KR100208316B1 - Improved cyclic conjugated diene polymer and process for producing the same - Google Patents

Abstract

The present invention relates to a cyclic conjugated diene polymer, wherein the group backbone comprises a mixture of at least one cyclic conjugated diene monomer unit or at least one other monomer copolymerizable with the cyclic conjugated diene monomer. The diene monomer units are bonded to each other in the main chain through 1,2- and 1,4-bonds in a relatively high molar ratio of 1,2-bonds to 1,4-bonds, and the cyclic conjugated diene polymer has a relatively narrow molecular weight. Distribution and improved thermal and mechanical properties. The present invention also represents an industrially beneficial method for producing diene polymers having excellent characteristics using unique catalysts.

Description

[Name of invention]

Improved cyclic conjugated diene polymer and preparation method thereof

[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 a backbone comprising at least one cyclic conjugated diene monomer unit or at least one cyclic conjugated diene monomer unit and at least one monomer derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer. The present invention relates to a novel cyclic conjugated diene polymer comprising a cyclic conjugated diene monomer, wherein the cyclic conjugated diene monomer is bonded to the main chain by 1,2-bond and 1,4-bond, and the 1,2-bond / 1,4-bond molar ratio is relatively high. high. The cyclic conjugated diene polymer of the present invention has a relatively narrow molecular weight distribution and is improved in thermal and mechanical properties. The present invention also relates to an industrially advantageous process for producing such excellent cyclic conjugated diene polymers, in which a unique catalyst is used.

[Prior technology]

In recent years, polymer chemistry has made continuous progress through various innovations to meet the industrial demand for increasing diversification. Particularly in the field of polymers used as industrially important materials, extensive research has been directed at improving polymers with better thermal and mechanical properties. There has been a proposal for polymers and methods for their preparation.

For example, there has been a proposal for conjugated diene polymers such as polybutadiene and polyisoprene. This reason lies in the fact that the structure of the polymer molecular chain of the conjugated diene polymer can be relatively easily adjusted to obtain a polymer material having desired properties. Some conjugated diene polymers produced by such proposed techniques have been widely used as industrially important materials.

However, according to recent outstanding methods of the art in this field, it has improved properties, in particular excellent thermal properties (eg melting temperature, glass transition temperature and heat deformation temperature) and excellent mechanical properties (eg tensile modulus and flexural modulus) There is a strong demand for improvement of polymer materials.

As one of the most practical means to meet such needs, it is possible to homopolymerize or air-reduce monomers with relatively small steric hindrances, for example butadiene or isoprene, as well as those with large steric hindrances, for example cyclic conjugated diene monomers. At the time of incorporation, attempts have been made to develop techniques to improve the structure of the polymer molecular chains of polymers of conjugated diene monomers in order to obtain polymer materials having excellent thermal and mechanical properties.

For homopolymerization or copolymerization of relatively small steric hindrance monomers, for example butadiene or isoprene, catalyst systems with somewhat satisfactory polymerization activity have been successfully developed. However, no catalyst system has yet been developed that exhibits satisfactory polymerization activity of homopolymerization or copolymerization of large steric hindrance monomers, for example cyclic conjugated diene monomers.

That is, with conventional techniques, homopolymerization of cyclic conjugated dienes is difficult, and homopolymers of the desired high molecular weight cannot be obtained. In addition, attempts have been made to copolymerize cyclic conjugated dienes with monomers other than cyclic conjugated dienes in order to obtain polymers of optimum thermal and mechanical properties for a wide range of industrial needs, but the resulting product is the only oligomer of low molecular weight. Did not succeed.

As is evident from the above, it is impossible to obtain cyclic conjugated diene polymers with satisfactory properties by traditional techniques. Thus, there was a strong intention to solve the problem.

J. Am. Chem. Soc., 81, 448 (1959), disclose a cyclohexadiene homopolymer and its polymerization method, wherein the homopolymer is prepared using 1,3-cyclohexadiene (a complex catalyst consisting of titanium tetrachloride and triisobutylaluminum). Typical examples of the cyclic conjugated diene monomer are obtained by polymerization.

However, the polymerization process shown in the prior art documents is not advantageous in that it requires the use of a large amount of catalyst, the polymerization reaction must be carried out for a long time, and the obtained polymer has only a very low molecular weight. Therefore, the polymers obtained by the prior art literature have no industrial value.

In addition, J. Polym. Sci., Pt. A, 2,3277 (1964) shows a process for the preparation of cyclohexadiene homopolymers, wherein the polymerization of 1,3-cyclohexadiene can be carried out by various polymerization methods such as radical polymerization, cationic polymerization, anionic polymerization and coordination polymerization. Is performed.

Among the methods shown in this prior art document, however, the polymer obtained has only a very low molecular weight. Thus, polymers obtained by the techniques of the prior art literature have no industrial value.

British Patent Application No. 1,042,625 describes a process for preparing cyclohexadiene homopolymers, wherein the polymerization of 1,3-cyclohexadiene is carried out using a large amount of organolithium compounds as catalyst.

In the polymerization process shown in British Patent Application No. 1,042,625, the catalyst is used in amounts as large as 1 to 2% by weight, based on the total weight of the monomers. Thus, this method is not industrially beneficial. In addition, the polymer obtained by this method has only a very low molecular weight. Also in this prior art document there is no teaching or suggestion for obtaining a copolymer. Moreover, the polymers obtained contain large amounts of catalyst residues, which makes the process of the prior art literature in view of very difficult to remove from the polymers, and the polymers obtained in this way are of industrial value. none.

J. Polym. Sci., Pt. A, 3, 1553 (1965) represents a cyclohexadiene homopolymer, which is obtained by polymerizing 1,3-cyclohexadiene using an organolithium compound as a catalyst. In this prior art document, the polymerization reaction should continue for 5 weeks, but the polymer obtained has only a number average molecular weight of 20,000 or less.

Polym. Prepr. (Amer. Chem. Soc., Div. Polym. Chem.) 12, 402 (1971) discloses the cyclohexadiene obtained when the polymerization of 1,3-cyclohexadiene is carried out using an organolithium compound as a catalyst. It indicates that the upper limit of the number average molecular weight of the polymer is only 10,000 to 15,000. This document also shows that the reason for such a small molecular weight lies in the fact that the transition reaction by extraction of lithium cations present at the polymer end occurs simultaneously with the polymerization reaction and the removal reaction of lithium hydride occurs.

Die Makromolekulare Chemie., 163, 13 (1973) shows a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using a large amount of organolithium compound as a catalyst. However, the polymers obtained in this prior art document are oligomers having only a number average molecular weight of 6,500.

European polymer J., 9, 895 (1973) shows a copolymer obtained by copolymerizing butadiene and / or isoprene with 1,3-cyclohexadiene using an n-allyl nickel compound as a polymerization catalyst. However, the polymer obtained in the prior art document is an oligomer having a very small molecular weight. It is also reported that the polymers of this prior art document have a single glass transition temperature, which indicates that the polymer has a random copolymer structure.

Polymer Publication No. 34, No. 5,333 (1977), shows a method for synthesizing a copolymer of 1,3-cyclohexadiene and acrylonitrile using zinc chloride as a polymerization catalyst. However, the alternating copolymers obtained in these prior art documents are oligomers with very low molecular weight.

J. Polym. Sci., Polym. Chem. Ed., 20, 901 (1982) shows a cyclohexadiene homopolymer obtained by polymerizing 1,3-sigolohexadiene using an organosodium compound as a catalyst. In this prior art document, the organosodium compound used is sodium naphthalene and the radical anions derived from sodium naphthalene form dianions which serve as polymerization initiation sites. This means that although the cyclohexadiene homopolymer reported in this document has an apparent number average molecular weight of 38,700, this homopolymer is actually the only bond of two polymerized molecular chains, each of which has a number average molecular weight of 19,350 Each extends from the polymerization start position in two different directions. In addition, in the polymerization process shown in this document, it is necessary to carry out the polymerization reaction at a very low temperature. Thus, the technique of this document is of no industrial value.

Makromol. Chem., 191, 2743 (1990) show a method of polymerizing 1,3-cyclohexadiene using polystyryllithium as a polymerization initiator. In this prior art document, according to the description, the transition reaction by the extraction of the lithium cation present at the polymer terminal occurs simultaneously with the polymerization reaction and the removal reaction of the lithium hydride occurs vigorously. Furthermore, according to the report, even if the polymerization is carried out using polystyryllithium as the polymerization initiator, the styrenecyclohexadiene block copolymer cannot be obtained at room temperature, and the obtained product is only a cyclohexadiene homopolymer. Also in this prior art document, according to the report, when the polymerization reaction is carried out at -10 ° C, a styrene-cyclohexadiene block copolymer having a molecular weight of about 20,000 is obtained in very low yield with a cyclohexadiene homopolymer. . However, the content of cyclohexadiene block in the obtained copolymer is very low. This prior art document also teaches or suggests for block copolymers of chain conjugated diene monomers and cyclohexadienes as well as multiblock copolymers that are at least triblock copolymers of cyclohexadiene, or radical block copolymers of cyclohexadiene. none.

Reportedly, among the conventional techniques for the preparation of cyclohexadiene polymers by the polymerization of 1,3-cyclohexadiene, the monomer units derived from 1,3-cyclohexadiene monomers are monomers by only 1,3-bonding. Bound in the backbone of the polymer, the polymer has a glass transition temperature (Tg) of only 89 ° C. or less.

As easily understood above, it is impossible to obtain a cyclic conjugated diene copolymer having excellent properties by any conventional technique and can be satisfactorily used as an industrial material. Nevertheless, a process for producing such conjugated diene copolymers is not known.

[Summary of invention]

In this situation, the present inventors have conducted extensive research to solve the above problems. As a result, it has been successful to develop a technique for producing an improved cyclic conjugated diene polymer comprising a main chain partially or wholly contained in monomer units derived from cyclic conjugated diene monomers. In particular, the use of specific catalysts has made it possible to synthesize cyclic conjugated diene polymers by anionic polymerization, preferably living anionic polymerization, of cyclic conjugated diene monomers under industrially beneficial conditions for polymerization reactions. The monomer units derived from are introduced as part or all monomer units constituting the main chain of the polymer in a desired ratio and form. In addition, in the polymer obtained by the technique of the present invention, the cyclic conjugated diene monomer unit is bonded to the main chain of the polymer by 1,2-bond and 1,4-bond.

More specifically, the present inventors describe complexing agents (first complexing agents) with one or more organometallic compounds containing metals belonging to group IA of the periodic table (hereinafter referred to as group IA metals), and also complexing agents (second complexing agents). When a mixture of complexes with (where the first complexing agent and the second complexing agent may be the same or different) is used as a catalyst for the polymerization of the cyclic conjugated diene monomer (extract is due to the cyclic conjugated diene monomer) Transition reactions due to the extraction of lithium cations present, and the removal of lithium hydride, such as the removal of lithium hydride, can be prevented from occurring in a variety of adverse phenomena necessarily accompanied by conventional techniques, such catalysts are subjected to high temperature conditions, i. Excellent polymerization activity at about 70 ° C., and the cyclic conjugated diene polymer may be industrially produced, in which the cyclic conjugated diene monomer may be combined with 1,2-bonds. 1,4-bonds are bonded to the main chain of the polymer (also, the polymer has a relatively high 1,2-bond content), and the polymer has excellent thermal and mechanical properties as well as a narrow molecular weight distribution. The present invention has been completed based on this new finding.

Typically, in the field of organometallic chemistry, it is known that organometallic compounds containing Group IA metals, and complexing agents such as amines, ethers and metalalkoxides together form a high reactive complex. Thus such complexes are used as effective reaction reagents in the organic synthesis of monomers.

However, in polymer polymer chemistry, it should be considered that complexes of organometallic compounds containing Group IA metals are not preferred for the use of polymerization reactions, however, the reactivity of the complexes is extremely extreme due to ionization of organometallic compounds containing Group IA metals. As a result, side reactions such as adverse metallization occur.

However, as mentioned above, by the inventors, unexpectedly and surprisingly, when a mixture of a first complexing agent and a complex of a second complexing agent and at least one Group IA metal containing organometallic compound is used as a catalyst, a cyclic conjugated diene Polymerization of the monomer can proceed advantageously without the risk of occurrence of side reactions such as metallization, where the structure of the complex of the catalyst can be kept thermally stable. In addition, the present inventors have found that the use of a complexing agent of a first complexing agent and a second complexing agent with at least one group IA metal-containing organometallic compound as a catalyst for the preparation of the cyclic conjugated diene polymer may be applied to the living anion polymerization reaction of the cyclic conjugated diene polymer. Not only enables the synthesis of cyclic conjugated diene polymers but also has a relatively high ratio of cyclic conjugated diene monomer units bonded in the main chain of the cyclic conjugated diene polymer by 1,2-bonds, and the conjugated diene polymer has a high glass transition temperature and high heat. It has been found surprisingly industrially beneficial in terms of having excellent thermal properties such as strain temperature.

Accordingly, it is an object of the present invention to provide an improved cyclic conjugated diene having not only narrow molecular weight distribution but also excellent thermal properties such as high melting temperature, high glass transition temperature and high thermal strain temperature, excellent mechanical properties such as high tensile modulus and high flexural modulus. It is to provide a polymer.

It is another object of the present invention to provide a process for producing the above excellent cyclic conjugated diene polymer, which has a large steric hindrance, which makes it possible to polymerize cyclic conjugated diene monomer which makes polymerization difficult and to 1,2-bonds. This is advantageous in that the ratio of the cyclic conjugated diene monomer bonded to the main chain of the cyclic conjugated diene polymer is relatively high.

These and other objects, features and advantages of the present invention will become apparent from the following description and claims taken in conjunction with the accompanying drawings.

[Brief Description of Drawings]

In the accompanying drawings:

FIG. 1 (a) is a diagram showing the structure of a cyclohexadiene monomer having 1,2-bonds.

FIG. 1 (b) is a diagram showing the structure of a cyclohexadiene monomer having a 1,4-bond.

FIG. 2 is a chart showing the 2-D (two-dimensional) NMR spectrum of the cyclohexadiene homopolymer obtained in Example 22 as measured by HH COSY method, wherein each cyclohexanone in the main chain of the cyclohexadiene homopolymer Cross peaks due to hydrogen atoms bonded to a pair of carbon atoms (bonded to each other with olefinic bonds) in the diene monomer unit, and to carbon atoms in contact with the pair of carbon atoms bonded to each other with oliphene bonds; The cross peak attributable to the hydrogen atom can be observed.

3 is a chart showing the 2-D (two-dimensional) NMR spectrum of the cyclohexadiene homopolymer obtained in Example 22 measured by HH COSY method, wherein each cyclohexanone in the main chain of the cyclohexadiene homopolymer Cross peaks due to hydrogen atoms bonded to a pair of carbon atoms (bonded to each other with olefin bonds) of the diene monomer unit can be observed.

4 is a chart showing the ¹ H-NMR spectrum of a complex having a molar ratio of Li / tetramethylethylenediamine (TMEDA) 4/2 [in n-butyl lithium (n-Buli) obtained in Example 1. FIG.

5 is a chart showing ⁷ Li-NMR spectra of complexes having a Li / TMEDA molar ratio 4/2 (in n-Buli) obtained in Example 1. FIG.

FIG. 6 is a chart showing ¹ N-NMR spectra of complex-TMEDA mixtures having a Li / TMEDA molar ratio of 4/5.

7 is a chart showing ⁷ Li-NMR spectra of the complex-TMEDA mixture having a Li / TMEDA molar ratio of 4/5.

8 is a chart showing the ¹ H-NMR spectrum of n-Buli used in Comparative Example 8.

9 is a chart showing the spectrum of n-Buli used in Comparative Example 8.

10 is a chart showing the ¹ H-NMR spectrum of the cyclic conjugated diene homopolymer of the present invention obtained in Example 22.

FIG. 11 is a chart showing the ¹ H-NMR spectrum of the homopolymer of the present invention, composed of saturated cyclic molecular units derived from a cyclic conjugated diene monomer, obtained in Example 24.

12 is a chart showing the ¹ H-NMR spectrum of the polycyclohexadiene-polyisoprene-polycyclohexadiene triblock copolymer of the present invention obtained in Example 38.

13 is a chart showing the ¹ H-NMR spectrum of the copolymer of the present invention obtained by hydrogenation of the polycyclohexadiene-polyisoprene-polycyclohexadiene triblock copolymer of Example 44.

14 is a chart showing the ¹ H-NMR spectrum of the polycyclohexadiene-polystyrene-polycyclohexadiene triblock copolymer of the present invention obtained in Example 47.

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

FIG. 16 is a chart showing the ¹ H-NMR spectrum of the copolymer of the present invention obtained by hydrogenation of the polycyclohexadiene-polystyrene-polycyclohexadiene triblock copolymer of Example 70.

