carry out the polymerization reaction. I stopped. The number average molecular weight (Mn) of the obtained polymer was 40,600 and the molecular weight distribution (Mw / Mn) was 1.21. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 56/44 (mol ratio), and the glass transition temperature of the CHD block measured by the DSC method ( Tg)
Was 162 ° C. The flexural strength (FS) of this polymer is 33.5 MPa (1 MPa = 10.20 kg · f / cm).
² ) and the flexural modulus (FM) was 2,980 MPa. The heat distortion temperature (HDT: 1.82 MPa) was 88 ° C.

Example 47 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 10.0 mmol of n-BuLi in terms of lithium atom is added, and further, TME is added.
After adding 5.0 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
7.5 mmol of MEDA (second complexing agent) was added additionally.
1,3-CHD 100g was introduced into the autoclave,
Polymerization reaction was carried out at 40 ° C. for 2 hours to obtain a CHD homopolymer (polymer 1). Next, 400 g of St was introduced into the autoclave, and the polymerization reaction was carried out at 40 ° C. for 3 hours.
HD-St diblock copolymer (polymer 2) was obtained.
Further, 100 g of 1,3-CHD was introduced into the autoclave, and the polymerization reaction was carried out at 40 ° C. for 5 hours to obtain CHD-St-
A CHD triblock copolymer (Polymer 3) was obtained.

After the completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. Number average molecular weight (Mn) of the obtained polymers 1 to 3
Are 10,300, 49, 800, 60, 700, respectively, and the molecular weight distribution (Mw / Mn) is 1.04, 1.
It was 10, 1.25. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer 3 is 53.
/ 47 (mol ratio), and the glass transition temperature (Tg) of the CHD block measured by the DSC method was 156 ° C. The tensile strength (TS) of this polymer is 18.9MP
a (1 MPa = 10.20 kg · f / cm ² ),
Tensile elongation (TE) is 2% and bending strength is (FS) 46.2.
MPa, flexural modulus (FM) was 3,232 MPa. The heat distortion temperature (HDT: 1.82 MPa) was 78 ° C.

Example 48 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TME was further added.
After adding 7.5 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After heating the autoclave to 40 ° C., T
11.25 mmol of MEDA (second complexing agent) was additionally added. 1,3-CHD 300g and St 300g are mixed,
It was introduced into the autoclave and a polymerization reaction was carried out at 40 ° C. for 6 hours. G. C. 1,3-CHD after 6 hours by analysis
The conversion rate was 98.3 mol%. When 1,3-CHD and St coexist, St is preferentially polymerized, and when St is consumed, the polymerization of 1,3-CHD starts again.
The resulting polymer was a St-CHD diblock copolymer.

After the completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 40,
It was 080 and the molecular weight distribution (Mw / Mn) was 1.23. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 57/43 (mol ratio)
The glass transition temperature (Tg) of the CHD block measured by the DSC method was 161 ° C. The flexural strength (FS) of this polymer was 18.5 MPa (1 MPa = 1
0.20 kg · f / cm ² ) and the flexural modulus (FM) was 5,430 MPa. Heat distortion temperature (HDT: 1.
82 MPa) was 72 ° C.

Example 49 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TME was further added.
After adding 7.5 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
11.25 mmol of MEDA (second complexing agent) was additionally added. 1,3-CHD200g, Ip200g, St20
0g was mixed and introduced into the autoclave, and the mixture was mixed at 40 ° C for 6
The polymerization reaction was carried out for a time. G. C. The 1,3-CHD conversion rate after 6 hours by analysis was 99.5 mol%.
When 1,3-CHD, Ip and St coexist, St is preferentially polymerized, and when St is consumed, Ip is polymerized and Ip
The polymer obtained was a St-Ip-CHD triblock copolymer, because the polymerization of 1,3-CHD started when almost all of was consumed.

After the completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 40,
It was 200 and the molecular weight distribution (Mw / Mn) was 1.21. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 53/47 (mol ratio)
And the glass transition temperature (Tg) of the CHD block measured by the DSC method was 156 ° C. The tensile strength (TS) of this polymer was 22.4 MPa (1 MPa = 1
0.20 kgf / cm ² ) and tensile elongation (TE)
Was 4%, flexural strength (FS) was 45.0 MPa, and flexural modulus (FM) was 1,470 MPa.

Example 50 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1500 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 46 was introduced into an autoclave, and then titanocene dichloride (TC) and diisobutylaluminum hydride (DIBAL-H) were added as TC / DIB as a hydrogenation catalyst.
The catalyst solution prepared by adding to cyclohexane at AL = 1/6 (molar ratio) was added to the polymer so as to be 290 ppm in terms of Ti metal atom.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 35 kg / cm ² G
As a result, the hydrogenation reaction was performed for 10 hours. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated CHD-St.
A -CHD triblock copolymer was obtained. ¹ H-NMR
Hydrogenation rate of CHD part calculated by measurement is 96%
And the St moiety was not hydrogenated.

The number average molecular weight (Mn) of the obtained polymer was 40,400, and the molecular weight distribution (Mw / Mn) was 1.
It was 20. The glass transition temperature (Tg) of the CHD block portion measured by the DSC method was 232 ° C. The flexural strength (FS) of this polymer is 38.8 MPa (1MP
a = 10.20 kg · f / cm ² ), flexural modulus (F
M) was 4,060 MPa. Heat distortion temperature (HD
T: 1.82 MPa) was 90 ° C.

Example 51 Example 5 except that the polymer obtained in Example 48 was used.
The hydrogenation reaction was carried out in the same manner as in 0. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated St-CHD.
A diblock copolymer was obtained. The hydrogenation rate of the CHD portion calculated by ¹ H-NMR measurement was 96%, and S
The t portion was not hydrogenated.

The number average molecular weight (Mn) of the obtained polymer was 40,400 and the molecular weight distribution (Mw / Mn) was 1.
It was 19. The glass transition temperature (Tg) of the CHD block portion measured by the DSC method was 234 ° C. The flexural strength (FS) of this polymer is 22.8 MPa (1MP
a = 10.20 kg · f / cm ² ), flexural modulus (F
M) was 5,810 MPa. Heat distortion temperature (HD
T: 1.82 MPa) was 82 ° C.

Example 52 The interior of a sufficiently dried 4 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1000 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1000 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 46 was introduced into an autoclave, and 50 g of a solid catalyst in which 5 wt% of palladium (Pd) was carried on barium sulfate (BaSO ₄ ) was added.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 55 kg / cm ² G
As a result, the hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction,
Desolvation operation is performed according to a conventional method, and hydrogenated CHD-St-C is used.
An HD triblock copolymer was obtained. The hydrogenation rates of the CHD portion and the St portion calculated by ¹ H-NMR measurement were both 100%.