Detailed description of the invention

In an aspect of the invention, the invention is

Formula 1:

(Where A to E are monomer units constituting the main chain, monomer units A to E are arranged in any order, and a to e are the weights of the monomer units A to E based on the total weight of the monomer units A to E, respectively). %ego;

here,

A is selected from the class constituting the cyclic conjugated diene monomeric unit,

B is selected from the class constituting the chain conjugated diene monomeric unit,

C is selected from the class constituting the vinyl aromatic monomer unit,

D is selected from the class constituting the polar monomer unit,

E is selected from the classes comprising ethylene monomer units and α-olefin monomer units,

here,

a to e satisfy the following relationship,

a + b + c + d + e = 100,

0.1 ≤ a ≤ 100,

0 ≤ b 100

0 ≤ c 100,

0 ≦ d 100, and

0 ≦ e 100;

The monomer unit A is bonded in the main chain by 1,2-bond and 1,4-bond, and the molar ratio of 1,2-bond / 1,4-bond is 40/60 to 90/10)

It provides a cyclic conjugated diene polymer comprising a backbone represented by, having a number average molecular weight of 500 to 5,000,000.

In another aspect of the invention,

Formula 3:

(Where A to E are monomer units constituting the main chain, monomer units A to E are arranged in any order, and a to e are the weights of the monomer units A to E based on the total weight of the monomer units A to E, respectively). %ego;

here,

A is selected from the class constituting the cyclic conjugated diene monomeric unit,

B is selected from the class constituting the chain conjugated diene monomeric unit,

C is selected from the class constituting the vinyl aromatic monomer unit,

D is selected from the class constituting the polar monomer unit,

E is selected from the classes comprising ethylene monomer units and α-olefin monomer units,

here,

a to e satisfy the following relationship,

a + b + c + d + e = 100,

0.1 ≤ a ≤ 100,

0 ≤ b 100,

0 ≤ c 100,

0 ≦ d 100, and

A method for producing a cyclic conjugated diene polymer comprising a main chain represented by 0 ≦ e100) and having a number average molecular weight of 500 to 5,000,000, comprising:

Providing a complex of at least one first complexing agent with at least one organometallic compound containing a metal belonging to group IA of the periodic table,

One or more comonomers (chain conjugated diene monomers, vinyl aromatic monomers, polar monomers) copolymerizable with one or more cyclic conjugated diene monomers, or one or more cyclic conjugated diene monomers in the presence of a catalyst comprising a mixture of a complex and one or more second complexing agents , Ethylene monomers, and α-olefin monomers).

In order to facilitate understanding of the present invention, essential features and embodiments of the present invention are listed below.

1. Formula (I):

(Wherein A to E are monomer units constituting the main chain, monomer units A to E are arranged in any order, and a to e are the weights of the monomer units A to E based on the total weight of the monomer units A to E, respectively). %ego;

here,

A is selected from the class constituting the cyclic conjugated diene monomeric unit,

B is selected from the class constituting the chain conjugated diene monomeric unit,

C is selected from the class constituting the vinyl aromatic monomer unit,

D is selected from the class constituting the polar monomer unit,

E is selected from the classes comprising ethylene monomer units and α-olefin monomer units,

here,

a to e satisfy the following relationship,

a + b + c + d + e = 100,

0.1 ≤ a ≤ 100,

0 ≤ b 100,

0 ≤ c 100,

0 ≦ d 100, and

0 ≦ e 100;

here,

The monomer unit A is bonded in the main chain by 1,2-bond and 1,4-bond, and the molar ratio of 1,2-bond / 1,4-bond is 40/60 to 90/10)

A cyclic conjugated diene polymer containing a main chain represented by the above and having a number average molecular weight of 500 to 5,000,000.

2. The cyclic conjugated diene polymer according to item 1 above, which is a block copolymer.

3. The cyclic conjugated diene polymer of item 1 or 2 above, wherein the glass transition temperature (Tg) is at least 150 ° C.

4. The cyclic conjugated diene polymer of item 2 above, wherein the block copolymer contains a polymer block having a glass transition temperature (Tg) of at least 150 ° C.

5. The cyclic conjugated diene polymer according to any one of items 2 to 4, which is at least one tri-block copolymer.

6. The cyclic conjugated diene polymer according to any one of items 2 to 5, which is a block copolymer having a polymer block containing two or more monomer units A.

7. The cyclic conjugated diene polymer according to any one of items 2 to 5, which is a block copolymer having a polymer block constituting two or more monomer units A.

8. at least two blocks comprising at least one polymer block constituting at least two monomer units A and at least one polymer block constituting at least one monomer unit selected from B to E in any one of items 2 to 4 above. A cyclic conjugated diene polymer characterized by being a copolymer.

9. In any one of the items 2 to 4, one polymer block X containing one or more monomer units A, and one polymer block Y mainly composed of one or more monomer units selected from B and E. A diblock copolymer comprising a cyclic conjugated diene polymer, wherein the weight ratio of X / Y is 1/99 to 99/1.

10. A polymer which is at least a triblock copolymer comprising at least one block X containing at least one monomer unit A and at least one polymer block Y mainly composed of at least one monomer unit selected from B and E. The cyclic conjugated diene polymer, wherein the weight ratio of X / Y is 1/99 to 99/1.

11. The triblock copolymer according to item 5, which comprises two blocks X containing at least one monomer unit A and one block Y mainly composed of at least one monomer unit selected from B and E. Cyclic conjugated diene polymer.

12. The cyclic conjugated diene polymer of item 10, wherein the at least triblock copolymer has a structure represented by a formula selected from the group consisting of:

(Where X and Y are the same as above, p is an integer of 1 or more, and q is an integer of 2 or more)

(Wherein X and Y are the same as above, p is an integer of 1 or more, and q is an integer of 2 or more).

13. The cyclic conjugated diene polymer according to any one of items 1 to 12, wherein the monomer unit A is selected from the class constituting the monomer unit represented by the following formula (5):

(식중, R³는 R¹과 동일하고, n은 1 내지 10의 정수이다)으로 표현되는 브리지를 함께 형성한다).Wherein m is an integer of 1 to 4, each of R ¹ is independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon group, a C ₅ -C ₂₀ aryl group, C _{A 3} -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cyclodienyl group or a 5-10 membered heterocyclic group having at least one nitrogen, oxygen or sulfur atom as a hetero atom, each R ² independently represents a hydrogen atom, a halogen atom, C At least one nitrogen, oxygen, or as a ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon group, a C ₅ -C ₂₀ aryl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cyclodienyl group or a hetero atom Or a 5 to 10 membered heterocyclic group having a sulfur atom, or each R ² independently represents a bonding group or a group, and two R ² groups are

(Wherein R ³ is the same as R ¹ and n is an integer of 1 to 10) together to form a bridge.

14. The cyclic conjugated diene polymer according to item 13, wherein the monomer unit A is selected from the class consisting of monomer units represented by the following formula (6):

Wherein each of R ² is the same as in formula (5).

15. The class of the above item 13, wherein the monomer unit comprises 1,3-cyclopentadiene monomer unit, 1,3-cyclohexadiene monomer unit, 1,3-cyclooctadiene monomer unit, and derivatives thereof. Cyclic conjugated diene polymer, characterized in that at least one cause selected from.

16. The cyclic conjugated diene polymer according to item 14, wherein the monomer unit A is a 1,3-cyclohexadiene monomer unit or a derivative thereof.

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

18. A polymer prepared by carrying out at least one reaction of hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening and dehydrogenation with respect to the cyclic conjugated diene polymer of any one of items 1 to 17 above.

19. Formula 7:

(Wherein A to E are monomer units constituting the main chain in which the monomer units A to E are arranged in a certain order, and a to e are the weights of the monomer units A to E based on the total weight of the monomer units A to E, respectively). %ego;

A is selected from the class constituting the cyclic conjugated diene monomeric unit,

B is selected from the class constituting the chain conjugated diene monomeric unit,

C is selected from the class constituting the vinyl aromatic monomer unit,

D is selected from the class constituting the polar monomer unit,

E is selected from the classes comprising ethylene monomer units and α-olefin monomer units,

here,

a to e satisfy the following relationship,

a + b + c + d + e = 100,

0.1 ≤ a ≤ 100,

0 ≤ b 100,

0 ≤ c 100,

0 ≦ d 100, and

A method for producing a cyclic conjugated diene polymer, comprising a polymer represented by 0 ≦ e100) and having a number average molecular weight of 500 to 5,000,000, comprising the following:

Providing a complex of at least one first complexing agent with at least one organometallic compound containing a metal belonging to group IA of the periodic table,

At least one cyclic conjugated diene monomer, or at least one comonomer (chain conjugated diene monomer, vinyl aromatic monomer) copolymerizable with the monomer and at least one cyclic conjugated diene monomer in the presence of a catalyst comprising a mixture of a complex and at least a second complexing agent , Selected from the group consisting of polar monomers, ethylene monomers, and α-olefin monomers.

20. At least one of item 19, wherein the first and second complexing agents are each independently selected from the group consisting of oxygen (O), nitrogen (N), sulfur (S) and phosphorus (P). It is an organic compound containing an element.

21. The method of item 19, wherein each of the first and second complexing agents is independently an organic compound selected from the group consisting of ethers, metal alkoxides, amines and thioethers.

22. The method according to item 19, wherein each of the first and second complexing agents is independently an ether or an amine.

23. The method according to item 19, wherein each of the first and second complexing agents is independently an amine.

24. The method according to item 19, wherein each of the first and second complexing agents is independently diamine.

25. The method according to item 19, wherein each of the first complexing agent and the second complexing agent is independently aliphatic diamine.

26. The method according to item 19, wherein each of the first and second complexing agents is independently a tertiary amine.

27. The method according to item 24, wherein the diamine is selected from the group consisting of tetramethylethylenediamine (TMEDA) and diazabicyclo [2,2,2] -octane (DABCO).

28. The method according to any one of items 19 to 27, wherein the organometallic compound containing a metal belonging to group IA of the periodic table is an organolithium compound.

29. In item 19, the organometallic compound containing a metal belonging to group IA of the periodic table includes normal butyllithium (n-BuLi), secondary butyllithium (s-BuLi) and tertiary butyllithium (t-BuLi). An organolithium compound selected from the group consisting of: wherein the first complexing agent and the second complexing agent are each independently tetramethylethylenediamine (EMEDA) and diazabicyclo [2,2,2] -octane (DABCO) And selected from the group consisting of:

30. The complex of any one of items 19 to 29, wherein the complexing agent is prepared by reacting the first complexing agent with the organometallic compound containing a metal belonging to group IA of the periodic table. How to:

A ₁ / B ₁ = 200/1 to 1/100

(Wherein A ₁ represents the molar amount of the Group IA metal contained in the organometallic compound used in the reaction, and B ₁ represents the molar amount of the first complexing agent used in the reaction).

31. The compound according to any one of items 19 to 29, wherein the complex contains the organometallic compound containing the metal belonging to the Group IA metal of the periodic table and the first complexing agent in a molar ratio represented by the following formula: How to:

A ₂ / B ₂ = 1 / 0.25 to 1/1

(Wherein A ₂ represents the molar amount of the Group IA metal contained in the organometallic compound constituting the complex, and B ₂ represents the amount of the first complexing agent constituting the complex).

32. The method according to the above items 19 to 29, wherein in the catalyst, the organometallic compound, the first complexing agent and the second complexing agent are present in a molar ratio relationship represented by the following formula:

A ₃ / B ₃ = 100/1 to 1/200

(Wherein A ₃ represents the molar amount of the Group IA metal contained in the organometallic compound, and B ₃ represents the total molar amount of the first complexing agent and the second complexing agent).

In the present invention, the monomer unit of the polymer is called according to the nomenclature, and the name of the original monomer from which the monomer unit is derived is used as the term unit. For example, a cyclic conjugated diene monomer unit means a monomer unit formed from a polymer obtained by polymerization of a cyclic conjugated diene monomer and having a molecular structure in which a corresponding cycloolefin is bonded at two carbon atoms of a skeleton in a cyclic conjugated diene monomer. . In addition, a cyclic olefin monomer unit means the monomer unit which has a molecular structure formed in the polymer obtained by superposition | polymerization of a cyclic olefin monomer, and the cycloalkane corresponding to a cyclic olefin monomer is couple | bonded at two carbon atoms of a skeleton.

In the present invention, the cyclic conjugated diene polymer is a polymer comprising a main chain composed partially or entirely of cyclic conjugated diene monomers and / or monomer units derived from the monomer units.

Representative examples of the cyclic conjugated diene polymer of the present invention are polymers comprising a main chain uniquely contained in at least one monomer unit selected from the class constituting the cyclic conjugated diene monomer unit, and copolymerizable with the cyclic conjugated diene monomer unit and the conjugated diene monomer. And polymers comprising a backbone composed of one or more monomer units selected from the class comprising monomer units derived from one or more monomers.

More specific examples of the cyclic conjugated diene polymer of the present invention are homopolymers of cyclic conjugated diene monomers, copolymers of at least two kinds of cyclic conjugated diene monomers, and copolymerizable with at least one type of cyclic conjugated diene monomers and cyclic conjugated diene monomers. Copolymers of at least one copolymer.

Preferred examples of the cyclic conjugated diene polymer of the present invention are composed of at least one monomer unit selected from the group consisting of a cyclic conjugated diene monomer having a cyclohexane ring in its molecular structure and a cyclic conjugated diene monomer having a cyclohexane ring in its molecular structure. Polymers comprising a main chain.

In another aspect of the present invention, the present invention provides a polymer prepared by carrying out at least one of hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation of a cyclic conjugated diene polymer.

In the present invention, the term cyclic conjugated diene monomer means a cyclic conjugated diene having at least a 5-membered carbocyclic structure.

It is preferable that the cyclic conjugated diene monomer is a cyclic conjugated diene having a 5 to 8 membered carbocyclic structure.

Most preferably, the cyclic conjugated diene monomer is a 6-membered cyclic conjugated diene having a carbocyclic structure.

Examples of cyclic conjugated diene monomers include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, and derivatives thereof. Preferred examples of the cyclic conjugated diene monomers include 1,3-cyclohexadiene and 1,3-cyclohexadiene derivatives. Of these, 1,3-cyclohexadiene is most preferred.

In the present invention, examples of the comonomer copolymerizable with the cyclic conjugated diene monomer may be the above monomers which can be polymerized by anionic polymerization.

Examples of such monomers are chain conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and their derivative; Vinyl aromatic monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, 1,3-dimethylstyrene, divinylbenzene, vinylnaphthalene, vinylatracene, 1,1-di Phenylethyrene, m-diisopropenylbenzene, vinylpyridine and derivatives thereof; Polar vinyl monomers such as methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone and methyl α-cyanoacrylate; Polar monomers such as ethyl oxide, propylene oxide, cyclohexene oxide, lactones, lactams and cyclosiloxanes; Ethylene monomers and α-olefin monomers. Each of these monomers may be used independently or in combination.

In the present invention, the copolymer of the comonomer and the cyclic conjugated diene monomer may be in any form.

For example, the copolymer may be a block copolymer such as diblock, triblock, tetrablock, multiblock, radical block, asymmetric radical block, graft block, star block, or comb block copolymer. , Graft copolymers, taper copolymers, random copolymers or alternating copolymers.

In the cyclic conjugated diene polymer of the present invention, the monomer units derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer may be monomer units formed by postpolymerization treatment such as hydrogenation, halogenation, alkylation, arylation, and the like. .

In the cyclic conjugated diene polymer of the present invention, the content of the cyclic conjugated diene monomer unit is not particularly limited and may vary depending on the intended use of the polymer. However, the content of the cyclic conjugated diene monomer unit is usually in the range of 0.1 to 100% by weight, preferably 0.5 to 100% by weight, more preferably 1 to 100% by weight based on the weight of the main chain of the cyclic conjugated diene monomer. .

In addition, in order to obtain the cyclic conjugated diene polymer of the present invention which can be used when the polymer requires high thermal and mechanical properties, the content of the cyclic conjugated diene monomer unit in the cyclic conjugated diene polymer is based on the weight of the main chain of the cyclic conjugated diene polymer. In the range of 5 to 100% by weight, more preferably 10 to 100% by weight, most preferably 15 to 100% by weight.

In the present invention, the cyclic conjugated diene polymer can be prepared by living anionic polymerization, where the molecular weight of the polymer can be appropriately controlled.

In view of the productivity of producing such polymers on an industrial scale, it is recommended that the number average molecular weight of the polymer be in the range of 500 to 5,000,000.

For example, when the polymer is used as a functional material, the number average molecular weight of the polymer is in the range of 500 to 2,000,000, preferably 1,000 to 1,000,000, more preferably 2,000 to 8,000,000, most preferably 3,000 to 500,000.

On the other hand, when using a polymer as a structural material, the number average molecular weight of the polymer is 20,000 to 5,000,000, preferably 30,000 to 4,000,000, more preferably 40,000 to 3,000,000, even more preferably 40,000 to 2,000,000, most preferably 40,000 To 1,000,000.

For the cyclic conjugated diene polymer of the present invention, in order to control the molecular weight of the polymer or to obtain the above in the form of a star-shaped polymer, the ends of the plurality of polymerized molecular chains are conventional at least bifunctional coupling agents such as dimethyldichloridesilane, methyl Trichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soymilk, or esters We can estimate the concatenated array using.

In the present invention, the number average molecular weight (Mn) is determined by gel permeation chromatography using a calibration curve obtained for standard polystyrene samples.

In the present invention, the Mw / Mn value (molecular weight distribution standard) of the cyclic conjugated diene polymer is 1.01 to 10, preferably 1.03 to 7.0, more preferably 1.03 to 5.0, even more preferably 1.03 to 2.50, most preferably In the range of 1.03 to 2.00.

In the cyclic conjugated diene polymer of the present invention, the polymerized molecular chain is a structure in which the monomer unit A is bonded by 1,2- or 1,4-bond. The content of each 1,2-bond and 1,4-bond is determined by ¹ H-NMR. In the present invention, it is necessary for the polymer to have 40 to 90 mole% of 1,2-bonds based on the total moles of 1,2-bonds and 1,4-bonds.

If the cyclic conjugated diene polymer has a 1,2-bond content within the above range, such cyclic conjugated diene polymer advantageously has a high glass transition temperature (Tg), which has excellent thermal properties.

If the 1,2-bond content of the polymer is less than 40 mol%, the Tg value of the polymer is advantageously low, which polymer has inferior thermal properties. On the other hand, when the 1,2-bond content of the polymer exceeds 90 mol%, the Tg value of the polymer becomes very high, and the difference between the decomposition temperature of the polymer and the temperature useful for forming or processing the polymer becomes small.

Further, from the viewpoint of the properties, from the viewpoint of the productivity, formability and processability of the cyclic conjugated diene polymer of the present invention, the polymer is preferably 40 to 40 based on the total moles of 1,2-bond and 1,4-bond. It has a 1,2-bond content of 85% by weight, more preferably 40 to 80 mol%, most preferably 40 to 70 mol%.

Furthermore, in order to obtain cyclic conjugated diene polymers having excellent thermal and mechanical properties, most preferably the cyclic conjugated diene polymer has a 1,2-bond content of 40 to 90 mol% and a Tg value of 150 ° C. or higher.

In the case where the cyclic conjugated diene polymer of the present invention is a cyclic conjugated diene block copolymer containing a plurality of different polymer blocks in the polymerized molecular chain, the block copolymer is composed of monomer units uniquely derived from at least one cyclic conjugated diene monomer. At least one polymer copolymer comprising a polymer block, a monomer unit derived from at least one cyclic conjugated diene monomer and a monomer unit derived from at least one comonomer copolymerizable with the cyclic conjugated diene, or at least one copolymerizable with a cyclic conjugated diene monomer It may contain a polymer block composed of monomer units uniquely derived from the comonomer of. For various purposes, each kind of polymer block can be designed and polymerized. By appropriate selection and bonding of such polymers, cyclic conjugated diene block copolymers having properties suitable for the intended use can be obtained.

In the present invention, the polymer block contains at least one cyclic conjugated diene monomer unit when the polymer block, in part or in whole, consists of monomer units selected from the class constituting the cyclic conjugated diene monomer units. Also in this case, the polymer block is at least two cyclic conjugated diene monomer units, preferably 5 or more cyclic conjugated diene monomer units, more preferably in view of improving the thermal and mechanical properties of the cyclic conjugated diene block polymer of the present invention. Preferably, it contains a continuous array of at least 10 cyclic conjugated diene monomer units.

As a process for producing the cyclic conjugated diene block copolymer of the present invention, a method comprising the following may be mentioned: a block unit polymer composed of monomers derived from at least one cyclic conjugated diene monomer, and at least one cyclic conjugated diene monomer Block unit polymers composed of monomer units derived from and monomeric units derived from at least one comonomer copolymerizable with cyclic conjugated diene monomers, and monomer units derived from at least one comonomer copolymerizable with cyclic conjugated diene monomers. Preparing a constructed block unit polymer; Selecting appropriate bonds of these block unit polymers; The block unit polymer is polymerized to obtain a cyclic conjugated diene block comonomer having suitable properties for the intended use of the polymer. If desired, the cyclic conjugated diene block comonomer can be subjected to at least one reaction selected from hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

Specific examples of preferred embodiments of the method of the present invention include the following embodiments.

The method of one embodiment comprises polymerizing and forming a block unit polymer containing monomeric units derived from at least one cyclic conjugated diene monomer, and a block unit polymer uniquely derived from cyclic conjugated diene monomers; Polymerizing at least one comonomer copolymerizable with the cyclic conjugated diene monomer and a block unit polymer, wherein the comonomer is polymerized and successfully bonded to one or both ends of the block unit polymer. If desired, the obtained block copolymer is subjected to at least one kind of reaction during hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

Another aspect of the method comprises polymerizing at least one comonomer copolymerizable with the cyclic conjugated diene monomer to obtain a block unit polymer; Polymerizing at least one type of cyclic conjugated diene monomer and at least one type of comonomer copolymerizable with the cyclic conjugated diene monomer and a block unit polymer, wherein the cyclic conjugated diene monomer and any comonomer are polymerized block unit polymers. Successfully binding to one or both ends of the. If desired, the obtained block copolymer is subjected to at least one reaction among hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

Another embodiment of the method is formed by polymerizing a block unit polymer containing a monomer unit derived from at least one cyclic conjugated diene monomer, or a block unit polymer derived solely from a cyclic conjugated diene monomer, and forming a cyclic conjugated diene monomer. Polymerizing at least one copolymerizable comonomer with a block unit polymer to obtain a polymer; Polymerizing the block unit polymer containing monomer units derived from at least one cyclic conjugated diene monomer or the block unit polymer uniquely derived from the cyclic conjugated diene monomer to successfully bind to the polymer. If desired, the obtained block copolymer is subjected to at least one reaction among hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

In addition, another aspect of the process further comprises polymerizing at least one comonomer copolymerizable with the cyclic conjugated diene monomer to obtain a block unit polymer; Polymerizing a block unit polymer containing a monomer unit derived from at least one cyclic conjugated diene monomer or a block unit polymer uniquely derived from a cyclic conjugated diene polymer and a block unit polymer; And successfully binding to the polymer obtained by polymerizing at least one comonomer copolymerizable with the cyclic conjugated diene monomer. If desired, the obtained block copolymer is subjected to at least one reaction among hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

Another aspect of the method also includes polymerizing at least one type of comonomer and at least one type of cyclic conjugated diene monomer copolymerizable with the cyclic conjugated diene monomer, wherein at least one type of comonomer is at a different polymerization rate than the cyclic conjugated diene monomer. Since the tapered block copolymer is obtained. If desired, the obtained block copolymer is subjected to at least one reaction among hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

In another aspect, the method comprises polymerizing and forming a block unit polymer containing a monomer unit derived from at least one cyclic conjugated diene monomer or a block unit polymer uniquely derived from a cyclic conjugated diene monomer; Polymerizing at least one comonomer and a block unit polymer copolymerizable with a cyclic conjugated diene monomer; Traditional at least bifunctional coupling agents (e.g. dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium Tetrachloride, tin tetrachloride, epoxidized duyu, or ester) to bond the ends of the polymerized molecular chains of the polymer. If desired, the obtained block copolymer is subjected to at least one reaction among hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

Still another aspect of the method includes polymerizing at least one comonomer copolymerizable with the cyclic conjugated diene monomer and the cyclic conjugated diene monomer, wherein the ratio of the cyclic conjugated diene monomer to the at least one copolymer is not primary. . If desired, the obtained block copolymer is subjected to at least one reaction among hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

Yet another aspect of the process is to polymerize and form a block unit polymer containing monomeric units derived from at least one cyclic conjugated diene monomer or a block unit polymer derived solely from cyclic conjugated diene monomers, providing any desired conversion. The polymerization was carried out until any amount of the cyclic conjugated diene monomer remained unreacted; Polymerizing any amount of unreacted cyclic conjugated diene monomer to obtain a block copolymer. If desired, the obtained block copolymer is subjected to at least one reaction among hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation.

In the present invention, the block unit polymer composed of at least one monomer unit selected from the class constituting the cyclic conjugated diene monomer unit may further include a monomer unit derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer. Can be.

Further, in the present invention, the block unit polymer composed of monomer units derived from at least one comonomer copolymerizable with the cyclic conjugated diene monomer includes at least one monomer unit selected from the class constituting the cyclic conjugated diene monomer unit. do.

In the present invention, with respect to the polymer block composed of at least one cyclic conjugated diene monomer and such monomeric units, each monomer comprising a monomer unit composed of a cyclohexene ring and a monomer unit composed of a cyclorexane unit or composed of a cyclohexene ring It is preferable to use each polymer block which comprises a unit.

If desired, the monomer unit and the polymer block may be a monomer unit and a polymer block obtained by subjecting the monomer unit and the block unit to at least one of hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction, and dehydrogenation. Can be.

For cyclic conjugated diene monomer units contained as part or all monomer units constituting the main chain of the cyclic conjugated diene polymer of the present invention, preferred examples are represented by the following formula (8) and most preferred examples are represented by the following formula (9):

(식중, R³는 R¹와 동일한 의미이고 n은 1 내지 10의 정수이다)로 나타내는 다리를 형성하고,{Wherein m is an integer of 1 to 4, and each R ¹ is independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon, a C ₅ -C ₂₀ aryl group, C ₃ A C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cyclodienyl group or a 5-10 membered heterocyclic group having at least one nitrogen, oxygen or sulfur atom as a heteroatom, each R ² independently represents a hydrogen atom, a halogen atom, C ₁ - C ₂₀ alkyl group, C ₂ - C ₂₀ unsaturated aliphatic hydrocarbons, C ₅ - C ₂₀ aryl group, C ₃ - C ₂₀ cycloalkyl unit, C ₄ - C ₂₀ cycloalkyl cyclopentadienyl group or at least one kinds of a heteroatom Or a 5 to 10 membered heterocyclic group having a nitrogen, oxygen or sulfur atom of R ² , each R ² independently represents a bond or a group, wherein two R ² groups are

Forming a bridge represented by (wherein, R ³ is the same as R ¹ and n is an integer of 1 to 10),

Wherein each R ² is the same as formula (8)}.

In each of Formulas 8 and 9, preferably, the alkyl group has 2 to 10 carbon atoms, the unsaturated aliphatic hydrocarbon group has 2 to 10 carbon atoms, the allyl group has 5 to 10 carbon atoms, and the cycloalkyl group has 5 to 10 carbon atoms. It has 10 carbon atoms, the cyclodienyl group has 5 to 10 carbon atoms and the heterocyclic group has a 5 to 8 membered ring structure.

Specific examples of R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, secondary butyl group, tertiary butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group , Vinyl group, phenyl group, tolyl group, naphthyl group, cyclopentadienyl group, indenyl group, pyridyl group, and piperidyl group.

In the present invention, in order to obtain a cyclic conjugated diene block polymer having elastic properties (rubber elasticity), the block copolymer has at least two polymer blocks (binding phase, i.e., hard segments) having a glass transition temperature (Tg) of not less than room temperature and It is necessary to consist of at least one polymer block (rubber phase, ie soft segment) having a Tg lower than room temperature and these two types of blocks need to form a microphase separation structure.

In the polymerized molecular chains of such block copolymers, the confining phase acts at physical crosslinking sites at temperatures lower than Tg, and the block copolymers have elastic properties.

On the one hand, at temperatures higher than Tg or Tg, the confining phase is fluidized and the block copolymer is provided with fluidity. Thus, in this case, melt molding (eg injection molding, brow molding or extrusion molding) or cast molding (eg cast film molding) can be performed.

In the present invention, the polymerized molecular chain of the cyclic conjugated diene copolymer is crosslinked to provide the copolymer with elastic properties (rubber elasticity).

In the following, preferred embodiments of the cyclic conjugated diene block copolymer of the present invention are listed.

(1) A cyclic conjugated diene block copolymer having a glass transition temperature (Tg) of 150 ° C or higher.

(2) Cyclic conjugated diene block copolymer in which a block copolymer contains the polymer block which has a glass transition temperature (Tg) of 150 degreeC or more.

(3) The cyclic conjugated diene block copolymer which is at least a triblock copolymer.

(4) A cyclic conjugated diene block copolymer, which is a block copolymer having a polymer block containing at least two monomer units A.

(5) The cyclic conjugated diene block copolymer, which is a block copolymer having a polymer block constituting at least two monomer units A.

(6) at least a diblock copolymer comprising at least one polymer block constituting at least two monomer units A and at least one polymer block constituting at least one monomer unit selected from the group of B to E monomer units Cyclic conjugated diene block copolymers.

(7) a diblock copolymer comprising one polymer block X comprising at least one monomer unit A and one polymer block Y composed mainly of at least one monomer unit selected from B to E monomer units, wherein And the weight ratio of block X to block Y is 1/99 to 99/1).

(8) at least triblock copolymers comprising at least two blocks X comprising at least one monomer unit A and one polymer block Y mainly composed of at least one monomer unit selected from B-E monomer units ( Wherein the weight ratio of at least two blocks X to at least one block Y is 1/99 to 99/1).

(9) A cyclic conjugated diene block, which is a triblock copolymer comprising two blocks X comprising at least one monomer unit A and one block Y mainly composed of at least one monomer unit selected from B-E monomer units. Copolymer.

(10) A cyclic conjugated diene block copolymer, which is at least a triblock copolymer having a structure represented by a formula selected from the group consisting of:

(Where X and Y are the same as above, p is an integer of 1 or more, and 9 is an integer of 2 or more)

In order to obtain cyclic conjugated diene block copolymers having elastic properties (rubber elasticity), preferably, the cyclic conjugated diene block copolymers have at least two blocks X [each block X (the total weight of the monomer units constituting the block X At least one cyclic conjugated diene monomer unit and / or at least one species of cyclic conjugated diene monomer unit mainly contained in monomer units derived from at least one cyclic conjugated diene monomer unit and / or cyclic conjugated diene monomer unit) Vinyl aromatic monomeric units of; and at least one chain conjugated diene monomeric unit and / or chain conjugated diene monomer (in an amount of at least 50% by weight based on the total weight of the monomer units constituting block Y) At least one block Y mainly comprised of monomeric units derived from the unit. More preferably, the cyclic conjugated diene block copolymer comprises at least two blocks X (in an amount of at least 50% by weight based on the total weight of the monomer units constituting block Y), wherein each block X is at least one type of cyclic Consisting of monomer units derived from conjugated diene monomer units and / or cyclic conjugated diene monomer units), and at least one consisting mainly of monomer units derived from at least one kind of chain conjugated diene monomer units and / or chain conjugated diene monomer units Contains block Y. Particularly preferably, the cyclic conjugated diene block copolymer comprises at least two blocks X (each block X (in block X) in an amount of at least 50% by weight based on the total weight of the monomer units constituting block Y). At least one cyclic conjugated diene monomer unit and / or monomer units derived from cyclic conjugated diene monomer units, in an amount of at least 50% by weight based on the total weight of the monomer units A conjugated diene monomer unit and at least one vinyl aromatic monomer unit], and at least one block Y mainly composed of monomer units derived from at least one chain conjugated diene monomer unit and / or chain conjugated diene monomer unit. It is a polymer obtained by hydrogenation of the cyclic conjugated diene block copolymer containing. Most preferably the cyclic conjugated diene monoblock copolymer comprises at least two blocks X and at least one chain cyclic conjugate (in an amount of at least 50% by weight based on the total weight of the monomer units constituting block Y). A polymer obtained by hydrogenation of a cyclic conjugated diene block polymer comprising at least one block Y mainly composed of diene monomer units and / or monomer units derived from chain cyclic conjugated diene monomer units.

When the cyclic conjugated diene block copolymer of the present invention is used as an industrial material, the monomer units constituting block X are preferably monomer units derived from 1,3-cyclohexadiene, 1,3-cyclohexadiene and Monomer units derived from styrene, or monomer units derived from α-methylstyrene, and the monomer units constituting block Y are hydrogenable monomer units derived from 1,3-butadiene and / or isoprene.

When block Y is formed by the polymerization of 1,3-butadiene monomer and / or isoprene monomer, the vinyl bond content of the monomer can be appropriately controlled without particular limitation. However, in order to obtain a cyclic conjugated diene copolymer having excellent low temperature properties, the total amount of vinyl bonds is preferably 10 to 10 based on the total number of cis- and trans-1,4- and vinyl bonds present in the block Y. 90 mol%, more preferably 20 to 80 mol%.

In the present invention, in order to obtain a block copolymer having elastic properties (rubber elasticity), for example, preferably the block copolymer is a linear block copolymer represented by Formula 10 and a radical block copolymer represented by Formula 11, respectively. to be:

(Wherein p is an integer of 1 or more and each q is an integer of 2 or more);

Wherein each p and each q are as above and each z is independently a polyvalent coupling agent such as dimethyldichlorosilane, methylene chloride, silicon tetrachloride, tin tetrachloride or epoxidized soymilk, or residues of a polymerization initiator such as Multivalent organometallic compounds containing metals belonging to group IA of the periodic table).

Representative examples of the cyclic conjugated diene block copolymers of the present invention having thermoplastic elastic properties include cyclic conjugated diene block copolymers, which are triblock copolymers represented by the formula: XYX, wherein block X is 10 to 60% by weight, preferably Preferably in an amount of 15 to 50% by weight, block Y is present in an amount of 90 to 40% by weight, preferably 85 to 50% by weight, and the triblock copolymer has a number average molecular weight of 1,000 to 200,000. .

On the other hand, a representative example of the cyclic conjugated diene block copolymer of the present invention can be used as a reinforced plastic material, wherein: X-Y-X (wherein, Block X is 40 to 90% by weight, preferably 45 to 85% by weight) And block Y is present in an amount of from 60 to 10% by weight, preferably 55 to 15% by weight), including a cyclic conjugated diene block copolymer, which is a triblock copolymer represented by The copolymer has a number average molecular weight of 1,000 to 200,000.

In the present invention, the cyclic conjugated diene block copolymer having elastic properties may be a polymer that performs at least one of hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction, and dehydrogenation.