The number average molecular weight (Mn) of the obtained polymer was 41,600, and the molecular weight distribution (Mw / Mn) was 1.
29. The glass transition temperature (Tg) measured by the DSC method was 232 ° C. for the hydrogenated CHD block and 147 ° C. for the hydrogenated styrene block. The flexural strength (FS) of this polymer was 42.8 MPa (1 MPa = 10.2).
0 kg · f / cm ² ), flexural modulus (FM) is 5,02
It was 5 MPa. Heat distortion temperature (HDT: 1.82MP
a) was 129 ° C.

Example 53 Example 5 except that the polymer obtained in Example 48 was used.
The hydrogenation reaction was carried out in the same manner as in 2. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated St-CHD.
A diblock copolymer was obtained. The hydrogenation rates of the St portion and the CHD portion calculated by ¹ H-NMR measurement are both 1
00%.

The number average molecular weight (Mn) of the obtained polymer was 41,000 and the molecular weight distribution (Mw / Mn) was 1.
It was 26. The glass transition temperature (Tg) measured by the DSC method was 229 ° C. for the hydrogenated CHD block and 149 ° C. for the hydrogenated styrene block. The flexural strength (FS) of this polymer was 28.1 MPa (1 MPa = 10.2).
0 kg · f / cm ² ), flexural modulus (FM) is 6,10
It was 0 MPa. Heat distortion temperature (HDT: 1.82MP
a) was 128 ° C.

Example 54 The inside of a 100 ml Schlenk tube which had been sufficiently dried by a conventional method was replaced with dry argon. 1 g of the polymer obtained in Example 46 and 50 ml of trichlorobenzene were placed in a Schlenk tube and heated to 140 ° C. under a dry argon atmosphere and stirred to dissolve. To this polymer solution, tetrachloro-
1,4-benzoquinone (p-chloranil) was added so as to be 4 equivalents with respect to the hexene unit, and the mixture was added at 140 ° C for 2
The dehydrogenation reaction was performed for 0 hours. After completion of the reaction, desolvation operation was performed according to a conventional method to obtain a pale yellow polymer. From the UV spectrum, it was confirmed that 76% of the cyclohexene unit was a cyclic conjugated diene polymer in which a benzene ring was converted.

Example 55 The inside of a 100 ml Schlenk tube which had been sufficiently dried according to a conventional method was replaced with dry argon. 1 g of the polymer obtained in Example 48 and 50 ml of trichlorobenzene were placed in a Schlenk tube, and heated and stirred in 140 in a dry argon atmosphere to dissolve. To this polymer solution, tetrachloro-1,
4-Benzoquinone (p-chloranil) was added in an amount of 4 equivalents relative to the hexene unit, and a dehydrogenation reaction was performed at 140 ° C. for 20 hours. After completion of the reaction, desolvation operation was performed according to a conventional method to obtain a pale yellow polymer. From the UV spectrum, it was confirmed that 82% of the cyclohexene unit was a cyclic conjugated diene polymer in which a benzene ring was converted.

Example 56 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2700 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, add 30.0 mmol of n-BuLi in terms of lithium atom, and further add TME.
After adding 15.0 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
22.5 mmol of MEDA (second complexing agent) was added additionally. 45 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 700 g of a 30 wt% cyclohexane solution of butadiene (Bd)
(Bd210g) was introduced into the autoclave and kept at 40 ° C.
Polymerization reaction was carried out for 1 hour to obtain a CHD-Bd diblock copolymer. Furthermore, 45 g of 1,3-CHD was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 3 hours.
An HD-Bd-CHD triblock copolymer was obtained.

After the completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atom was added to carry out the polymerization reaction. I stopped. The number average molecular weight (Mn) of the obtained polymer was 10,100 and the molecular weight distribution (Mw / Mn) was 1.08. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer unit in the polymer was 46/54 (mol ratio).

Example 57 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1333 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 10.0 mmol of n-BuLi in terms of lithium atom is added, and further, TME is added.
After adding 5.0 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
7.5 mmol of MEDA (second complexing agent) was added additionally.
1,3-CHD 100g was introduced into the autoclave,
Polymerization reaction was carried out at 40 ° C. for 2 hours to obtain a CHD homopolymer. Then, 667 g (Bd 200 g) of a 30 wt% cyclohexane solution of butadiene (Bd) was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 2 hours to obtain CHD.
-Bd diblock copolymer was obtained. Furthermore, 1,3-C
HD100g is introduced into the autoclave and it is 5 at 40 ℃.
Polymerization reaction was carried out for a time to obtain a CHD-Bd-CHD triblock copolymer.

After the completion of the polymerization reaction, the reaction solution was pressure-fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atom was added to carry out the polymerization reaction. I stopped. The number average molecular weight (Mn) of the obtained polymer was 40,100, and the molecular weight distribution (Mw / Mn) was 1.15. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer was 51/49 (mol ratio), and the glass transition temperature of the CHD block unit measured by the DSC method ( Tg)
Was 158 ° C. The tensile strength (TS) of this polymer was 14.2 MPa (1 MPa = 10.20 kg · f / cm).
² ), the tensile elongation (TE) is 133%, the bending strength (FS) is 15.6 MPa, and the bending elastic modulus (FM) is 2,
It was 957 MPa. The Izod impact strength is N. B. (Not broken).

Example 58 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1467 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, 10.0 mmol of n-BuLi in terms of lithium atom is added, and further, TME is added.
After adding 5.0 mmol of DA (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
7.5 mmol of MEDA (second complexing agent) was added additionally.
1,3-CHD 100g was introduced into the autoclave,
Polymerization reaction was carried out at 40 ° C. for 2 hours to obtain a CHD homopolymer. Next, 1333 g (Bd 400 g) of a 30 wt% cyclohexane solution of butadiene (Bd) was introduced into the autoclave, and a polymerization reaction was carried out at 40 ° C. for 2 hours.
A D-Bd diblock copolymer was obtained. Furthermore, 1,3-
100 g of CHD was introduced into the autoclave and a polymerization reaction was carried out at 40 ° C. for 5 hours to obtain a CHD-Bd-CHD triblock copolymer.

After the completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 6
1,200 and the molecular weight distribution (Mw / Mn) is 1.1.
It was 7. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 51/49 (mol
Ratio), and the glass transition temperature (Tg) of the CHD block measured by the DSC method was 157 ° C. The tensile strength (TS) of this polymer was 19.5 MPa (1 MPa =
10.20 kg · f / cm ² ) and tensile elongation (T
E) was 810%.