In particular, in order to obtain cyclic conjugated diene block copolymers having excellent thermal, mechanical and chemical properties, the block copolymer is preferably hydrogenated.

In the following, a method for producing the improved cyclic conjugated diene polymer of the present invention is described. However, the manufacturing method is not limited to that described below.

For example, in the present invention, at least one complexing agent (first complexing agent), and also at least one complexing agent (second complexing agent) and at least one organic comprising a metal belonging to group IA of the periodic table A cyclic conjugated diene polymer is obtained using a stable catalyst comprising a mixture of complexing agents of metal compounds.

The catalyst used in the present invention is thermally stable and does not cause adverse side reactions such as metallization during the polymerization reaction.

Polymerization of at least one cyclic conjugated diene monomer, or at least one cyclic conjugated diene monomer (selected from the classes comprising chain cyclic conjugated diene monomers, vinyl aromatic monomers, polar monomers, methylene monomers, and α-olefin monomers) Using a catalyst for the polymerization of at least one monomer copolymerizable with a cyclic conjugated diene monomer, the cyclic conjugated diene polymer is synthesized from an cyclic conjugated diene monomer by anionic polymerization, particularly living anion polymerization, under industrially favorable temperature conditions, thereby narrowing the molecular weight distribution. A cyclic conjugated diene polymer having a high 1,2-content in the backbone and excellent thermal properties is obtained.

Examples of metals belonging to the Group IA of the periodic table that can be used in the present invention (hereinafter simply referred to as Group IA metals) include lithium, sodium, potassium, rubidium, cesium and francium. Of these, lithium, sodium and potassium are preferred. Of these, lithium and sodium are particularly preferred, and lithium is most preferred.

In the present invention, examples of organometallic compounds including Group IA metals include organometallics containing lithium, sodium, potassium, rubidium, cesium or francium.

Of these, organometallic compounds containing lithium, sodium or potassium are preferred.

Of these, organometallic compounds containing lithium or sodium are particularly preferred, and organometallic compounds containing lithium are most preferred.

Preferred examples of the organometallic compound used in the present invention include organolithium compounds, organosodium compounds and organopotassium compounds.

Of these, organolithium compounds and organosodium compounds are particularly preferred, and organolithium compounds are most preferred.

The organolithium compound preferably used in the present invention is an organic compound having a structure in which at least one lithium atom is bonded to an organic molecule containing at least one carbon atom, or a structure in which at least one lithium atom is bonded to an organic polymer. It is an organic polymer having.

Examples of organic molecules include C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon groups, C ₅ -C ₂₀ aryl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₄ -C ₂₀ cyclodienyl groups and the like do.

Examples of organic polymers include polybutadiene, polyisoprene, polystyrene, poly-α-methylstyrene, polyethylene, and the like.

Examples of organolithium compounds useful in the present invention include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, secondary butyllithium, tertiary butyllithium, pentyllithium, hexyllithium, allyllithium, cyclo Hexyllithium, phenyllithium, hexamethylenedilithium, cyclopentadiethyllithium, indenylithium, 9-fluorenyllithium, 9-anthrylmethyllithium, 1,1-diphenyl-n-hexyllithium, 1,1 -Diphenyl-3-methylpentyllithium, lithium naphthalene, butadienyldilithium, and isoprenyldilithium. In addition, lithium atoms in the polymerized molecular chain, such as polybutadienyllithium, polybutadienyllithium, polyisoprenylithium, polyisoprenyllithium, polystyryllithium, polystyryldilithium and poly-α-methyldi An oligomeric or polymeric organolithium compound containing lithium can be used.

There is no particular limitation on the type of organolithium compound as long as it can form a stable complex. Representative examples of such organolithium compounds include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, secondary butyllithium, tertiary butyllithium and cyclohexyl lithium.

From a commercial standpoint, preferred examples of organolithium compounds include n-butyllithium (n-BuLi), secondary-butyllithium (s-BuLi), and tertiary butyllithium (t-BuLi), of which n Most preferred is -butyllithium (n-BuLi).

In the present invention, each of the organometallic compounds containing a Group IA metal may be used alone or in combination if desired.

As above, the polymerization catalyst of the present invention is a mixture of at least one first complexing agent and a complexing agent of at least one second complexing agent and at least one group IA metal-containing organometallic compound. The first and second complexing agents may be the same or different.

There is no particular limitation on the form of the first and second complexing agents.

However, preferably, the first complexing agent and the second complexing agent are independently organic compounds having an element having a non-covalent electron pair integratable with a metal atom or a metal ion in the organometallic compound containing the Group IA metal. Examples of such organic compounds include organic compounds containing at least one element of oxygen (O), nitrogen (N), sulfur (S) and phosphorus (P).

Preferred examples of such organic compounds include ethers, metal alkoxides, amines, and thioethers. Particularly preferred examples of organic compounds include cyclic ethers such as tetrahydrofuran, crown ethers and the like, metalalkoxides, and amines. Of these, amines are most preferred.

In particular, examples of such amines include organic amines or organic polymerized amines, the amines comprising at least one R ¹ R ² N-group, wherein each R ¹ and R ² are independently an alkyl group, an aryl group, Or a hydrogen atom), which is a polar group having a lone pair of electrons that can be integrated with an organometallic compound containing a Group IA metal to form a complex.

Among these amines, tertiary amines are particularly preferred, and tertiary diamines are most preferred.

Specific examples of complexing agents useful in the present invention include diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyldetrahydrofuran, tetrahydrofuran, 18-crown-6, dibenzo -18-crown-6, 15-crown-5, dibenzo-24-crown-8, kryptand, lithium-t-butoxide, potassium-t-butoxide, di-t-butoxybarium, porphyrin, 1 , 2-dipiperazinoethane, trimethylamine, triethylamine, tri-n-butylamine, quinuclidin, pyridine, 2-methylpyridine, 2,6-dimethylpyridine, dimethylaniline, diethylaniline, tetramethyldia Minomethane, tetramethylethylenediamine, tetramethyl-1,3-propanediamine, tetramethyl-2-butene-1,4-diamine, tetramethyl-1,4-butanediamine, tetramethyl-1,6-hexane Diamine, tetramethyl-1,4-phenylenediamine, tetramethyl-1,8-naphthalenediamine, tetramethylbenzidine, tetraethylethylenediamine, tetraethyl-1,3-propanedia Min, tetramethyldiethylenetriamine, tetraethyldiethylenetriamine, pentamethyldiethylenetriamine, pentaethyldiethylenetriamine, diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3. 0] -5-nonene, 1,8-diazabisilclo [5.4.0] -7-undecene, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotedecane , Tetrakis (dimethylamino) ethylene, tetraethyl-2-butene-1,4-diamine, (-)-2,3-dimethoxy-1,4-bis (dimethylamino) butane (DBB), (+) -1- (2-pyrrolidinylmethyl) pyrrolidine, 2,2'-bipyridine, 4,4'-bipyridyl, 1,10-phenalthrolidine, hexamethylformoramide (HMPA), and Hexamethylphospho triamide (HMPT).

Preferred examples of tertiary amines useful in the present invention include trimethylamine, triethylamine, tri-n-butylamine, quinuclidin, pyridine, 2-methylpyridine, 2,6-dimethylpyridine, dimethylaniline, diethylaniline, Tetramethyldiaminomethane (tetramethylmethylenediamine), tetramethylethylene, tetramethyl-1,3-propanediamine (tetramethylpropylenediamine), tetramethyl-2-butene-1,4-diamine, tetramethyl-1, 4-butanediamine (tetramethylbutylenediamine), tetramethyl-1,6-hexanediamine (tetramethylhexanediamine), tetramethyl-1,4-hethylenediamine, tetramethyl-1,8-naphthalenediamine, tetra Methylbenzidine, tetraethylethylenediamine, tetraethyl-1,3-propanediamine, tetramethyldiethylenetriamine, tetraethyldiethylenetriamine, pentamethyldiethylenetriamine, pentaethyldiethylenetriamine, 1,4- 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicycle [4.3.0] -5-nonene, 1,8-diazabicyclo [5,4.0] -7-undecene, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclo Tetradecane, tetrakis (dimethylamino) ethylene, tetraethyl-2-butene-1,4-diamine, (-)-2,3-dimethoxy-1,4-bis (dimethylamino) butane (DDB), ( +)-1- (2-pyrrolidinylmethyl) pyrrolidine, 2,2'-bipyridyl, 4,4'-bipyridyl, 1,10-phenanthroline, hexamethylphosphoramide (HMPA ), And hexamethylphospho triamide (HMPT).

Particularly preferred examples of complexing agents useful in the present invention include aliphatic amines, of which aliphatic diamines are most preferred.

Most preferred examples of aliphatic diamines are tetramethylmethylenediamine (TMMDA), tetraethylmethylenediamine (TEMDA), tetramethylethylenediamine (TMEDA), tetraethylethylenediamine (TEEDA), tetramethylpropylenediamine (TMPDA), tetraesyl Propylenediamine (TEPDA), tetramethylbutylenediamine (TMBDA), tetraethylbutylenediamine (TEBDA), tetramethylpentanediamine, tetraethylpentanediamine, tetramethylhexanediamine (TEHDA), tetraethylhexanediamine (TEHDA), And 1,4-diazabisilcyclo [2.2.2] octane (DABCO).

From a commercial point of view, it is most preferably to use aliphatic diamines represented by the following formula (12) to form stable complexes with organolithium compounds.

(Wherein each R ¹ , R ² , R ³ and R ⁴ independently represent a C ₁ -C ₂₀ alkyl group and n represents an integer of 1 to 20).

Preferably such aliphatic diamines can be diamines having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms and most preferably 2 carbon atoms between two nitrogen atoms.

Particularly preferred examples of complexing agents useful in the present invention include tetramethylethylenediamine (TMEDA), and 1,4-diazabicyclo [2.2.2] octane (DABCO). Of these, tetramethylethylene diamine (TMEDA) is most preferred.

The above complexing agents, preferably amines, can be used in combination if desired independently.

From a commercial standpoint, preferably, the catalyst used in the present invention is methyllithium (MeLi), ethyllithium (EtLi), n-propyllithium (n-PrLi), iso- containing at least one group IA metal. Organic selected from the group consisting of propyllithium (i-PrLi), n-butyllithium (n-BuLi), secondary butyllithium (s-BuLi), tertiary butyllithium (t-BuLi), and cyclohexyllithium Metal compounds (particularly organolithium compounds) and tetramethylmethylenediamine (TMMDA), tetramethylethylenediamine (TMEDA), tetramethylpropylenediamine (TMEDA), tetramethylhexanediamine (TMHDA) and 1,4-diazabicyclo [ 2.2.2] from at least one complexing agent (particularly an amine) selected from octane (DABCO).

In the present invention, most preferably, the catalyst is an organometal selected from the group consisting of n-butyllithium (n-BuLi), secondary butyllithium (s-BuLl), and tertiary butyllithium (t-BuLi) Compound and at least one amine selected from tetramethylpropylenediamine (TMEDA) and 1,4-diazabicyclo [2.2.2] octane (DABCO).

In the present invention, there is no particular limitation on the method for synthesizing a complex of at least one organometallic compound containing a Group IA metal with at least one first complexing agent. Synthesis is performed by traditional techniques.

Specific examples of conventional techniques include dissolving organometallic compounds containing Group IA metals in organic solvents in an atmosphere of dried inert gas and adding a solution of the first complexing agent thereto, and organic in an atmosphere of dried inert gas. And a method of dissolving a first complexing agent in a solvent and adding a solution of an organometallic compound containing a Group IA metal thereto. Of these methods, preferred methods are appropriately selected.

With respect to the organic solvent, preferably, the organic solvent used is appropriately selected depending on the kind and amount of the organometallic compound and the kind and amount of the first complexing agent, degassed and dried before use.

Further, preferably, a reaction for obtaining a complex of at least one kind of first complexing agent with at least one kind of organometallic compound is carried out at -100 to 100 ° C.

From a commercial standpoint, the reaction for obtaining the complex is preferably carried out at room temperature to 80 ° C, more preferably at room temperature to 60 ° C.

Examples of inert gases include helium, nitrogen and argon. Among these, nitrogen and argon are preferable from a commercial point of view.

In the present invention, the complexing agent is formed by reacting at least one kind of complexing agent with at least one kind of Group IA metal-containing organometallic compound.

In addition, in the present invention, preferably, the Group IA metal in the complex is present in the form of associating 2 to 10 metal atoms, more preferably 2 to 8 metal atoms, most preferably 2 to 6 metal atoms.

In the preparation of said complex of at least one kind of Group IA metal containing organometallic compound with at least one kind of first complexing agent, the following molar ratio of the Group IA metal contained in the organometal to the complexing agent is preferably used. . The molar ratio is as follows:

Normal,

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 to 1/50,

Even more preferably,

A ₁ / B ₁ = 50/1 to 1/20,

Even more preferably,

A _l / B ₁ = 20/1 to 1/10,

Most preferably,

A ₁ / B ₁ = 1 / 0.2 to 1 / 1.2

(Wherein A ₁ is the molar amount in the group IA contained in the organometallic compound, and B ₁ is the molar amount of the first complexing agent).

As a specific example of the polymerization process of the present invention, the polymerization may be carried out by a catalyst comprising a complex mixture of at least one group IA metal containing organometallic compound and at least one first complexing agent and at least one second complexing agent. In presence, the method is shown below:

(1) adding a second complexing agent to the polymerization solvent, adding a complex of the first complexing agent and the group IA-containing organometallic compound to form a catalyst therein, and then polymerizing in the presence of the catalyst;

(2) adding a complex of a first complexing agent and a Group IA metal-containing organometallic compound to a solvent, adding a second complexing agent to form a catalyst therein, and then polymerizing in the presence of a catalyst;

(3) forming a complex of the first complexing agent and the Group IA metal-containing organometallic compound in the polymerization solvent, adding a second complexing agent to form a catalyst therein, and then polymerizing in the presence of the catalyst;

(4) A complex of the first complexing agent and the IA metal-containing organic metal compound is formed by using the first complexing agent in a large amount in which some of the added first complexing agent does not form a complex and remains unreacted. Process of polymerization in the presence of unreacted first complex (acting as second complexing agent).

Among these methods, a preferable method can be selected suitably. However, when the polymerization reaction is carried out at a high temperature, in particular 60 ° C. or higher, as in the method of (1) to (3), preferably, forming a complex and substantially mixing the complex with the second complexing agent Get in the way of inclusion.

In addition, there is no particular limitation on the amount of the second complexing agent that coexists with the complex in forming the mixture. In the present invention, however, preferably at least one kind of first complexing agent and at least one kind of second complexing agent are present in the following molar relationship at the start of the polymerization reaction of the cyclic conjugated diene monomer.

The molar ratio is as follows:

Normal,

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,

Even more preferably,

A ₃ / B ₃ = 20/1 to 1/50,

Most preferably,

A ₃ / B ₃ = 10/1 to 1/20,

(Wherein A ₃ is the molar amount of the Group IA metal contained in the organometallic compound, and B ₃ is the molar amount of the entire first complexing agent and the second complexing agent).

In the process of the present invention, in order to obtain a cyclic conjugated diene polymer having a high content of monomer units A having 1,2-bonds and thus having excellent thermal stability, the molar ratio is as follows:

Preferably,

A ₃ / B ₃ = 2/1 to 1/10;

Most preferably (in commercial terms),

A ₃ / B ₃ = 1.25 / 1 to 1/5

(Wherein A ₃ and B ₃ are the same as above).

In a most preferred embodiment of the process of the invention, a complex is formed comprising at least one organometallic compound containing a Group IA metal and at least one first complexing agent, and then the complex is at least one second complexation. Mixing with the agent to form a catalyst having the following molar ratio and polymerizing in the presence of the catalyst:

A ₂ / B ₂ = l / 0.25 to 1/1

(Wherein A ₂ is the molar amount of the Group IA metal contained in the organometallic compound contained in the complex, and B ₂ is the molar amount of the first complexing agent contained in the complex).

Representative examples of the polymerization process of the present invention are A ₂ moles selected from the group consisting of n-butyllithium (n-BuLi), secondary butyllithium (s-BuLi), and tertiary butyllithium (t-BuLi). An organolithium compound is reacted with at least one amine of B ₂ mole selected from the group consisting of tetramethylethylenediamine (TMEDA) and 1,4-diazabicyclo [2.2.2] octane (DABCO) To form a complex having the following molar ratio of the metal-containing organometallic complex and the first complexing agent,

[The molar ratio is as follows:

A ₂ / B ₂ = 1 / 0.25-l / 1

(Where A and B ₂ are the same as above)],

The complex and the second complexing agent are a method of performing a polymerization reaction under the same conditions as the relationship between A ₃ / B ₃ .

In the present invention, for example, the preferred form of the complex has a structure that can be represented, for example, by the formula

(Wherein G represents at least one organometallic compound containing a Group IA metal, J represents at least one kind of first complexing agent, and each g, j and k is an integer of 1 or more).

The complex obtained by any of the above methods is thermally unstable. However, in the catalyst used in the present invention, it comprises a mixture of a complex and a second complexing agent, and the thermally stable complex is stabilized with a second complexing agent coexisting with the complex.

Thus, using such a catalyst, it becomes possible to form living anionic polymerization of the cyclic conjugated diene monomer even at relatively high temperatures such as above room temperature, especially above 60 ° C. Moreover, such catalysts can be used to produce cyclic conjugated diene polymers having a narrow molecular weight distribution at relatively high temperatures, such as at or above room temperature.

In addition, in the process of the present invention, when a large amount of complexing agent is present in the polymerization system, undesirable side reactions, such as metallization, are unlikely to occur, and the cyclic conjugated diene monomer can produce a cyclic conjugated diene polymer in units. have.

With respect to the kind of the second complexing agent used with the complex, there is no special limitation,

The kind of the first complexing agent and the second complexing agent may be the same or different. However, from an economic point of view, the kind of the first complexing agent and the second complexing agent is preferably the same.

There is no particular limitation on the polymerization method. Suitable polymerization methods can be selected. Examples of the polymerization method include gas phase polymerization, bulk polymerization and solution polymerization.

The polymerization can be carried out in a variety of ways, for example batchwise, semibatch or continuously.

The reactor for carrying out the polymerization may also be selected according to the properties of the polymer obtained, the reaction conditions and the like. Examples of reactors include high pressure vessels, coil reactors, kneaders and extruders.

When performing the polymerization process of the present invention by solution polymerization, suitable examples of the polymerization solvents used are aliphatic hydrocarbons such as butane, n-pentane, n-hexane, n-heptane, n-octane, iso-octane, n- Nonane and n-decane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene; And ethers such as diethyl ether, tetrahydrofuran, and tetrahydropyran. Suitable solvents can be selected according to the properties of the polymers obtained, reaction conditions and the like.

These polymerization solvents may be used alone or in combination if desired. Preferred examples of polymerization solvents are aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and combinations of these solvents.

Specific examples of the most preferred polymerization solvent of the present invention are at least one polymerization solvent selected from n-hexane, cyclohexane, and methylcyclohexane.

In the polymerization method of the present invention, the amount of the polymerization catalyst is not particularly limited and may vary depending on the intended use of the polymer to be produced. However, the polymerization catalyst is usually 1 × 1 ^-6 mol to 5 × 10 ^-1 mol, preferably 5 × 10 ^-6 mol to 1 × 10 ^-1 mol, in terms of molar amount of metal atoms relative to the moles of monomer or monomers. It is used in the amount of.

In the polymerization method of the present invention, the polymerization reaction may vary depending on other polymerization reaction conditions. However, the polymerization reaction temperature is usually -100 to 150 占 폚, preferably -80 to 120 占 폚, more preferably -30 to 110 占 폚, and most preferably 0 to 100 占 폚.

In addition, from a commercial point of view, the polymerization reaction temperature is advantageously from room temperature to (0 ° C, more preferably from 30 to 85 ° C, most preferably from 40 to 80 ° C.

In the polymerization method of the present invention, the polymerization reaction time is not particularly limited, and the polymerization reaction may vary depending on the intended use of the polymer and other polymerization reaction conditions. However, from a commercial point of view, the polymerization time is usually less than 48 hours, more preferably for 0.5 to 24 hours, most preferably for 1 to 10 hours.

In addition, the polymerization is preferably carried out in an atmosphere of an inert gas such as helium, nitrogen or argon. Particular preference is given to using well-dried inert gases, such as oxygen and carbon dioxide, which are highly purified in as small amounts as possible and contain impurities.

From a commercial point of view, preference is given to using highly purified and well dried nitrogen or argon, most preferably to highly purified and well dried nitrogen.

With respect to the pressure of the polymerization reaction system, there is no particular limitation, and a wide range of pressures can be selected as long as the pressure is sufficient to maintain the monomer or monomers and the solvent in the liquid state at the polymerization temperature in the above range.

It is also desirable to consider the intrusion of impurities, which impurities (eg, water, oxygen and carbon dioxide) inactivate the growth (activity) of the ends of the polymer formed into the polymerization catalyst or polymerization reaction system.

In the process of the present invention, to separate and recover the cyclic conjugated diene polymer from the polymer solution, the conventional technique used to recover the traditional polymer from the polymer solution (polymerization reaction mixture) is used.

Examples of such traditional methods include the following methods: steam coagulation, in which vapor and polymerization reaction mixtures are brought into direct contact; Precipitation method of precipitating the polymer by adding an inferior solvent for the polymer to the polymerization reaction mixture; Heating the polymerization reaction mixture in a polymerization reactor to distill off the solvent; Distilling off the solvent by bringing the heating roll into contact with the polymerization reaction mixture; A method of extruding the polymerization reaction mixture using an extruder with an outlet while distilling off the solvent through the outlet to obtain a small grain of polymer; And while distilling off the solvent and water through the outlet, the polymerization reaction mixture is placed in hot water, and then the obtained mixture is extruded using an extruder to obtain a small grain of polymer.

The most suitable method can be selected according to the properties of the cyclic conjugated diene polymer obtained and the solvent used.

According to the process of the invention, after the polymerization reaction, optionally at least one of hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening reaction and dehydrogenation is carried out.

Any of the above reactions can be carried out in the presence or absence of traditional catalysts.

For example, if the process of the present invention comprises two stages of polymerization and subsequent hydrogenation, the polymerization is first carried out to synthesize a polymer containing cyclic conjugated diene monomer units in the polymer's backbone, and then Thus, the hydrogenation reaction of the obtained polymer is carried out in the presence or absence of a hydrogenation catalyst to hydrogenate a portion or all carbon to carbon double bonds in the polymer to obtain a hydrogenated cyclic conjugated diene polymer.

Specific examples of the method for producing the hydrogenated cyclic conjugated diene polymer are as follows. The polymerization reaction is carried out to obtain a polymer containing or consisting essentially of the cyclic conjugated diene monomer unit, and after reaching a predetermined (targeted) degree of polymerization, the polymerization is terminated. Then, a hydrogenation catalyst is added to the reactor containing the obtained cyclic conjugated diene polymer, and hydrogen gas is introduced into a reactor for carrying out the hydrogenation reaction of the polymer to obtain a hydrogenated cyclic conjugated diene polymer.

More specifically, mention may be made of terminating the polymerization reaction in a conventional manner to add a hydrogenation catalyst and introducing hydrogen gas into the same reactor as used for the polymerization reaction to produce a batch hydrogenated polymer.

It will also be mentioned to terminate the polymerization reaction in a conventional manner, to deliver the reaction mixture to another reactor, to add a hydrogenation catalyst and to introduce hydrogen gas into the reactor containing the reaction mixture to produce a semi-batch hydrogenated polymer. Can be.

In addition, the polymerization reaction and the hydrogenation reaction can be carried out continuously in a tubular reactor to produce a hydrogenated polymer in a continuous manner.

Appropriate methods can be selected from these methods depending on the purpose and needs.

If the process of the invention comprises a hydrogenation reaction, the hydrogenation reaction is carried out in a hydrogen atmosphere, preferably in the presence of a hydrogenation catalyst.

In the present invention, the hydrogenation reaction is carried out by a method of maintaining the predetermined temperature in an atmosphere of long-phase hydrogen gas or inert gas and adding the hydrogenation catalyst to the polymer solution while stirring or not stirring. After maintaining the solution at the reaction temperature, hydrogen gas is introduced into the reaction system until a predetermined pressure level is reached.

The hydrogenation reaction can be carried out in conventional manner, ie batch, semibatch or continuous. These methods can be used alone or in combination.

The type and amount of hydrogenation catalyst used in the present invention is not particularly limited as long as the catalyst used provides the desired degree of hydrogenation. In practice, however, the hydrogenation catalyst used in the present invention may be selected from homogeneous catalysts (eg organometallic compounds, organometallic complexes) and heterogeneous catalysts (eg solid catalysts, catalysts supported by a carrier), each of which At least one member selected from the group consisting of Group IV A to VIII metals and rare earth metals of the periodic table.

Most preferred hydrogenation catalysts of the present invention are homogeneous hydrogenation catalysts containing at least one member selected from the group consisting of Group IV A to Group VIII metals and rare earth metals, ie organometallic compounds or complexes, or Group VIII metals (solid catalysts). Is a catalyst supported by a carrier containing.

As homogeneous hydrogenation catalysts these organometallic compounds or complexes may be supported by inorganic or organic compounds such as silica, zeolites or crosslinked polystyrene.

Particularly preferred examples of metals contained in the hydrogenation catalyst used in the present invention include titanium, cobalt, nickel, ruthenium, rhodium and palladium.

If the metal is contained in a homogeneous hydrogenation catalyst, it is essential that ligands such as hydrogen, halogens, nitrogen compounds or organic compounds are integrated with or bonded to such metals. These ligands can be used alone or in combination. When these ligands are used in combination, it is particularly preferred that the appropriate binding of the ligand is selected such that the organometallic compound or complex obtained is dissolved in the solvent used.

Various hydrogenation catalysts may be used alone or in combination if desired.

Also, from a commercial point of view, at least one member selected from the group consisting of Group IV A to VIII metals and rare earth metals as hydrogenation catalysts, and Group IA to IIA metals and Group IIIB metals such as alkyllithium, alkylmagnesium And combinations of organometallic compounds or complexes containing at least one organometallic compound containing a metal selected from the group consisting of alkylaluminum.

When the hydrogenation catalyst is a solid catalyst, the metal can be used as it is. However, it is usually preferred that the metal used as the catalyst is in a state supported by a carrier such as carbon, alumina, silica or barium sulfate.

Preferred solid catalysts include carrier supported catalysts containing at least one metal selected from rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum. Particularly preferred solid catalysts include carrier supported catalysts containing at least one metal selected from ruthenium, rhodium and palladium.

These catalysts may be used alone or in combination.

When the cyclic conjugated diene polymer obtained by the method of the present invention is a hydrogenated polymer, the amount of hydrogenation catalyst used in the hydrogenation reaction may be the type of hydrogenated polymer (eg, the structure and molecular weight of the main chain), or the hydrogenation reaction conditions (eg, a solvent). , Temperature, concentration and viscosity of the solution) may be appropriately determined. However, the amount of hydrogenation catalyst is usually 0.1 to 100,000 ppm, preferably 1 to 50,000, more preferably 5 to 10,000 ppm, most preferably 10 to 10, in terms of the concentration of metal atoms based on the amount of hydrogenated polymer. In the range of 10,000 ppm.

If the amount of hydrogenation catalyst is very small, a satisfactory ratio of hydrogenation reactions cannot be obtained. When the amount of the hydrogenation catalyst is very large, the ratio of the hydrogenation reaction becomes high, but it is disadvantageous from an economic point of view due to the use of a large amount of the hydrogenation catalyst. In addition, when the amount of the hydrogenation catalyst is too large, the separation and recovery of the hydrogenation catalyst becomes difficult and an undesirable result is shown, for example, the adverse effect of the residue on the polymer.

In the process of the present invention, it is preferable that the solvent used for the hydrogenation reaction is inert to the hydrogenation catalyst and can dissolve the polymer to be hydrogenated well.

From a commercial point of view, it is preferable to select a solvent used for the hydrogenation reaction from aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons. Most preferred solvents are aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and mixtures of these solvents.

In the present invention, from a commercial point of view, it is advantageous to carry out the polymerization reaction and the hydrogenation reaction continuously. Therefore, it is preferable that the solvent used for the hydrogenation reaction is the same as the solvent used for the polymerization reaction.

In the present invention, there is no particular limitation on the concentration of the polymer solution which has undergone the hydrogenation reaction. However, the polymer concentration of the polymer solution is preferably 1 to 90% by weight, more preferably 2 to 60% by weight, most preferably 3 to 40% by weight.

If the polymer concentration of the polymer solution is smaller than the above range, the hydrogenation reaction operation becomes ineffective and disadvantageous from an economic point of view. On the other hand, when the concentration of the polymer solution is higher than the above range, the clay of the polymer solution becomes high and the reaction rate is low.

In the present invention, the reaction temperature of hydrogenation is appropriately selected, but is usually -78 to 500 ° C, preferably -10 to 300 ° C, more preferably 20 to 250 ° C.

If the reaction temperature is lower than the above range, a satisfactory high reaction rate can be obtained. On the other hand, when the reaction temperature is higher than the above range, it becomes a cause of disadvantage that the hydrogenation catalyst is inactivated and the polymer is inferior.

The pressure of the hydrogenation reaction system is usually 0.1 to 500 kg / cm ² G, preferably 1 to 400 kg / cm ² G, more preferably 2 to 300 kg / cm ² G.

If the pressure of the hydrogenation reaction system is lower than the above range, a satisfactory high reaction rate cannot be obtained. If the pressure is higher than the above range, the reaction rate becomes high, but an expensive pressure resistant device is required, which is disadvantageous commercially. In addition, such high pressures can cause hydrocracking of the polymer during the hydrogenation reaction.

The reaction time of the hydrogenation is not particularly limited and may vary depending on the type and amount of the hydrogenation catalyst, the concentration of the polymer solution and the temperature and pressure of the reaction system. However, the reaction time of hydrogenation is usually 5 minutes to 240 hours, preferably 10 minutes to 100 hours, more preferably 30 minutes to 48 hours.

If desired, after the completion of the hydrogenation reaction, the hydrogenation catalyst is recovered from the hydrogenation reaction mixture obtained by conventional methods such as adsorption-separation of the catalyst by adsorbents or removal of the catalyst by washing of water or lower alcohols in the presence of organic or inorganic acids. Can be.

Separation and recovery of the hydrogenated cyclic conjugated diene polymer of the present invention from the hydrogenation reaction mixture can be carried out by conventional methods commonly used to recover conventional polymers from the polymerization reaction mixture.

Examples of such traditional methods include the following methods: steam coagulation, in which vapor and polymerization reaction mixtures are brought into direct contact; Precipitation method of precipitating the polymer by adding an inferior solvent for the polymer to the polymerization reaction mixture; Heating the polymerization reaction mixture in a polymerization reactor to distill off the solvent; Distilling off the solvent by bringing the heating roll into contact with the polymerization reaction mixture; A method of extruding the polymerization reaction mixture using an extruder with an outlet while distilling off the solvent through the outlet to obtain a small grain of polymer; And while distilling off the solvent and water through the outlet, the polymerization reaction mixture is placed in hot water, and then the obtained mixture is extruded using an extruder to obtain a small grain of polymer. The most suitable method can be selected according to the properties of the cyclic conjugated diene polymer obtained and the solvent used.

By hydrogenating the monomer unit A of the cyclic conjugated diene polymer of the present invention having a high content of the monomer unit A having 1,2-bonds, it is possible to obtain a polymer which is the most commercially preferred material having particularly excellent thermal and mechanical properties. .

As above, in the process of the invention, if desired, the polymerization reaction is carried out at least one of hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring-opening and dehydrogenation.

In the process of the invention, the dehydrogenation reaction can be carried out using conventional techniques.

More specifically, the cyclic conjugated diene polymer of the present invention is prepared by the polymerization method of the present invention, and the cyclic conjugated diene polymer is recovered and separated continuously or from the reaction mixture, and then the partial or all monomer units A contained in the polymer are aromatic. Switch to the ring.

For the dehydrogenation reaction of the present invention, there is no particular limitation and conventional methods of dehydrogenation can be used. Preferably, however, part or all monomer units A in the polymer chain are converted to aromatic rings, more preferably to benzene rings.

The dehydrogenation reaction of the present invention may be a catalytic reaction or a stoichiometric reaction. Usually, dehydrogenation is carried out as follows. The cyclic conjugated diene polymer is used as is, or if desired, the polymer is diluted with a solvent, preferably an organic solvent. If desired, a dehydrogenation catalyst or dehydrogenation reagent is added to the polymer. Subsequently, the dehydrogenation reaction is carried out under predetermined conditions.

About the kind of dehydrogenation reaction of this invention, a conventional kind of dehydrogenation reaction can be used as needed. Examples of the traditional class of dehydrogenation reactions include reactions by removing hydrogen atoms or hydrogen molecules directly from monomer units in the polymer backbone; Reaction by a method of removing hydrogen in the state contained in a compound such as sulfonated hydrogen and hydrogen halide; And a reaction by a method of removing hydrogen by a disproportionation reaction.

As an example of a simple and easy method for dehydrogenation using commonly available reagents, mention may be made of the use of quinones as dehydrogenation reagents.

Representative examples of quinones include 1,4-benzoquinone (quinone), tetrachloro-1,2-benzoquinone (o-chloranyl), tetrachloro-1,4-benzoquinone (p-chloranyl), 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-iodoanthra Quinones, 2,6-dihydroxyanthraquinones, 1,5-dihydroxyanthraquinones, 1,4,4a, 9a-tetrahydroanthraquinones, and phenanthhraquinones.

From a commercial standpoint, preferred examples of quinones as dehydrogenation reagents include 1,4-benzoquinone (quinone), tetrachloro-1,2-benzoquinone (o-chloranyl), tetrachloro-1,4-benzoquinone (p -Chloranyl), tetrabromo-1,2-benzoquinone (o-bromanyl), and tetrabromo-1,4-benzoquinone (p-bromanyl). Of these, tetrachloro-1,4-benzoquinone (p-chloranyl) is most preferred.

In the case of performing the dehydrogenation reaction of the present invention by dissolving the cyclic conjugated diene polymer in an organic solvent, the kind and amount of the organic solvent are not particularly limited as long as the solvent can satisfactorily dissolve the cyclic conjugated diene polymer. The organic solvent may be appropriately selected depending on the solubility of the cyclic conjugated diene polymer.