Example 59 The interior of a sufficiently dried 5 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1500 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 57 was introduced into an autoclave, and then titanocene dichloride (TC) and diisobutylaluminum hydride (DIBAL-H) were used as a hydrogenation catalyst, TC / DIB.
The catalyst solution prepared by adding to cyclohexane at AL = 1/6 (molar ratio) was added to the polymer so as to be 290 ppm in terms of Ti metal atom.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 35 kg / cm ² G
As a result, the hydrogenation reaction was performed for 10 hours. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated CHD-Bd.
A -CHD triblock copolymer was obtained. ¹ H-NMR
Hydrogenation rate of CHD part calculated by measurement is 92%
And the hydrogenation rate of the Bd portion was 98%.

The number average molecular weight (Mn) of the obtained polymer was 41,200, and the molecular weight distribution (Mw / Mn) was 1.1.
It was 7. The glass transition temperature (Tg) of the CHD block measured by the DSC method was 232 ° C. The tensile strength (TS) of this polymer was 19.6 MPa (1 MPa =
10.20 kg · f / cm ² ) and tensile elongation (T
E) is 153%, flexural strength (FS) is 17.0 MPa,
The flexural modulus (FM) was 3,254 MPa. The Izod impact strength is N. B. (Without breaking)
Met.

Example 60 Example 5 except that the polymer obtained in Example 58 was used.
A hydrogenation reaction was carried out in the same manner as in 9. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated CHD-Bd.
A -CHD triblock copolymer was obtained. ¹ H-NMR
Hydrogenation rate of CHD part calculated by measurement is 98%
And the hydrogenation rate of the Bd portion was 100%.

The number average molecular weight (Mn) of the obtained polymer was 60,900, and the molecular weight distribution (Mw / Mn) was 1.
It was 11. The glass transition temperature (Tg) of the CHD block measured by the DSC method was 227 ° C. The tensile strength (TS) of this polymer was 24.3 MPa (1 MPa
= 10.20 kg · f / cm ² ) and the tensile elongation (T
E) was 850%.

Example 61 The interior of a sufficiently dried 4 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1000 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1000 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 57 was introduced into an autoclave, and 10 g of a solid catalyst in which 5 wt% of palladium (Pd) was supported on alumina (Al ₂ O ₃ ) was added.

After replacing the inside of the autoclave with hydrogen, 1
The temperature was raised to 60 ° C. Furthermore, hydrogen pressure is 55 kg / cm ² G
As a result, the hydrogenation reaction was performed for 6 hours. After completion of the hydrogenation reaction,
Desolvation operation is performed according to a conventional method, and hydrogenated CHD-Bd-C is used.
An HD triblock copolymer was obtained. The hydrogenation rates of the CHD portion and the Bd portion calculated by ¹ H-NMR measurement were both 100%.

The number average molecular weight (Mn) of the obtained polymer was 40,700, and the molecular weight distribution (Mw / Mn) was 1.1.
It was 6. The glass transition temperature (Tg) of the hydrogenated cyclohexadiene block measured by the DSC method is 232.
° C. The tensile strength (TS) of this polymer is 21.4.
MPa (1 MPa = 10.20 kg · f / cm ² ), tensile elongation (TE) is 147%, bending strength (FS) is 19.2 MPa, and bending elastic modulus (FM) is 3,350 MP.
It was a. The Izod impact strength is N.
B. (Not broken).

Example 62 Example 6 except that the polymer obtained in Example 58 was used.
The hydrogenation reaction was carried out in the same manner as in 1. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated CHD-Bd.
A -CHD triblock copolymer was obtained. ¹ H-NMR
The hydrogenation rates of the CHD portion and the Bd portion calculated by the measurement were both 100%.

The number average molecular weight (Mn) of the obtained polymer was 62,300, and the molecular weight distribution (Mw / Mn) was 1.
It was 15. The glass transition temperature (Tg) of the hydrogenated cyclohexadiene block measured by the DSC method is 22.
It was 9 ° C. The tensile strength (TS) of this polymer was 25.
It was 2 MPa (1 MPa = 10.20 kg · f / cm ² ) and the tensile elongation (TE) was 810%.

Example 63 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1500 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 56 was introduced into an autoclave, and then titanocene dichloride (TC) and n-BuLi were used as a hydrogenation catalyst in TC.
/ N-BuLi = 1/1 (molar ratio) was added to the cyclohexane to prepare a catalyst solution, which was added to the polymer at 100 ppm in terms of Ti metal atoms.

After replacing the inside of the autoclave with hydrogen, 7
The temperature was raised to 5 ° C. Further, hydrogenation reaction was carried out for 30 minutes at a hydrogen pressure of 8 kg / cm ² G. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated CHD-Bd-CHD.
A triblock copolymer was obtained. The hydrogenation rate of the CHD part calculated by ¹ H-NMR measurement was 0%, and
The hydrogenation rate of the d portion was 100%. The number average molecular weight (Mn) of the obtained polymer was 10,200, and the molecular weight distribution (Mw / Mn) was 1.09.

Example 64 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1947 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Then, the polymerization catalyst (complex) synthesized in Example 1 was converted into lithium atom and converted to 5.0 mm.
ol was added. After keeping the autoclave at 30 ° C., 3.75 mmol of TMEDA (second complexing agent) was additionally added.

60 g of 1,3-cyclohexadiene was placed in an autoclave and a polymerization reaction was carried out at 30 ° C. for 4 hours to obtain a CHD homopolymer. Then, butadiene (B
933 g of a 30 wt% cyclohexane solution of (d) (Bd2
80 g) was introduced into an autoclave and a polymerization reaction was carried out at 45 ° C for 1 hour to obtain a CHD-Bd diblock copolymer. Further, 60 g of 1,3-CHD was introduced into the autoclave, and the polymerization reaction was carried out at 30 ° C. for 4 hours to obtain CHD-B.
A d-CHD triblock copolymer was obtained.

After the completion of the polymerization reaction, the reaction solution was pressure fed to another 5 L high-pressure autoclave equipped with an electromagnetic induction stirrer (fully dried according to a conventional method), and dehydrated n-heptanol equivalent to Li atoms was added to carry out the polymerization reaction. I stopped. To this polymer solution, as a hydrogenation catalyst, titanocene dichloride (T
C) and n-BuLi, TC / n-BuLi = 1/1
The catalyst solution prepared by adding (molar ratio) to cyclohexane was added to the polymer at 250 pp as metal atom (Ti).
m was added. The inside of the autoclave was replaced with hydrogen, the temperature was raised to 75 ° C., the hydrogen pressure was adjusted to 10 kg / cm ² G, and the hydrogenation reaction was performed for 30 minutes. After completion of the hydrogenation reaction, the autoclave was cooled to room temperature, the pressure was reduced to normal pressure, and then the inside was replaced with nitrogen. Methanol was added according to a conventional method to treat n-BuLi.

As a stabilizer in a polymer solution, a product of Ciba-Geigy Co., Ltd. [Irganox B215 (0037H
X)] was added and the solvent was removed according to a conventional method to obtain a hydrogenated CHD-Bd-CHD triblock copolymer exhibiting rubber elasticity. The hydrogenation rate of the CHD portion calculated by ¹ H-NMR of the obtained polymer was 0%, and the Bd portion was 1,
The hydrogenation rates of the 2-vinyl part, 1,4-cis and trans parts were all 100%. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer unit in the polymer is 48/5.
2 (mol ratio), CH measured by DSC method
The glass transition temperature (Tg) of the D block was 153 ° C. The number average molecular weight (Mn) of the polymer was 79,600, and the molecular weight distribution (Mw / Mn) was 1.09. The polymer had a tensile strength (TS) of 17.8 MPa and a tensile elongation (TE) of 850%.

Example 65 The interior of a sufficiently dried 5 L high pressure autoclave with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1947 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Next, the polymerization catalyst (complex) synthesized in Example 1 was converted into lithium atom to 10.0 m.
mol was added.

After keeping the autoclave at 30 ° C., T
7.5 mmol of MEDA (second complexing agent) was added additionally.
120 g of 1,3-cyclohexadiene was charged into an autoclave and a polymerization reaction was carried out at 30 ° C. for 4 hours to obtain a CHD homopolymer.

Next, 30 wt% of butadiene (Bd)
Introduce 933 g (Bd280 g) of cyclohexane solution into the autoclave and carry out polymerization reaction at 45 ° C. for 1 hour.
A CHD-Bd diblock copolymer was obtained. 2.5 mmol of silicon tetrachloride (SiCl ₄ ) was added to this polymer solution, and a coupling reaction was carried out at 60 ° C. for 30 minutes.

As a stabilizer in a polymer solution, a product of Ciba-Geigy Co., Ltd. [Irganox B215 (0037H
X)] was added and the solvent was removed according to a conventional method to obtain a CHD-Bd-CHD triblock copolymer exhibiting rubber elasticity. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 50/50 (molar ratio)
The glass transition temperature (Tg) of the CHD block measured by the DSC method was 155 ° C. The number average molecular weight (Mn) of the obtained polymer was 112,000,
The molecular weight distribution (Mw / Mn) was 2.08. The tensile strength (TS) of this polymer was 16.8 MPa (1 MPa = 1
0.20 kgf / cm ² ) and tensile elongation (TE)
Was 600%.

Example 66 The inside of a 100 ml Schlenk tube which had been sufficiently dried by a conventional method was replaced with dry argon. 1 g of the polymer obtained in Example 64 and 50 ml of trichlorobenzene were placed in a Schlenk tube and heated to 140 ° C. under a dry argon atmosphere and stirred to dissolve. To this polymer solution, tetrachloro-
1,4-benzoquinone (p-chloranil) was added so as to be 4 equivalents with respect to the hexene unit, and the mixture was added at 140 ° C. for 2 hours.
The dehydrogenation reaction was performed for 0 hours. After completion of the reaction, solvent removal operation was performed according to a conventional method to obtain a polymer showing pale yellow rubber elasticity. From the UV spectrum, it was confirmed that 89% of the cyclohexene unit was a cyclic conjugated diene polymer in which a benzene ring was converted.

Example 67 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2400 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. Then, 15.0 mmol of n-BuLi in terms of lithium atom was added, and TMED was further added.
After adding 7.5 mmol of A (first complexing agent), the mixture was stirred at room temperature for 10 minutes.

After raising the temperature of the autoclave to 40 ° C., T
11.25 mmol of MEDA (second complexing agent) was additionally added. Introduce ethylene (Et) into the autoclave, and
Polymerization was carried out at a t-pressure of 40 kg / cm @ 2 G and 40 DEG C. for 1 hour. Next, after depressurizing Et and replacing it with dry nitrogen,
300 g of 1,3-CHD was introduced into the autoclave,
Polymerization reaction was carried out at 40 ° C. for 7 hours to obtain an Et-CHD diblock copolymer. G. C. The 1,3-CHD conversion rate after 7 hours by analysis was 98.2 mol%.

After the completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The Et content calculated by ¹ H-NMR measurement in the obtained polymer was 15 wt%. The number average molecular weight (Mn) of the polymer was 23,400, and the molecular weight distribution (Mw / Mn) was 1.62. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer was 53/47 (mol ratio), and the glass transition temperature of the CHD block measured by the DSC method ( Tg) is 1
It was 57 ° C.

Example 68 The inside of a 100 ml Schlenk tube which had been sufficiently dried by a conventional method was replaced with dry argon. Cyclohexane 18.0
2.0 g of n-hexane was injected into the Schlenk tube. The temperature of the solution was kept at room temperature, and the polymerization catalyst (complex) obtained in Example 1 was converted into lithium atom to 0.07 m.
mol was added. Then, a 1.0 M-cyclohexane solution of TMEDA (second complexing agent) was prepared. This solution was additionally added so that n-BuLi / TMEDA = 4/5 (mol ratio), and the mixture was reacted at room temperature for 10 minutes. 1,3-
1.50 g of CHD was added, and a polymerization reaction was performed at room temperature for 3 hours in a dry argon atmosphere to obtain a CHD homopolymer.
This polymer solution was cooled to −10 ° C., 1.50 g of methyl methacrylate (MMA) was additionally added, and a polymerization reaction was performed at −10 ° C. for 3 hours to obtain a CHD-MMA diblock copolymer.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer with a yield of 81 wt%. The number average molecular weight (Mn) of the obtained CHD-MMA diblock copolymer was 34,500, and the molecular weight distribution (Mw / Mn) was 1.72. 1,2-bond of cyclic conjugated diene monomer unit in polymer /
The 1,4-bond ratio was 54/46 (molar ratio), and D
The glass transition temperature (Tg) of the CHD block measured by SC method was 154 ° C.

Example 69 The inside of a 100 ml Schlenk tube which had been sufficiently dried by a conventional method was replaced with dry argon. Cyclohexane 18.0
g was injected into a Schlenk tube, and the temperature of cyclohexane was kept at room temperature. An n-hexane solution (1.6M) of n-BuLi was converted into a lithium atom and was 0.10 mm.
and added for 10 minutes. Then TMEDA
A 1.0 M cyclohexane solution of (first complexing agent) was prepared. This solution was added to n-BuLi / TMEDA = 4/2.
(Mol ratio), and the mixture was reacted at room temperature for 10 minutes and then heated to 40 ° C. and maintained.