Examples of organic solvents used in the dehydrogenation reaction include aliphatic hydrocarbons such as butane, n-pentane, n-hexane, n-heptane, n-octane, iso-octane, n-nonane, and d-decane; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene: ethers such as diethyl ether, tetrahydrofuran and tetrahydropyran; And halogenated hydrocarbons such as chloroform, methylene chloride, chlorobenzene, dichlorobenzene and trichlorobenzene.

With respect to the dehydrogenation reaction temperature, the temperature may vary depending on other reaction conditions. However, the dehydrogenation reaction temperature is usually 0 to 350 ° C, preferably 0 to 300 ° C, more preferably 0 to 250 ° C, and most preferably 0 to 200 ° C. It is also beneficial from the commercial standpoint to carry out the dehydrogenation reaction at temperatures from room temperature to 200 ° C.

The dehydrogenation reaction time is not specifically limited, and the dehydrogenation reaction time may vary depending on the intended use of the dehydrogenated polymer and other dehydrogenation reaction conditions. However, the dehydrogenation reaction time is usually 48 hours or less, preferably 1 to 24 hours.

It is also preferable to carry out the dehydrogenation reaction in an atmosphere of inert gas such as nitrogen, argon or helium. In order to suppress side reactions, it is particularly preferred that such inert gas is a fixed and well dried inert gas.

With respect to the pressure of the dehydrogenation reaction system, there is no particular limitation, and a wide range of pressures can be selected which are sufficient to keep the catalyst, reagent and solvent in the liquid state at the dehydrogenation temperature in the above range.

In addition, impurities (eg, water, oxygen and carbon dioxide) may inactivate the dehydrogenation catalyst or dehydrogenation reagent or cause crosslinking or decomposition of the cyclic conjugated diene polymer, thus preventing the introduction of impurities into the dehydrogenation reaction system. It is desirable to consider.

After completion of the dehydrogenation reaction, the separation and recovery of the polymer of the present invention from the dehydrogenation reaction mixture can be carried out by conventional methods commonly used to recover conventional polymers from the polymerization reaction mixture.

Examples of such traditional methods include the following methods: steam coagulation, in which vapor and polymerization reaction mixtures are brought into direct contact; Precipitation method of precipitating the polymer by adding an inferior solvent for the polymer to the polymerization reaction mixture; Heating the polymerization reaction mixture in a polymerization reactor to distill off the solvent; Distilling off the solvent by bringing the heating roll into contact with the polymerization reaction mixture; A method of extruding the polymerization reaction mixture using an extruder with an outlet while distilling off the solvent through the outlet to obtain a small grain of polymer; And while distilling off the solvent and water through the outlet, the polymerization reaction mixture is placed in hot water, and then the obtained mixture is extruded using an extruder to obtain a small grain of polymer. The most suitable method can be selected according to the properties of the cyclic conjugated diene polymer obtained and the solvent used.

In addition, examples of the ring-opening reaction of the present invention include ozone oxidation reaction and nitric acid oxidation reaction.

If desired, depending on the intended use of the final polymer, additives, reinforcing agents and the like used in traditional polymer materials can be incorporated into the cyclic conjugated diene polymo of the present invention. Examples of such additives and reinforcing agents are stabilizers such as thermal stabilizers, antioxidants, and ultraviolet absorbers, lubricants, nucleating agents, plasticizers, dyes, pigments, crosslinkers, foaming agents, antistatic agents, antislip agents, antiblocking agents , Release agents, other polymeric materials, and inorganic reinforcing agents (eg, glass fillers, mineral fibers, and inorganic fillers).

For stabilizers such as thermal stabilizers, antioxidants, and ultraviolet absorbers, traditional stabilizers can be used as known in the art.

Examples of thermal stabilizers, antioxidants and ultraviolet absorbers include phenolic, organic phosphate, organic phosphites, organic amine and organic sulfur stabilizers.

The amount of each stabilizer such as thermal stabilizer, antioxidant and ultraviolet absorber is usually from 0.001 to 10% by weight, based on the weight of the cyclic conjugated diene polymer.

The cyclic conjugated diene polymer of the present invention may be in the form of a single material or in the form of a composite with other polymeric materials (eg traditional cyclic conjugated diene polymers), inorganic reinforcing materials or organic reinforcing agents, depending on the intended use of the polymer.

If the cyclic conjugated diene polymer of the present invention is intended to be used in a composite form (resin composition) with other polymer materials, such other polymer materials may be suitably selected from traditional organic polymers. There is no particular limitation on the type and amount of organic polymer.

The cyclic conjugated diene polymer of the present invention can be used as an excellent industrial material (eg, structural material or functional material). Specifically, the cyclic conjugated diene polymer of the present invention is a high performance plastic, a general purpose plastic, a special elastomer, a thermoplastic elastomer, an elastic fiber, a sheet, a film, a tube, a hose, an optical material, a coating agent, an insulation, a lubricant, a plasticizer, a separator, a selective permeation Membranes, microporous membranes, functional membranes, anti-vibration materials, anti-noise materials, damping materials, noise insulation materials, functional films (e.g. conductive films, photosensitive films), functional beads (e.g. molecular sieves), Polymer catalysts, substrates for supporting polymer catalysts), automotive parts, electrical parts, aerospace parts, railway parts, marine parts, electronic parts, battery parts, electronic parts, multimedia device parts, plastic materials for batteries, solar cell parts, functional Textiles, functional sheets, machine parts, building materials, civil engineering materials, medical equipment parts, pharmaceutical packaging materials, sustained-release materials, pharmacological support substrates, printed board materials It is useful for food containers, general packaging, clothing, sports and leather products, general goods, tire materials, belt materials, and other resin modifiers. If desired, a crosslinking agent is added to the cyclic conjugated diene polymer of the present invention to obtain a cured resin (eg, a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, a wet curable resin, or the like).

BEST MODE FOR CARRYING OUT THE INVENTION

In the following, the present invention will be described in detail with reference to the following examples and comparative examples, but should not be understood as being limited to the scope of the present invention.

In Examples and Comparative Examples, for drugs, those having high purity among commercially available ones are used. For solvents, treatment is carried out by conventional methods before using commercially available solvents. That is, the solvent is degassed, dehydrated under reflux on an active metal in an atmosphere of inert gas, and purified by distillation.

The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn ratio) of the polymer were determined by the liquid chromatography (HLC-8080) manufactured by Tosho Kabuki Kaisha Co., Ltd. and the column manufactured by Showa Co., Ltd. (Showdex: K805 + K804 +). It is measured by gel permeation chromatography (GPC) using K802). The number average molecular weight and Mw / Mn ratio are obtained using the calibration curve obtained for standard polystyrene.

The polymer chain structure of the polymer is analyzed using an NMR measuring apparatus (JEOL α-400) manufactured by JEOL LTD. (Japan). The measurement frequencies are 400 MHz ( ¹ H) and 100 MHz ( ¹³ C).

To carry out the NMR measurement, the polymer is dissolved in o-dichlorobenzene-d ₄ to obtain a 10% by weight polymer solution. The measurement temperature is 135 ° C. The 1.4 ppm peak of cyclohexane is used as the reference peak.

The molar ratio of 1,2-bond / 1,4-bond (molar ratio of monomer unit having 1,2-bond to monomer unit having 1,4-bond) of polycyclohexadiene is determined by the following method.

For cyclohexadiene (CHD) monomer units (1,2-CHD monomer units) having 1,2-bonds and CHD monomer units (1,4-CHD monomer units) having 1,4-bonds, 1,2 The -CHD monomer units and the 1,4-CHD monomer units differ in the number of protons (Ha) bonded to carbon atoms adjacent to carbon atoms bonded to each other by double bonds (see FIG. 1).

1,2-CHD monomer units satisfy the formula Ha / (Ha + Hb) = 1/2.

The 1,4-CHD monomer unit satisfies the formula Ha / (Ha + Hb) = 1/3.

Therefore, the molar ratio of 1,2-bond / 1,4-bond to the polymer is determined by calculating the ratio of protons related to carbohydrate atoms bonded to each other by double bonds.

2-D NMR spectrum of the polymer is measured by the H-H COSY method. Cross peaks are observed at 5.5 ppm to 5.8 ppm of hydrogen atoms bonded to carbon atoms bonded to each other by double bonds, with peaks also observed at 1.85 ppm to 2.35 ppm of hydrogen atoms (see FIGS. 2 and 3). . For the HH COSY Act, see, for example, Kobunshi Seitaibunshi no NMR (NMR of polymers and micromolecules), edited by Richiro Chujo, Isao Ando and Yoshio Inoue, and published by Tokyo Kagaku Dozin Co., Ltd, Japan, pages 31-41 ( 1992).

Thus, hydrogen atoms having peaks of 1.85 ppm to 2.35 ppm in the molecular chain of the polymer are bonded to carbon atoms adjacent to carbon atoms bonded to each other by double bonds.

The molar ratio of 1,2-CHD monomer units to all CHD monomer units is expressed as α and spans the range of peaks of all protons except protons bonded to carbon atoms bonded to each other by double bonds (bonded to each other with double bonds). When the ratio (Ha / Ha + Hb) of the region of the peak of 1.85 to 2.25 ppm (of protons bonded to a carbon atom adjacent to the carbon atom) is represented by β, α and β satisfy the following formula:

The molar ratio of 1,2-CHD to 1,4-CHD is determined by calculating α according to the above formula.

The chemical shift of a polymerization catalyst (complex) is measured using an NMR measuring apparatus (JEOL α-400) (manufactured by JEOL LTD., Japan). The measurement frequencies are 400 MHz ( ¹ H), 100 MHz ( ¹³ C), 155 MHz ( ⁷ Li) and 58.7 MHz ( ⁶ Li).

Chemical shifts of ⁷ Li and ⁶ Li are determined assuming that the peak of the 1M solution of LiCl in D ₂ O corresponds to 0 ppm.

The glass transition temperature (Tg) of the polymer is measured by DSC method using DSC200 (manufactured by Seiko Instruments Inc., Japan).

The conversion rate (mol%) of the monomer of the polymer reaction is calculated by the internal standard method from the absolute amount of monomer remaining in the polymer reaction mixture using gas chromatography (GC14A) (manufactured by Shimadzu Corporation). Ethylbenzene is used as internal standard.

The mechanical and thermal properties of the polymer are measured according to the following method.

(1) Tensile Test (1/8 inch):

Tensile strength (TS) and tensile elongation (TE) of a 1/8 inch thick polymer are measured according to ASTM D638.

(2) Bending test (1/8 inch):

The flexural strength (FS) and flexural modulus (FM) of a 1/8 inch thick polymer are measured according to ASTM D790.

(3) Izod impact test:

Izod lamination tests of polymers are measured according to ASTM D256 at room temperature.

(4) Heat distortion temperature (HDT: ℃)

The heat distortion temperature of the polymer is measured according to ASTM D648 under high weight 1.82 MPa and low cost 0.46 MPa.

In this measurement, the result is as follows.

1 MPa = 10.20 kg · f / cm ² ; And

1 J / m = 0.102 kgcm / cm.

In the following examples and comparative examples, for example, polycyclohexadiene-polyisoprendiblock copolymers are simply indicated as CHD-Ip diblock copolymers. Other block copolymers are similarly indicated.

Example 1

[Compound Synthesis of Group IA Metal-Containing Organometallic Compound and First Complexing Agent]

In a dry argon gas atmosphere, a predetermined amount of N, N, N ', N'-tetramethylethylenediamine (TMEDA) used as the first complexing agent is dissolved in cyclohexane to obtain 1.0 M EMEDA solution in cyclohexane. .

Then, the obtained cyclohexane solution of EMEDA is cooled and kept at -10 degreeC. Then, in a dry argon gas atmosphere, the n-hexane solution of n-butyllithium (n-BuLi) was gradually (as BuLi) Li / TMEDA molar ratio 4/2 (as first complexing agent) cyclohexane of TMEDA To the solution.

When the n-hexane solution of n-BuLi is added to the cyclohexane solution of TMEDA, it is found that the complex of TMEDA and n-BuLi forms quickly in the form of white crystals.

The resulting mixture containing the complex of TMEDA and n-BuLi is heated to 70 ° C. to dissolve the complex in cyclohexane and then gradually cooled to −78 ° C. As a result, a complex of white (plate) crystal form is precipitated.

Subsequently, the precipitated complex is separated by filtration in a dry argon gas atmosphere. The separated complex is washed several times with cyclohexane to give the final purified complex in the form of white (plate) crystals.

The molar ratio of Li / TMEDA in the complex (of n-BuLi) is 4/2 as determined by ¹ H-NMR.

[polymerization]

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into the Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, the obtained complex having a molar ratio of Li / TMEDA of 2/2 (of n-BuLi) was added and dissolved in cyclohexane in an amount of 0.3 mmol in terms of the amount of lithium atoms, , Obtain a complex solution. The complex solution is heated to and maintained at 70 ° C.

To the obtained complex solution, a 1.0M solution of TMEDA in cyclohexane (as the second complexing agent) was added in an amount sufficient to add 0.225 mmol of TMEDA (as the second complexing agent) to the complex solution, thereby resulting in a Li / TMEDA molar ratio. A cyclohexane solution of 4/5 complex-TMEDA mixture is obtained.

In an atmosphere of dry argon gas, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the obtained complex-TMEDA mixture solution and the polymerization reaction is carried out at 70 ° C. for 1 hour.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C. to yield a white polymer with a yield of 100% by weight.

The resulting cyclohexadiene (CHD) homopolymer has a number average molecular weight of 9,700 and an Mw / Mn ratio (molecular weight distribution) of 1.28.

For the polymer obtained, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 61 /. 39. The glass transition temperature (Tg) of the obtained polymer is 158 degreeC measured by the DSC method.

Example 2

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into the Schlenk tube. While maintaining the temperature of cyclohexane at 40 DEG C, a 1.6M solution of n-BuLi in n-hexane is added and dissolved in cyclohexane in an amount of 0.3 mmol in terms of the amount of lithium atoms to obtain a solution. The resulting solution is stirred for 10 minutes.

To the solution obtained was added 1.0 M solution of TMEDA (as first complexing agent) in cyclohexane in an amount of 4/2 molar ratio of Li / TMEDA (of n-BuLi) and the reaction was carried out at 40 ° C. for 10 minutes. To obtain the complex solution. The obtained complex solution is heated and kept at 70 degreeC.

To the obtained complex solution, a 1.0M solution of TMEDA in cyclohexane (as the second complexing agent) was added in an amount sufficient to add 0.225 mmol of TMEDA (as the second complexing agent) to the complex solution, thereby providing a Li / TMEDA molar ratio. A cyclohexane solution of 4/5 complex-TMEDA mixture is obtained.

In an atmosphere of dry argon gas, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the obtained complex-TMEDA mixture solution and the polymerization reaction is carried out at 70 ° C. for 1 hour.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Then, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C. to yield a white polymer with a yield of 100% by weight.

The obtained CHD single polymer has a number average molecular weight of 9,300 and an Mw / Mn ratio (molecular weight distribution) of 1.36.

For the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 51/49. to be. The glass transition temperature (Tg) of the obtained polymer is 152 degreeC measured by the DSC method.

Comparative Example 1

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, a solution of 1.6M n-BuLi in n-hexane in terms of lithium atoms is added to the cyclohexane in an amount of 0.30 mmol to obtain a solution. The resulting solution is stirred for 10 minutes.

To the obtained complex solution was added 3.0 g of 1,3-cyclohexadiene (1,3-CHD) in an atmosphere of dry argon gas, and the polymerization reaction was carried out at room temperature for 6 hours. After addition of 1,3-CHD, the color characteristic of the anion quickly disappears from the mixture.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then vacuum dried at 80 ° C. to obtain a low yield of 23 wt% polymer.

The obtained cyclohexadiene (CHD) homopolymer has a number average molecular weight of 3,200 and an Mw / Mn ratio (molecular weight distribution) of 2.89.

For the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 5/95. to be. The glass transition temperature (Tg) of the obtained polymer is as low as 88 ° C. when measured according to the DSC method.

Comparative Example 2

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into the Schlenk tube. While maintaining the temperature of cyclohexane at 40 ° C., a solution of 1.6 M of n-BuLi in n-hexane in terms of the amount of lithium atoms is added to the cyclohexane in an amount of 0.30 mmol to obtain a solution. The resulting solution is stirred for 10 minutes.

To the solution obtained was added 3.0 g of 1,3-cyclohexadiene (1,3-CHD) in an atmosphere of dry argon gas, and the polymerization reaction was carried out at 40 ° C. for 6 hours.

After addition of 1,3-CHD, the color characteristic of the anion quickly disappears from the mixture.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then vacuum dried at 80 ° C. to obtain a polymer with a low yield of 20% by weight.

The cyclohexadiene (CHD) homopolymer obtained has a number average molecular weight of 2,920 and an Mw / Mn ratio (molecular weight distribution) of 2.92.

For the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 2/98. to be. The glass transition temperature (Tg) of the obtained polymer is as low as 87 ° C. when measured according to the DSC method.

[Examples 3 to 6]

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into the Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, the amount of the complex having a Li / TMEDA molar ratio 4/2 (of n-BuLi) obtained in substantially the same manner as in Example 1 was converted into the amount of lithium atoms in an amount of 0.15 mmol In addition, it dissolves in cyclohexane and obtains a complex solution. The complex solution is heated to maintain at 40 ° C.