To this solution, a solution of TMEDA in 1.0 M-cyclohexane was added 0.02% by TMEDA (second complexing agent).
The complex was added to 75 mmol, and the complex was added to TMEDA.
A cyclohexane solution of the mixture was obtained. At this point Li
/ TMEDA = 4/5 (molar ratio). Furthermore, 2.0 g of 1,3-CHD was added to the cyclohexane solution of the mixture of the obtained complex and TMEDA, and the polymerization reaction was carried out at 40 ° C. for 4 hours in a dry argon atmosphere to obtain a CHD homopolymer. Then, 2.0 g of methyl methacrylate (MMA) was added, and the mixture was dried in an atmosphere of dry argon at 40 ° C. for 2.
Polymerization reaction was carried out for 5 hours to obtain a CHD-MMA diblock copolymer.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and vacuum dried at 60 ° C. to obtain a white polymer with a yield of 98 wt%. The number average molecular weight (M
n) is 38,700, and molecular weight distribution (Mw / Mn)
Was 1.89. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in the polymer is 52/48.
(Mol ratio), and CHD measured by the DSC method
The glass transition temperature (Tg) of the block was 155 ° C.

Example 70 Example 5 except that the polymer obtained in Example 47 was used.
The hydrogenation reaction was carried out in the same manner as in 2. After completion of the hydrogenation reaction, desolvation operation is carried out according to a conventional method to obtain hydrogenated CHD-St.
A -CHD triblock copolymer was obtained.

St calculated by ¹ H-NMR measurement
The hydrogenation rates of the portion and the CHD portion were both 100 mol%. The number average molecular weight (Mn) of the obtained polymer was 41,
The molecular weight distribution (Mw / Mn) was 1.28. Glass transition temperature (T
g) had a hydrogenated CHD block of 230 ° C and a hydrogenated styrene block of 149 ° C. The flexural strength (FS) of this polymer was 50.1 MPa (1 MPa = 10.20 kg).
・ F / cm ² ), flexural modulus (FM) is 6,200MP
It was a. The heat distortion temperature (HDT: 1.82 MPa) was 130 ° C.

Example 71 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1947 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. 1,3-CHD 60g, TM
3.0 mmol of EDA (second complexing agent) was introduced into the autoclave and the temperature was raised to 40 ° C.

Then, the polymerization catalyst (complex) obtained in the same manner as in Example 1 was converted into lithium atom to 4.0 mmol.
Was added and the polymerization reaction was carried out at 40 ° C. for 2 hours to obtain a CHD homopolymer. Then, 30w of butadiene (Bd)
A t% cyclohexane solution (933 g, Bd280 g) was introduced into the autoclave, and a polymerization reaction was performed at 40 ° C. for 2 hours to obtain a CHD-Bd diblock copolymer. Furthermore,
60 g of 1,3-CHD was introduced into the autoclave, and 4
Polymerization reaction was performed at 0 ° C for 5 hours to obtain a CHD-Bd-CHD triblock copolymer.

After the completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried by a conventional method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 98,
It was 900, and the molecular weight distribution (Mw / Mn) was 1.04. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 50/50 (molar ratio)
And the glass transition temperature (Tg) of the CHD block unit measured by the DSC method was 156 ° C. The tensile strength (TS) of this polymer was 19.2 MPa (1 Mpa =
10.20 kgf / cm ² ), tensile elongation (TE) is 9
It was 10%.

Example 72 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1947 g of cyclohexane was introduced into the autoclave and kept at room temperature under dry nitrogen. 1,3-CHD 60g, TM
4.875 mmol of EDA (second complexing agent) was introduced into the autoclave, and the temperature was raised to 40 ° C.

Then, the polymerization catalyst (complex) obtained in the same manner as in Example 1 was converted into lithium atom to 6.5 mmol.
After the addition, a polymerization reaction was carried out at 40 ° C. for 2 hours to obtain a CHD homopolymer. Then, 30 wt% of butadiene (Bd)
% Cyclohexane solution (933 g (Bd280 g)) was introduced into the autoclave and a polymerization reaction was carried out at 40 ° C. for 2 hours to obtain a CHD-Bd diblock copolymer. Furthermore,
60 g of 1,3-CHD was introduced into the autoclave, and 4
Polymerization reaction was performed at 0 ° C for 5 hours to obtain a CHD-Bd-CHD triblock copolymer.

After the completion of the polymerization reaction, the temperature was raised to 70 ° C., and then another (fully dried according to the usual method) electromagnetic induction stirrer equipped 5
The reaction solution was pressure-fed to an L high-pressure autoclave, and dehydrated n-heptanol in an amount equal to that of Li atoms was added to terminate the polymerization reaction. The number average molecular weight (Mn) of the obtained polymer was 62,
And the molecular weight distribution (Mw / Mn) was 1.06. 1, of the cyclic conjugated diene-based monomer units in the polymer
2-bond / 1,4-bond ratio is 49/51 (mol ratio)
And the glass transition temperature (Tg) of the CHD block unit measured by the DSC method was 154 ° C. The tensile strength (TS) of this polymer was 17.2 MPa (1 Mpa =
10.20 kg · f / cm ² ) and tensile elongation (T
E) was 800%.

Example 73 The inside of a 100 ml Schlenk tube which had been sufficiently dried by a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into the Schlenk tube, and the temperature of cyclohexane was kept at room temperature. Further, n obtained in the same manner as in Example 1
-BuLi / TMEDA = 4/1 (mol ratio), 0.3 mmol of lithium atom conversion was added.
It melted and the temperature of the solution was kept at 40 ° C. In this solution,
A 1.0 M solution of TMEDA in cyclohexane was added to TME.
DA (second complexing agent) was additionally added so as to be 0.30 mmol to obtain a cyclohexane solution of a mixture of the complex and TMEDA. At this point, Li / TMEDA = 4/5 (mo
1 ratio). Furthermore, in a cyclohexane solution of the mixture of the obtained complex and TMEDA, 3.0 g of 1,3-CHD was added.
Was added, and a polymerization reaction was carried out at 40 ° C. for 2 hours in a dry argon atmosphere.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further added with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer with a yield of 100 wt%. The number average molecular weight (Mn) of the obtained CHD homopolymer was 10,200, and the molecular weight distribution (Mw / Mn) was 1.19. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene-based monomer units in this polymer was 47/53 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method. Was 154 ° C.