In Examples 3 to 6, 1.0M solution of TMEDA in cyclohexane was obtained in each amount of 0.0375 mmol, 0.0750 mmol, 0.1125 mmol and 0.150 mmol (as the second complexing agent) separately added to the complex solution. Add to one complex solution to obtain a cyclohexane solution of the complex-TMEDA mixture having a Li / TMEDA molar ratio of 4/3, 4/4, 4/5 and 4/6, respectively.

In a dry argon gas atmosphere, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the individual complex-TMEDA mixture solution obtained above, and the polymerization reaction is carried out at 40 ° C. for 4 hours. After this time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the separately obtained polymerization reaction mixture to terminate the polymerization reaction. Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the individual polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymers are washed separately with methanol and then vacuum dried at 80 ° C. to obtain 100% by weight of polymer, respectively.

For the obtained polymer, the molar ratio of each 1,2-bond / 1,4-bond (ie, the molar ratio of the 1,2-bond cyclic conjugated diene monomer to the 1,4-bond cyclic conjugated diene monomer) was 48 /. 52, 51/49, 52/48 and 54/46.

[Comparative Examples 3 to 6]

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into the Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, a 1.6 M solution of n-BuLi in n-hexane is added to the cyclohexane in an amount of 0.15 mmol in terms of the amount of lithium atoms to obtain a solution. The obtained solution is heated and kept at 40 degreeC.

In Comparative Examples 3 to 6, 0.0047 mmol, 0.0094 mmol, 0.0188 mmol, and 0.0375 mmol of TMEDA were separately added to the solution, and each amount added to the obtained solution in each amount stirred for 10 minutes was cyclo TMEDA of 0.1M solution in hexane was added to the obtained solution, containing complexes of TMEDA and n-BuLi with respective Li / TMEDA molar ratios of 4 / 0.125, 4 / 0.25, 4 / 0.5 and 4/1, respectively. Obtain a mixture.

In a dry argon gas atmosphere, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the individual mixture obtained above, and the polymerization reaction is carried out at 40 ° C. for 4 hours. After this time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the separately obtained polymerization reaction mixture to terminate the polymerization reaction. Then, a large amount of mixed solvent of methanol and hydrochloric acid is added to the individual polymerization reaction mixture containing the target polymer to separate the target polymer.

The separated polymer is washed separately with methanol and then vacuum dried at 80 ° C. to obtain a polymer.

With respect to the obtained polymer, the molar ratio of each 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 6 /. 94, 9/91, 21/79 and 29/71.

Example 7

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, a 1.6M solution of n-BuLi in n-hexane is added and dissolved in cyclohexane in an amount of 0.30 mmol in terms of the amount of lithium atoms to obtain a solution. The resulting solution is stirred for 10 minutes.

To the obtained solution was added a 1.0M solution of N, N, N ', N'-tetramethylpropylenediamine (TMPDA) in cyclohexane (as first complexing agent) (molar ratio of Li / TMPDA of n-BuLi) 4 / In an amount of 2, at room temperature, the reaction is carried out for 10 minutes to obtain a complex solution. The obtained complex solution is heated and kept at 40 degreeC.

To the obtained complex solution, a 1.0 M solution of TMPDA in cyclohexane (as the second complexing agent) was added in an amount sufficient to add 0.225 mmol of TMPDA (as the second complexing agent) to the complex solution, thereby providing a Li / TMPDA molar ratio. A cyclohexane solution of 4/5 complex-TMPDA mixture is obtained.

In an atmosphere of dry argon gas, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the obtained complex-TMPDA mixed solution, and the polymerization reaction is carried out at 40 ° C. for 4 hours. To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction.

Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C., yielding 100% by weight of polymer.

With respect to the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 47/53. to be.

[Examples 8 to 12]

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 20.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, the amount of the complex having a Li / TMEDA molar ratio 4/2 (of n-BuLi) obtained in substantially the same manner as in Example 1 was converted to the amount of lithium atoms in an amount of 0.07 mmol In addition, it dissolves in cyclohexane and obtains a complex solution. The complex solution is heated to maintain 60 ° C.

To the complex solution obtained above was added (as a second complexing agent) to the complex solution in each of the amounts shown in Table 1, 1.0M solution of TMEDA in cyclohexane was added to vary the Li / TMEDA molar ratio. A cyclohexane solution of the complex-TMEDA mixture of is obtained.

In an atmosphere of dry argon gas, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the obtained individual complex-TMEDA mixed solution and the polymerization reaction is carried out at 60 ° C. for 4 hours.

After this time, a 10% by weight solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to the obtained polymerization reaction mixture to terminate the polymerization reaction. Then, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the individual polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymers are individually washed with methanol and then vacuum dried at 80 ° C. to yield 100% by weight of polymer, respectively.

For the polymers obtained, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) was 44 /, respectively. 56, 52/48, 54/46, 56/44 and 60/40.

The results are shown in Table 1.

[Examples 8 to 12]

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, a 1.6 M solution of n-BuLi in n-hexane is added to the cyclohexane in an amount of 0.15 mmol in terms of the amount of lithium atoms to obtain a solution. The resulting solution is heated to maintain 60 ° C. and stirred for 10 minutes.

In an atmosphere of dry argon gas, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the obtained solution, and the polymerization reaction is carried out at 60 ° C. for 4 hours.

After addition of the 1,3-CHD monomer, the color characteristic of the cyclohexadienyl anion rapidly disappears from the mixture. In the reaction, the desired polymer is not obtained.

Example 13

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. Inject 27.0 g of cyclohexane into the Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, a 1.6M solution of n-BuLi in n-hexane is added and dissolved in cyclohexane in an amount of 0.15 mmol in the amount of lithium atoms to obtain a solution. The resulting solution is stirred for 10 minutes.

To the obtained solution was added a 1.0M solution of TMEDA (as first complexing agent) in cyclohexane in an amount of 4/2 molar ratio of Li / TMEDA (of n-BuLi) and the reaction was carried out at room temperature for 10 minutes. Obtain the complex solution. The complex solution is heated and kept at 40 ° C.

To the obtained complex solution, a 1.0 M solution of TMEDA in cyclohexane (as the second complexing agent) was added in an amount sufficient to add 0.1125 mmol of TMEDA (as the second complexing agent) to the complex solution, thereby resulting in a Li / TMEDA molar ratio. A cyclohexane solution of 4/5 complex-TMEDA mixture is obtained.

In an atmosphere of dry argon gas, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the obtained complex-TMEDA mixture solution and the polymerization reaction is carried out at 40 ° C. for 4 hours.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C. to yield a white polymer with a yield of 100% by weight.

The obtained CHD single polymer has a number average molecular weight of 19,750 and an Mw / Mn ratio (molecular weight distribution) of 1.09.

For the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 50/50. to be. The glass transition temperature (Tg) of the obtained polymer is 156 degreeC measured according to the DSC method.

Example 14

The polymerization was carried out in substantially the same manner as in Example 13, but the reaction temperature of TMEDA and n-BuLi was 60 ° C.

The obtained cyclohexadiene (CHD) homopolymer has a number average molecular weight of 20,800 and an Mw / Mn ratio (molecular weight distribution) of 1.26.

For the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 52/48. to be. The glass transition temperature (Tg) of the obtained polymer is 155 degreeC measured according to the DSC method.

Example 15

The polymerization was carried out in substantially the same manner as in Example 13, but the reaction temperature of TMEDA and n-BuLi was 40 ° C.

The obtained cyclohexadiene (CHD) homopolymer has a number average molecular weight of 20,060 and an Mw / Mn ratio (molecular weight distribution) of 1.14.

With respect to the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 54/46. to be. The glass transition temperature (Tg) of the obtained polymer is 159 degreeC when it measures by DSC method.

Comparative Example 8

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, a 1.6M solution of n-BuLi in n-hexane is added to the cyclohexane in an amount of 0.15 mmol in terms of the amount of lithium atoms to obtain a solution. The resulting solution is stirred for 10 minutes.

In a dry argon gas atmosphere, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the obtained solution and the polymerization reaction is carried out at room temperature for 6 hours.

After addition of 1,3-CHD, the color characteristic of the anion quickly disappears from the mixture.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then vacuum dried at 80 ° C. to obtain a low yield of 18% by weight of polymer.

The obtained cyclohexadiene homopolymer (CHD) has a number average molecular weight of 2,750 and an Mw / Mn ratio (molecular weight distribution) of 3.19.

For the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 2/98. to be. The glass transition silver (Tg) of the obtained polymer is as low as 87 ° C. as measured according to the DSC method.

Example 16

The well dried 300 ml pressure-resistant glass bottle is replaced with dry argon gas in a conventional manner. Inject 120.0 g of cyclohexane into the vial. While maintaining the temperature of cyclohexane at room temperature, a 1.6 M solution of n-BuLi in n-hexane is added to the cyclohexane in an amount of 3.0 mmol in terms of the amount of lithium atoms. The resulting mixture is stirred for 10 minutes.

Subsequently, a 1.0 M solution of TMEDA (as first complexing agent) in cyclohexane is added to the mixture to give a Li / EMEDA molar ratio of 4 (of n-BuLi) and the reaction is carried out for 10 minutes at room temperature. Thereby forming a complex of EMEDA and n-BuLi.

The resulting mixture containing the complex of EMEDA and n-BuLi is maintained at 40 ° C. by heating to obtain a complex solution.

To the obtained complex solution, a 1.0 M solution of TMEDA in cyclohexane (as secondary complexing agent) was added in an amount sufficient to add 2.25 mmol of TMEDA (as secondary complexing agent) to the complex solution, thereby resulting in a Li / TMEDA molar ratio. A cyclohexane solution of 4/5 complex-TMEDA mixture is obtained.

In a dry argon gas atmosphere, 4.5 g of 1,3-CHD is added to the obtained complex-TMEBA mixed solution, and the polymerization reaction is carried out at 40 ° C. for 1 hour.

In a dry argon gas atmosphere, 21.0 g of isoprene (Ip) is added to the obtained polymerization reaction mixture, and the polymerization reaction is further performed at 40 ° C for 1 hour to form a CHD-Ip diblock copolymer.

In a dry argon gas atmosphere, 4.5 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing a CHD-Ip diblock copolymer, and the polymerization reaction was further performed at 40 DEG C for 2 hours, whereby CHD-Ip- To form a CHD triblock copolymer.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the CIB-Ip-CHD triblock copolymer to separate the triblock copolymer. The separated triblock copolymer is washed with methanol and then dried in vacuo at 60 ° C. to yield 100% by weight of the CHD-Ip-CHD triblock copolymer in viscous form.

The obtained CHD-Ip-CHD triblock copolymer has a number average molecular weight of 9,890 and an Mw / Mn ratio (molecular weight distribution) of 1.04.

The polymer chain structure of the copolymer Determined by H-NMR. Certainly, the polymer chain of the copolymer has a ratio of cyclic conjugated diene monomers substantially equal to the ratio of cyclic conjugated dienes injected into the glass bottle.

With respect to the obtained copolymer, the molar ratio of 1,2-bond / 1,4-bond is 43/57.

Example 17

The well dried 300 ml pressure-resistant glass bottle is replaced with dry argon gas in a conventional manner. Inject 120.0 g of cyclohexane into the vial. While maintaining the temperature of cyclohexane at room temperature, a 1.1 M solution of s-BuLi in n-hexane is added to the cyclohexane in an amount of 3.0 mmol in terms of the amount of lithium atoms. The resulting mixture is stirred for 10 minutes.

Subsequently, a 1.0 M solution of TMEDA (as first complexing agent) in cyclohexane is added to the mixture to provide a Li / EMEDA molar ratio 4/2 (of s-BuLi) and the reaction is carried out at room temperature for 10 minutes. Thereby forming a complex of EMEDA with s-BuLi.

The resulting mixture containing the complex of EMEDA and s-BuLi is maintained at 40 ° C. by heating to obtain a complex solution.

To the above obtained complex solution in blue, 1.0M solution of TMEDA in cyclohexane (as the second complexing agent) was added in an amount sufficient to add 2.25 mmol (as the second complexing agent) to the complex solution. A cyclohexane solution of the complex-TMEDA mixture at a / TMEDA molar ratio of 4/5 is obtained.

To the blue obtained complex-TMEDA mixed solution, 1.5 mmol of m-diisopropenylbenzene (m-DIPB) is added to obtain a mixture. After the blue mixture showing the presence of radicals turns orange, indicating the absence of radicals, 21.0 g of isoprene (Ip) is added to the mixture and the polymerization reaction is carried out at 40 ° C. for 1 hour to give an Ip-containing copolymer. Form.

In a dry argon gas atmosphere, 9.0 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing Ip-containing copolymer, and the polymerization reaction was further performed at 40 ° C. for 2 hours, thereby providing CHD-Ip-CHD The triblock copolymer is formed.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Then, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the CHD-Ip-CHD triblock copolymer to separate the triblock copolymer. The separated triblock copolymer is washed with methanol and then dried in vacuo at 60 ° C. to obtain a yield of 100% by weight of the CHD-Ip-CHD triblock copolymer in elastic form.

The obtained CHD-Ip-CHD triblock copolymer has a number average molecular weight of 19,890 and an Mw / Mn ratio (molecular weight distribution) of 1.34.

The polymer chain structure of the triblock copolymer Determined by H-NMR. Certainly, the polymer chain of the triblock copolymer has a ratio of cyclic conjugated diene monomers substantially equal to the ratio of cyclic conjugated dienes injected into the glass bottle.

For the obtained triblock copolymer, the molar ratio of 1,2-bond / 1,4-bond is 46/54.

Example 18

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. Inject 27.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, a 1.6 M solution of n-BuLi in n-hexane is added and dissolved in cyclohexane in an amount of 0.07 mmol in terms of the amount of lithium atoms to obtain a solution. The resulting solution is stirred for 10 minutes.

To the resulting solution was added 1.0 M solution of TMEDA in cyclohexane (as first complexing agent) in an amount of 4/2 molar ratio of Li / TMEDA (of n-BuLi), and the reaction was carried out at room temperature for 10 minutes. , Obtain a complex solution. The complex solution is heated and kept at 40 ° C.

To an amount of 0.0525 mmol of TMEDA (as the second complexing agent) added to the complex solution, a 1.0 M solution of TMEDA in cyclohexane (as the second complexing agent) was added to the complex solution to obtain a Li / TMEDA molar ratio. A cyclohexane solution of 4/5 complex-TMEDA mixture is obtained.

In an atmosphere of dry argon gas, 3.0 g of 1,3-cyclohexadiene (1,3-CHD) is added to the obtained complex-TMEDA mixture solution and the polymerization reaction is carried out at 40 ° C. for 6 hours.

To the obtained polymerization reaction mixture, a 10 wt% solution of BHT [2,6-bis (t-butyl) -4-methylphenol] in methanol is added to terminate the polymerization reaction. Next, a large amount of a mixed solvent of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C. to yield 100% by weight of a white polymer.

The obtained CHD single polymer has a number average molecular weight of 44,800 and an Mw / Mn ratio (molecular weight distribution) of 1.21.

For the obtained polymer, the molar ratio of 1,2-bond / 1,4-bond (ie, the molar ratio of 1,2-bond cyclic conjugated diene monomer to 1,4-bond cyclic conjugated diene monomer) is 51/49. to be. The glass transition temperature (Tg) of the obtained polymer is 165 degreeC measured according to the DSC method.

The tensile modulus (TM) of the obtained polymer was 4,612 MPa (1 MPa = 10.20 kgf / cm). ) to be.

Example 19

The well dried 100 ml Schlenk tube is replaced with dry argon gas in a conventional manner. 1 g of the polymer obtained in Example 18 and 50 ml of trichlorobenzene are injected into a Schlenk tube. In an atmosphere of dried argon gas, the resulting mixture is heated to 150 ° C. with stirring to dissolve the polymer in trichlorobenzene.

Tetrachloro-1,4-benzoquinone (p-chloranyl) is added to the resulting polymer solution in an amount of 4 equivalents to cyclohexane unit equivalents in the polymer. The dehydrogenation is carried out at 150 ° C. for 20 hours. After completion of the reaction, the solution is removed by conventional methods to obtain a pale yellow dehydrogenated polymer.

The UV spectrum of the obtained dehydrogenated polymer is measured. Certainly, in the dehydrocyclic cyclic conjugated diene polymer, 72% of the cyclohexane units in the polymer obtained in Example 18 are converted to the benzene ring.

Example 20

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,700 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure container in the amount of I5.0 mmol in terms of the amount of lithium atoms. 7.5 Hmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 60 ° C. and then 11.25 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

300 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 60 ° C. for 3 hours. After a long time, the conversion rate of 1,3-CHD measured by gas chromatography was 99.8 mol%.

The polymerization reaction mixture is delivered under pressure to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

A stabilizer [Irganox B2l5 (0037HX)] (manufactured and sold by CIBA GEIGY, Switzerland) is added to the polymerization reaction mixture, and then the solvent is removed in a conventional manner to obtain a CHD single polymer.

The number average molecular weight of the obtained polymer is 20,100. The Mw / Mn ratio is 1.27.

1,2-bond / 1,4-bond molar ratio is 48/52. The glass transition temperature (Tg) measured by the DSC method is 151 degreeC.

Example 21

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,700 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 60 ° C.

n-BuLi is added to the high pressure vessel in an amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the obtained mixture is stirred at 60 ° C. for 10 minutes.