Example 74 The inside of a 100 ml Schlenk tube which had been sufficiently dried by a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into the Schlenk tube, and the temperature of cyclohexane was kept at room temperature. Further, n obtained in the same manner as in Example 1
-BuLi / TMEDA = 2/2 (mol ratio), 0.3 mmol of lithium atom conversion
It melted and the temperature of the solution was kept at 40 ° C. In this solution,
A 1.0 M solution of TMEDA in cyclohexane was added to TME.
DA (second complexing agent) was additionally added to 0.075 mmol to obtain a cyclohexane solution of a mixture of the complex and TMEDA. At this point, Li / TMEDA = 4/5 (m
ol ratio). Furthermore, 1,3-CHD3.0 was added to a cyclohexane solution of the mixture of the obtained complex and TMEDA.
g was added, and a polymerization reaction was carried out at 40 ° C. for 2 hours in a dry argon atmosphere.

After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to terminate the reaction, and the polymer was further mixed with a large amount of a mixed solvent of methanol / hydrochloric acid. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer with a yield of 100 wt%. The number average molecular weight (Mn) of the obtained CHD homopolymer was 9,870, and the molecular weight distribution (Mw / Mn) was 1.14. The 1,2-bond / 1,4-bond ratio of the cyclic conjugated diene monomer unit in this polymer was 49/51 (mol ratio), and the glass transition temperature (Tg) measured by the DSC method. Was 154 ° C.

Example 75 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. 1,500 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 71 was introduced into an autoclave, and then titanocene dichloride (TC) as a hydrogenation catalyst and the complex obtained in Example 1 were mixed with Ti / Li. The catalyst solution prepared by adding to cyclohexane at a ratio of 1/1 (molar ratio) was added to the polymer in an amount of 100 ppm as metal atom (Ti).

The inside of the autoclave was replaced with hydrogen, the temperature was raised to 75 ° C., the hydrogen pressure was adjusted to 10 kg / cm ² G, and the hydrogenation reaction was carried out for 30 minutes. After completion of the hydrogenation reaction, the autoclave was cooled to room temperature, the pressure was reduced to normal pressure, and then the inside was replaced with nitrogen. Methanol (MeOH) was added according to a conventional method to treat n-BuLi.

As a stabilizer in the polymer solution, manufactured by Ciba-Geigy Co., Ltd. [Irganox B215 (0037H
X)] was added and the solvent was removed according to a conventional method to obtain a hydrogenated CHD-Bd-CHD triblock copolymer exhibiting rubber elasticity. The hydrogenation rate of the CHD portion calculated by ¹ H-NMR of the obtained polymer was 0%, and the Bd portion was 1,
The hydrogenation rates of the 2-vinyl part, 1,4-cis and trans parts were all 100%.

Example 76 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 1500 g of cyclohexane was introduced into the autoclave and kept at 70 ° C. under dry nitrogen. A hydrogenation reaction was carried out in the same manner as in Example 75 except that the polymer obtained in Example 72 was used. The hydrogenation rate of the CHD portion calculated by ¹ H-NMR of the obtained polymer was 0%, and the hydrogenation rate of the Bd portion was 1,2-
The hydrogenation rates of the vinyl part, 1,4-cis and trans parts were all 100%.

Example 77 The inside of a 100 ml Schlenk tube which had been sufficiently dried by a conventional method was replaced with dry argon. Cyclohexane 27.0
g was injected into the Schlenk tube, and the temperature of cyclohexane was kept at room temperature. Further, an n-BuLi solution of n-BuLi (1.6 M) was added in an amount of 0.15 in terms of lithium atom.
mmol was added and the temperature of the solution was kept at 40 ° C. Then, a 1.0 M cyclohexane solution of TMEDA (first complexing agent) was prepared. This solution is n-BuLi / TME
It was added so that DA = 4/4 (mol ratio), and 40 ° C.
And reacted for 10 minutes.

Furthermore, a 1.0 M solution of TMEDA in cyclohexane was added to the solution of TMEDA (second complexing agent) at 0.0375.
Additional addition was carried out so that it might become mmol and the cyclohexane solution of the mixture of a complex and TMEDA was obtained. Li / T at this point
MEDA was 4/5 (molar ratio). Furthermore, in a cyclohexane solution of the mixture of the obtained complex and TMEDA,
3.0 g of 1,3-CHD was added, and a polymerization reaction was carried out at 40 ° C. for 4 hours in a dry argon atmosphere. After the completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid. After washing with methanol, vacuum drying was performed at 80 ° C. The yields were all 100 wt%. 1,2-bonds / 1,4-bonds of cyclic conjugated diene-based monomer units in polymer
The binding ratio was 52/48 (molar ratio).

[0384]

The cyclic conjugated diene polymer of the present invention is excellent because it has a relatively high 1,2-bond / 1,4-bond molar ratio and the molecular weight distribution is relatively narrow. It has thermal and mechanical properties and functionality, and can be suitably used alone or as a composite with another resin material / inorganic material depending on the purpose and application. Further, the cyclic conjugated diene-based polymer of the present invention may be hydrogenated, halogenated, hydrohalogenated, alkylated, arylated, if necessary,
Various functionalities can be imparted by performing at least one reaction selected from ring opening and dehydrogenation.

The cyclic conjugated diene polymer of the present invention can be used as an excellent industrial material (structural material, functional material, etc.). Specifically, the cyclic conjugated diene-based polymer of the present invention is a high-performance plastic, a general-purpose plastic,
Special elastomer, thermoplastic elastomer, elastic fiber,
Sheets, films, tubes, hoses, optical materials, coating agents, insulating agents, lubricants, plasticizers, separation membranes, permselective membranes, microporous membranes, functional membranes, functional films (conductive films, photosensitive films, etc.), Functional beads (molecular sieve,
Polymer catalysts, polymer catalyst substrates, etc.), automobile parts, electrical parts, aviation / space parts, railway parts, marine parts, electronic parts,
Battery parts, electronics related parts, multimedia related parts, plastics for battery materials, solar cell parts, functional fibers, functional sheets, machine parts, medical device parts, pharmaceutical packaging materials, sustained release packaging materials, support for pharmacological substances Not only used as a base material, printed circuit board material, food container, general packaging material, clothing, sports / leisure goods, general miscellaneous goods, tires, belts, other resin modifiers, etc. By blending it, it can be used in applications and fields as a curable resin such as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin and a wet curable resin. The cyclic conjugated diene-based polymer of the present invention is a cyclic conjugated diene-based monomer or a cyclic conjugated diene-based monomer and another monomer copolymerizable therewith by the novel polymerization method of the present invention using a specific catalyst. It can be produced by living anion polymerization of a monomer.

[Brief description of drawings]

FIG. 1 is a structural explanatory view of a cyclohexadiene monomer unit having a 1,2-bond. FIG. 1B is a structural explanatory view of a cyclohexadiene monomer unit having a 1,4-bond.

FIG. 2 Example 22 measured by H-H COZY method.
2D (two-dimensional) of polycyclohexadiene obtained in
It is a NMR spectrum chart figure. H (hydrogen) bonded to a carbon atom bonded by an olefin bond in each cyclohexadiene monomer unit constituting the polymer main chain of polycyclohexadiene, and the carbon atom bonded by the above olefin bond A cross peak is observed in H (hydrogen) bonded to the carbon atom adjacent to.

FIG. 3 Example 22 measured by the H-H COZY method.
2D (two-dimensional) of polycyclohexadiene obtained in
It is a NMR spectrum chart figure. A cross peak is observed in H (hydrogen) bonded to a carbon atom bonded by an olefin bond in each cyclohexadiene monomer unit constituting the polymer main chain of polycyclohexadiene.

FIG. 4 is a ¹ H-NMR spectrum chart diagram of the complex [Li / tetramethylethylenediamine (TMEDA) = 4/2 in n-butyllithium (n-BuLi)] obtained in Example 1.

5 is a ⁷ Li-NMR spectrum chart showing the state of Li ions in the complex [Li / TMEDA = 4/2 (in n-BuLi)] obtained in Example 1. FIG.

6 is a mixture of the complex obtained in Example 22 and TMEDA [Li (in n-BuLi) / TMEDA = 4/5).
FIG. 3 is a ¹ H-NMR spectrum chart diagram of

FIG. 7: Mixture of complex obtained in Example 22 with TMEDA [Li (in n-BuLi) / TMEDA = 4/5)
FIG. ⁷ is a ⁷ Li-NMR spectrum chart showing the state of Li ions in FIG.

FIG. 8 ¹ H-NMR of n-BuLi used in Comparative Example 8
It is a spectrum chart figure.

9 is a ⁷ Li-NM of n-BuLi used in Comparative Example 8. FIG.
It is a R spectrum chart figure.

10 is a ¹ H-NMR spectrum chart diagram of the cyclohexadiene homopolymer obtained in Example 22. FIG.

11 is a ¹ H-NMR spectrum chart diagram of the hydrogenated cyclohexadiene homopolymer obtained in Example 24. FIG.

FIG. 12 is a ¹ H-NMR spectrum chart diagram of the polycyclohexadiene-polyisoprene-polycyclohexadient block copolymer obtained in Example 38.

13 is a ¹ H-NMR spectrum chart diagram of the hydrogenated polycyclohexadiene-polyisoprene-polycyclohexadienth block copolymer obtained in Example 44. FIG.

FIG. 14 is a ¹ H-NMR spectrum chart diagram of the polycyclohexadiene-polystyrene-polycyclohexadient block copolymer obtained in Example 47.

FIG. 15 is a ¹ H-NMR spectrum chart of the polycyclohexadiene-polybutadiene-polycyclohexadientry block copolymer obtained in Example 57.

16 is a ¹ H-NMR spectrum chart diagram of the hydrogenated polycyclohexadiene-polystyrene-polycyclohexadient block copolymer obtained in Example 70. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08F 297/06 MRG C08F 297/06 MRG (72) Inventor Yukiko Kabushi 3 Shiodori, Kurashiki, Okayama Prefecture 13-1 Asahi Kasei Kogyo Co., Ltd.

Claims (32)

[Claims] 1. A polymer having a polymer main chain represented by the following formula (I), wherein the monomer unit A has 1,2-bonds and 1,4-bonds in the polymer main chain. Connect, 1,2
-Molar ratio of bonds / 1,4-bonds 40/60 to 90/1
And the number average molecular weight of the polymer is 500 to
A cyclic conjugated diene polymer characterized by being in the range of 5,000,000. Embedded image [In the formula (1), A to E represent monomers constituting the polymer main chain, and A to E may be arranged in any order. a to e represent the respective wt% of the monomer units A to E with respect to the total weight of the monomer units A to E. A: One or more monomer units selected from cyclic conjugated diene monomer units. B: One or more monomer units selected from chain conjugated diene monomer units. C: One or more monomer units selected from vinyl aromatic monomer units. D: One or more monomer units selected from polar monomer units. E: One or more monomer units selected from ethylene and α-olefin monomer units. a to e satisfy the following relationships. a + b + c + d + e = 100, 0.1 ≦ a ≦ 100, 0 ≦ b <100, 0 ≦ c <100, 0 ≦ d <100, and 0 ≦ e <100. ] 2. The cyclic conjugated diene polymer according to claim 1, which is a block copolymer. 3. A glass transition temperature (Tg) of 150 ° C. or higher.
The cyclic conjugated diene-based polymer according to claim 1 or 2, wherein 4. A glass transition temperature (Tg) of 150 ° C. or higher.
The cyclic conjugated diene polymer according to claim 2, which is a block copolymer having a block unit having 5. The cyclic conjugated diene-based polymer according to claim 2, which is a block copolymer of at least a triblock. 6. The cyclic conjugated diene polymer according to any one of claims 2 to 5, which is a block copolymer having a block unit containing at least two or more monomer units A. 7. The cyclic conjugated diene-based polymer according to claim 2, which is a block copolymer having a block unit consisting of at least two or more monomer units A. 8. At least one block unit consisting only of at least two or more monomer units A and at least one block unit consisting only of at least one monomer unit selected from monomer units B to E. The cyclic conjugated diene-based polymer according to any one of claims 2 to 4, which is a block copolymer having at least a diblock. 9. One composed of one block unit X containing at least one monomer unit A, and at least one monomer unit mainly selected from a monomer unit B and a monomer unit E. Block unit Y and X / Y
The cyclic conjugated diene-based polymer according to claim 2, which is a block copolymer of a diblock having a weight ratio of 1/99 to 99/1. 10. Consists of at least two block units X containing at least one monomer unit A and at least one monomer unit mainly selected from a monomer unit B and a monomer unit E. And at least one block unit Y having a weight ratio of X / Y of 1/99 to 99/1.
6. The cyclic conjugated diene-based polymer according to claim 5, which is a block copolymer of at least a triblock within the range. 11. A constitution comprising two block units X containing at least one monomer unit A and at least one monomer unit mainly selected from a monomer unit B and a monomer unit E. Has one block unit Y and X /
The cyclic conjugated diene polymer according to claim 5, which is a triblock block copolymer having a weight ratio of Y in the range of 1/99 to 99/1. 12. The structure of the block copolymer of at least triblock is: [However, p is an integer of 1 or more and q is an integer of 2 or more. X and Y have the same meaning as defined above. ] The cyclic | annular conjugated diene type-polymer of Claim 10 represented by this. 13. The monomer unit A is at least one cyclic conjugated diene monomer unit selected from the monomer units represented by the following formula (II). The cyclic conjugated diene-based polymer as described above. Embedded image [M represents an integer of 1 to 4. Each R ¹ is independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, or a C ₂ to
A C ₂₀ unsaturated aliphatic hydrocarbon group, a C _{5 to} C ₂₀ aryl group, a C _{3 to} C ₂₀ cycloalkyl group, a C _{4 to} C ₂₀ cyclodienyl group, or a 5- to 10-membered ring and at least one Is a heterocyclic group containing nitrogen, oxygen or sulfur as a hetero atom, each R ² is independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, a C _{2 to} C ₂₀ unsaturated aliphatic carbon group. hydrogen group, an aryl group of _{C 5 ~C 20, C 3 ~C} 20
A cycloalkyl group of C ₄ -C ₂₀ cyclodienyl group,
Or a heterocyclic group having a 5- to 10-membered ring and containing at least one nitrogen, oxygen or sulfur as a hetero atom, or each R ² independently represents two R ^2- (CR ³
_{2) n} -R ³ have the same meaning as R ^1, n is such as to form a a a) integer of 1 to 10 indicates the bond or groups. ] 14. The cyclic according to claim 13, wherein the monomer unit A is at least one cyclic conjugated diene monomer unit selected from the monomer units represented by the following formula (III). Conjugated diene polymer. [Chemical 4] [Each R ² has the same meaning as defined in formula (II). ] 15. The monomer unit A comprises a 1,3-cyclopentadiene monomer unit, a 1,3-cyclohexadiene monomer unit, a 1,3-cyclooctadiene monomer unit and derivatives thereof. The cyclic conjugated diene polymer according to claim 13, which is at least one selected from the group. 16. The cyclic conjugated diene polymer according to claim 14, wherein the monomer unit A is a 1,3-cyclohexadiene monomer unit or a derivative thereof. 17. The cyclic conjugated diene-based polymer according to claim 14, wherein the monomer unit A is a 1,3-cyclohexadiene monomer unit. 18. The cyclic conjugated diene-based polymer according to claim 1, which is selected from hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation. A polymer obtained by carrying out at least one reaction. 19. A method for producing a cyclic conjugated diene-based polymer having a polymer main chain represented by the following formula (I): [In the formula (I), A to E represent monomer units constituting the polymer main chain, and A to E may be arranged in any order. a to e represent the respective wt% of the monomer units A to E with respect to the total weight of the monomer units A to E. A: One or more monomer units selected from cyclic conjugated diene monomer units. B: One or more monomer units selected from chain conjugated diene monomer units. C: One or more monomer units selected from vinyl aromatic monomer units. D: One or more monomer units selected from polar monomer units. E: One or more monomer units selected from ethylene and α-olefin monomer units. A to E satisfy the following relationships. a + b + c + d + e = 100, 0.1 ≦ a ≦ 100, 0 ≦ b <100, 0 ≦ c <100, 0 ≦ d <100, and 0 ≦ e <100. ], The number average molecular weight of the polymer is 500 to 5,000,0
In the range of 00, wherein the above-mentioned production method provides: a complex of at least one organometallic compound containing a metal of Group IA of the Periodic Table with at least one first complexing agent, and at least one cyclic conjugated diene -Based monomers, or at least one cyclic conjugated diene-based monomer and at least one other monomer copolymerizable therewith (chain conjugated diene-based monomers, vinyl aromatic-based monomers, A polar monomer, an ethylene monomer, and an α-olefin monomer) in the presence of a catalyst consisting of a mixture of the above complex and at least one second complexing agent. A manufacturing method characterized by: 20. Each of said at least one first complexing agent and at least one second complexing agent independently comprises oxygen (O), nitrogen (N), sulfur (S) and phosphorus (P). The method according to claim 19, which is an organic compound containing at least one element selected from the group consisting of: 21. Each of said at least one first complexing agent and at least one second complexing agent is independently selected from the group consisting of ether compounds, metal alkoxides, amine compounds and thioether compounds. 20. The method according to claim 19, which is an organic compound. 22. The method according to claim 19, wherein each of the at least one first complexing agent and the at least one second complexing agent is independently an ether compound or an amine compound. Production method. 23. The method according to claim 19, wherein each of the at least one first complexing agent and the at least one second complexing agent is independently an amine compound. 24. The method according to claim 19, wherein each of the at least one first complexing agent and the at least one second complexing agent is independently a diamine compound. 25. The method of claim 19, wherein each of the at least one first complexing agent and the at least one second complexing agent is, independently, an aliphatic diamine compound. Method. 26. The method of claim 19, wherein each of the at least one first complexing agent and the at least one second complexing agent is independently a tertiary amine compound. Method. 27. The method according to claim 24, wherein the diamine compound is selected from tetramethylethylenediamine (TMEDA) and diazabicyclo [2,2,2] octane (DABCO). 28. The method according to claim 19, wherein the at least one organometallic compound containing a metal of Group IA of the periodic table is an organolithium compound. 29. The at least one organometallic compound containing a metal of Group IA of the periodic table is normal butyl lithium (n-BuLi), secondary butyl lithium (s-BuLi) and tertiary butyl lithium (t). -BuLi), wherein each of the at least one first complexing agent and the at least one second complexing agent is independently tetramethylethylenediamine (TMEDA) and The manufacturing method according to claim 19, wherein the manufacturing method is selected from diazabicyclo [2,2,2] octane (DABCO). 30. The above complex is prepared by reacting at least one organometallic compound containing a metal of Group IA of the periodic table with at least one first complexing agent in a molar ratio shown by the following formula. Claims 19 to 2 characterized in that
9. The manufacturing method according to any one of 9. A ₁ / B ₁ = 200/1 to 1/100 (where A ₁ represents the molar amount of the group IA metal atom in at least _one organometallic compound used, and B ₁ is at least one first complexing agent used) The molar amount of 31. The above complex is composed of at least one organometallic compound containing a metal of Group IA of the periodic table and at least one first complexing agent in a molar ratio represented by the following formula. The manufacturing method according to any one of claims 19 to 29, characterized in that. A ₂ / B ₂ = 1 / 0.25 to 1/1 (where A ₂ represents the molar amount of the group IA metal atom in at least one organometallic compound in the complex, and B ₂ represents at least one in the complex) The molar amount of the first complexing agent is shown.) 32. In the above catalyst, the at least one organometallic compound, the at least one first complexing agent and the at least one second complexing agent are represented by the following formula: 20. It exists in a ratio, The said Claim 19- characterized by the above-mentioned.
29. The manufacturing method according to any one of 29. A ₃ / B ₃ = 100/1 to 1/200 (where A ₃ is the molar amount of Group IA metal atom in at least one organometallic compound in the catalyst, B ₃ is at least one first complex in the catalyst) Total molar amount of the agent and at least one second complexing agent)