While maintaining the temperature of the high pressure vessel at 60 ° C., 11.25 mmol of TMEDA (as second complexing agent) is added to the mixture obtained above.

300 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 60 ° C. for 3 hours. After this time, the conversion of 1,3-CHD measured by gas chromatography was 99.2 mol%.

The polymerization reaction mixture is pressurized and delivered to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, wherein the high pressure vessel is used for the amount of lithium atoms present in the polymerization reaction mixture to dehydrated n-heptanol, which is well dried by conventional methods. The polymerization reaction is terminated by adding to the polymerization reaction mixture in the same molar amount.

Stabilizer [Irganox B2l5 (0037HX)] (manufactured and sold by CIBA GEIGY, Switzerland) is added to the polymerization reaction mixture, and then the solvent is removed in a conventional manner to obtain a CHD single polymer.

The number average molecular weight of the obtained polymer is 20,500. The Mw / Mn ratio is 1.29.

1,2-bond / 1,4-bond molar ratio is 50/50. The glass transition temperature (Tg) measured by the DSC method is 152 degreeC.

Example 22

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,700 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and 11.25 mmol of TMEDAs (as second complexing agent) are added to the mixture obtained above.

300 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 4 hours. After the said time, the conversion rate of 1, 3-CHD measured by gas chromatography is 99.6 mol%.

The polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

A stabilizer [Irganox B2l5 (0037BS)] (manufactured and sold by CIBA GEIGY, Switzerland) is added to the polymerization reaction mixture, and then the solvent is removed in a conventional manner to obtain a CHD single polymer.

The number average molecular weight of the obtained polymer is 20,200. Mw / Mn 1 is 1.23.

1,2-bond / 1,4-bond molar ratio is 61/39. The glass transition temperature (Tg) measured by the DSC method is 158 degreeC.

Example 23

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 1500 g 10 wt% cyclohexane solution of the polymer obtained in Example 22 is added to a high pressure vessel. A catalyst solution is added to the obtained polymer solution. The solution is converted into an amount of titanium atoms based on the weight of the polymer as a hydrogenation catalyst in terms of 290 ppm of titanocene dichloride (TC) and diisobutyl aluminum hydride ( DIBAL-H) is added to cyclohexane (TC / DIBAL-H molar ratio: 1/6) to prepare.

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was carried out at 35 kg / cm for 6 hours. Performed under hydrogen pressure of .G.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain the hydrogenated CHD homopolymer.

The hydrogenation degree of carbon to carbon double bonds determined by H-NMR is 67 mol%.

The number average molecular weight is 21,400. The Mw / Mn ratio is 1.22. The glass transition temperature (Tg) measured according to the DSC method is 201 ° C.

Example 24

A well dried 4 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,000 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 1,000 g 10% by weight cyclohexane solution of the polymer obtained in Example 22 is added to a high pressure vessel. To the polymer solution obtained is added 10 g of solid catalyst, which comprises 5% by weight of palladium (Pd) supported on barium sulfate (BaSO).

Replace the high pressure vessel with hydrogen gas. The temperature of the high pressure vessel is raised to 160 ° C., and then the hydrogenation reaction is carried out under hydrogen pressure of 55 kg / cmg for 6 hours.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain a hydrogenated CHD homopolymer.

The hydrogenation degree of carbon to carbon double bonds determined by H-NMR is 100 mol%.

The number average molecular weight is 20,800. The Mw / Mn ratio is 1.24. The glass transition temperature (Tg) measured according to the DSC method is 233 ° C.

Example 25

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

N-BuLi is added to the high pressure vessel in the amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 11.25 mmol (as second complexing agent) of TMEDA is added to the mixture obtained above.

600 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 4 hours. After the said time, the conversion of 1,3-CHD measured by gas chromatography was 97.4 mol%.

700 g of cyclohexane is added to the obtained polymerization reaction mixture to dilute the polymerization reaction mixture. The diluted polymerization reaction mixture is heated to 80 ° C. and transferred to another 5 liter high pressure vessel equipped with an electromagnetic stirrer, which is well dried by conventional methods. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction. A stabilizer [Irganox B215 (00371B)] (drafted and sold by CIBA GEIGY, Switzerland) is added to the polymerization reaction mixture, and then the solvent is removed in a conventional manner to obtain a CHD homopolymer.

The number average molecular weight of the obtained polymer was 43,800. The Mw / Mn ratio is 1.28.

1,2-bond / 1,4-bond molar ratio is 58/42. The glass transition temperature (Tg) measured by the DSC method is 167 degreeC.

The tensile modulus (TM) of the obtained polymer was 4,710 MPa (1 MPa = 10,20 kg · f / cm ) to be.

The heat deflection temperature (HDT, 1.82 MPa) is 131 ° C.

Example 26

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 900 g of cyclohexane is poured into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

N-BuLi is added to the high pressure vessel in the amount of 7.5 mmol in terms of the amount of lithium atoms. To the obtained cyclohexane solution of n-BuLi is added 3.75 mmol (as first complexing agent) of TMEDA and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 5.63 mmol of TMEDA (as second complexing agent) is added to the mixture obtained above.

600 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 6 hours. After the said time, the conversion rate of 1, 3-CHD measured by gas chromatography is 94.7 mol%.

2,000 g of cyclohexane is added to the obtained polymerization reaction mixture to dilute the polymerization reaction mixture. The diluted polymerization reaction mixture is heated to 80 ° C. and transferred to another 5 liter high pressure vessel equipped with an electromagnetic stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction. A stabilizer [Irganox B215 (0037HX)] (manufactured and sold by CIBA GEIGY, Switzerland) is added to the polymerization reaction mixture, and then the solvent is removed by a conventional method to obtain a CHD single polymer.

The number average molecular weight of the obtained polymer is 81,800. The Mw / Mn ratio is 1.32.

The 1,2-bond / 1,4-bond molar ratio is 63/37. The glass transition temperature (Tg) measured by the DSC method is 171 degreeC.

The tensile modulus (TM) of the obtained polymer was 4,815 MPa (1 MPa = 10.20 kg · f / cm ) to be.

Heat distortion temperature (HDT, 1.82 MPa) is 135 ° C.

Example 27

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 1500 g 10 wt% cyclohexane solution of the polymer obtained in Example 25 is added to a high pressure vessel. A catalyst solution is added to the obtained polymer solution. The solution is converted into an amount of titanium atoms based on the weight of the polymer as a hydrogenation catalyst in terms of 290 ppm of titanocene dichloride (TC) and diisobutyl aluminum hydride ( DIBAL-H) is added to cyclohexane (TC / DIBAL-H molar ratio: 1/6) to prepare.

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was carried out at 35 kg / cm for 10 hours. Performed under hydrogen pressure of G.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain a hydrogenated CHD homopolymer.

The hydrogenation degree of carbon to carbon double bonds determined by N-NMR is 87 mol%.

The number average molecular weight is 45,300. The Mw / Mn ratio is 1.27. The glass transition temperature (Tg) measured according to the DSC method is 228 ° C.

The flexural strength (FS) of the obtained polymer was 37.80 MPa (1 MPa = 10.20 kg · f / cm ) to be. Flexural modulus (FM) is 6,049 MPa.

Heat deflection temperature (HDT, 1.82 MPa) is 188 ° C.

Example 28

The hydrogenation reaction was substantially carried out in the same manner as in Example 17, but the polymer obtained in Example 26 was used.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain a hydrogenated CHD homopolymer.

The hydrogenation degree of carbon to carbon double bonds determined by H-NMR is 79 mol%.

The number average molecular weight is 83,600. The Mw / Mn ratio is 1.41. The glass transition temperature 79 measured according to the DSC method is 223 ° C.

The flexural strength (FS) of the obtained polymer was 44.80 MPa (1 MPa = 10.20 kg · f / cm ) to be. Flexural modulus (FM) is 6,322 MPa.

Heat distortion temperature (HDT, 1.82 MPa) is 190 ° C.

Example 29

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,000 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

1,000 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 25 is added to a high pressure vessel. To the polymer solution obtained is added 10 g of solid catalyst, which comprises 5% by weight of palladium (Pd) supported on barium sulfate (BaSO).

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was allowed to proceed for 55 kg / cm for 6 hours. Performed under hydrogen pressure of G.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain a hydrogenated CHD homopolymer.

The hydrogenation degree of carbon to carbon double bonds determined by H-NMR is 100 mol%.

The number average molecular weight is 44,100. The Mw / Mn ratio is 1.23.

The glass transition temperature (Tg) measured according to the DSC method is 236 ° C.

The flexural strength (FS) of the obtained polymer was 45.54 MPa (1 MPa = 10.20 kg · f / cm ) to be. Flexural modulus (FM) is 6,764 MPa.

Heat deflection temperature (HDT, 1.82 MPa) is 192 ° C.

Example 30

The hydrogenation reaction was substantially carried out in the same manner as in Example 29, but the polymer obtained in Example 26 was used.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain a hydrogenated CHD homopolymer.

The hydrogenation degree of carbon to carbon double bonds determined by H-NMR is 100 mol%.

The number average molecular weight is 82,700. The Mw / Mn ratio is 1.25. The glass transition temperature (Tg) measured according to the DSC method is 238 ° C.

The flexural strength (FS) of the obtained polymer was 48.64 MPa (1 MPa = 10.20 kg · f / cm ) to be. Flexural modulus (FM) is 7,664 MPa.

The heat deflection temperature (HDT, 1.82 MPa) is 198 ° C.

Example 31

The hydrogenation reaction was substantially carried out in the same manner as in Example 29, but alumina (AlO) was used as a carrier for the hydrogenation catalyst.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain a hydrogenated CHD homopolymer.

The hydrogenation degree of carbon to carbon double bonds determined by H-NMR is 100 mol%.

The number average molecular weight is 81,900. The Mw / Mn ratio is 1.29.

The glass transition temperature (Tg) measured according to the DSC method is 238 ° C.

Example 32

The hydrogenation reaction was substantially carried out in the same manner as in Example 29, but silica (SiO) was used as a carrier for the hydrogenation catalyst.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain a hydrogenated CHD homopolymer.

The hydrogenation degree of carbon to carbon double bonds determined by N-NMR is 100 mol%.

The number average molecular weight is 82,100. The Mw / Mn ratio is 1.33.

The glass transition temperature (Tg) measured according to the DSC method is 238 ° C.

Example 33

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

N-BuLi is added to the high pressure vessel in the amount of 12.0 mmol in terms of the amount of lithium atoms. 6.0 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 9.0 mmol of TMEDA (as second complexing agent) are added to the mixture obtained above.

600 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 6 hours. After this time, the conversion of 1,3-CHD measured by gas chromatography was 98.4 mol%.

700 g of cyclohexane is added to the obtained polymerization reaction mixture to dilute the polymerization reaction mixture. The diluted polymerization reaction mixture is heated to 80 ° C. and transferred to another 5 liter high pressure vessel equipped with an electromagnetic stirrer, which is well dried by conventional methods. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The 1,2-bond / 1,4-bond molar ratio of the obtained polymer is 60/40. The glass transition temperature (Tg) measured by the DSC method is 170 degreeC.

A catalyst solution is added to the obtained polymer solution, which is a solution of 100% by weight of the polymer based on cyclohexane [Co (acac) / TIBAL molar ratio: 1/6] to Cohexane and Tri It is prepared by adding isobutyl aluminum (TIBAL).

Replace the high pressure vessel with hydrogen gas. The temperature of the high pressure vessel was raised to 185 ° C., and then the hydrogenation reaction was carried out at 50 kg / cm for 4 hours. Performed under hydrogen pressure of G.

After completing the hydrogenation reaction, the high pressure vessel is cooled to room temperature and the pressure in the high pressure vessel is lowered to atmospheric pressure. The high pressure vessel is then replaced with nitrogen gas and treated by addition of methanol to the reaction mixture from which TIBAL is obtained.

Stabilizer [Irganox 8215 (00371k)] (manufactured and sold by CIBA GEIGY, Switzerland) is added to the reaction mixture, and then the solvent is removed by conventional methods to obtain the CHD single polymer.

The hydrogenation of the cyclohexane ring of the CHD homopolymer determined by H-NMR is also 100 mol%. The number average molecular weight of the obtained polymer is 50,700. The Mw / Mn ratio is 1.21. The glass transition temperature (Tg) measured according to the DSC method is 235 ° C.

The flexural strength (FS) of the obtained polymer was 46.84 MPa (1 MPa = 10.20 kg · f / cm ) to be. Flexural modulus (FM) is 6,974 MPa.

Heat deflection temperature (HDT, 1.82 MPa) is 195 ° C.

Example 34

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,700 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure container in the amount of 30.0 mmol in terms of the amount of lithium atoms. 15.0 mmol (as first complexing agent) of TMEDA is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 22.5 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

In a dry nitrogen gas atmosphere, 45 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 1 hour.

210 g of isoprene (IP) is added to a polymerization reaction mixture obtained in an atmosphere of dried nitrogen gas, and the polymerization reaction is further performed at 40 ° C. for 1.5 hours to form a CHD-Ip diblock copolymer.

45 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing the CHD-Ip diblock copolymer in a dried nitrogen gas atmosphere, and the polymerization reaction was further performed at 40 ° C. for 3 hours, whereby CHD-Ip- To form a CHD triblock copolymer.

The resulting polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 9,700. The Mw / Mn ratio is 1.14.

1,2-bond / 1,4-bond molar ratio is 48/52.

Example 35

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,700 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in the amount of 37.5 mmol in terms of the amount of lithium atoms. To the obtained cyclohexane solution of n-BuLi is added 18.75 mmol (as first complexing agent) of TMEDA and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 28.1 mmol of EMEDA (as second complexing agent) are added to the mixture obtained above.

15 g of isoprene (Ip) is added to the high pressure vessel, then 30 g of 1,3-CHD is added to the high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 1.5 hours to form an Ip-CHD diblock copolymer. .

210 g of 1 g is added to the obtained polymerization reaction mixture containing the IP-CHD diblock copolymer, and the polymerization reaction is further performed at 40 ° C. for 1.5 hours to form a CHD-Ip-CHD triblock copolymer.

30 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing Ip-CHD-Ip triblock copolymer, and the polymerization reaction was further performed at 40 ° C. for 2 hours, whereby Ip-CHD-Ip-CHD tetra To form a block copolymer.

15 g of IP was added to the obtained polymerization reaction mixture containing Ip-CHD-Ip-CHD tetrablock copolymer, and the polymerization reaction was carried out at 40 ° C. for 1.5 hours to give Ip-CHD-Ip-CHD-Ip pentablock air. To form coalescing.

The resulting polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the pentablock copolymer obtained was 8,200. The Mw / Mn ratio is 1.08.

1,2-bond / 1,4-bond molar ratio is 43/57.

Example 36

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,700 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure container in the amount of 30.0 mmol in terms of the amount of lithium atoms. 15.0 mmol (as first complexing agent) of TMEDA is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 22.5 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

15 g of 1,3-CHD is added to a high pressure vessel, and then the polymerization reaction is carried out at 40 ° C. for 1 hour.

270 g of isoprene (Ip) is added to the obtained polymerization reaction mixture, and the polymerization reaction is further performed at 40 ° C. for 2 hours to form a CHD-Ip diblock copolymer.

15 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing the CHD-Ip diblock copolymer, and the polymerization reaction was further performed at 40 DEG C for 3 hours to thereby prepare the CHD-Ip-CHD triblock copolymer. Form.

The resulting polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 10,500. The Mw / Mn ratio is 1.04.

1,2-bond / 1,4-bond molar ratio is 45/55.

Example 37

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 1500 g 10% by weight cyclohexane solution of the polymer obtained in Example 36 is added to a high pressure vessel. A catalyst solution is added to the obtained polymer solution, which solution is converted into an amount of titanium atoms based on the weight of the polymer to 100 ppm of cyclohexane (TC / DIBAL-H molar ratio: 1/6) as a hydrogenation catalyst. It is prepared by adding titanocenedichloride (TC) and diisobutyl aluminum hydride (DIBAL-H).

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 100 ° C., the hydrogenation reaction was carried out for 1 hour at 8 kg / cm Performed under hydrogen pressure of G to obtain hydrogenated CHD-Ip-CHD triblock copolymer.

The hydrogenation degree of the isoprene (Ip) polymer block of the polymer determined by N-NMR is 100 mol%. The CHD polymer block is not hydrogenated.

Example 38

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 11.25 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

300 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 20 minutes. After this time, the conversion of 1,3-CHD measured by gas chromatography was 47.8%.

Subsequently, 300 g of isoprene (Ip) is injected into the high pressure vessel, and the polymerization is further performed at 40 ° C. for 5 hours.

When IP is added to the 1,3-CHD polymerization reaction system, the interruption of the polymerization reaction of 1,3-CHD occurs because the polymerization reaction of IP proceeds prior to the polymerization reaction of 1,3-CHD. When almost all of the added Ip monomers are consumed, the polymerization of 1,3-CHD begins again. As a result, a CHD-Ip-CHD triblock copolymer is obtained.

The resulting polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 41,500. The Mw / Mn ratio is 1.31. 1,2-bond / 1,4-bond molar ratio is 49/51. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 152 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 26.2 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 157%. The flexural strength (FS) is 23.0 MPa and the flexural modulus (FM) is 2,950 MPa.

Izod impact strength is not broken.

Example 39

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,800 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 10.0 mmol in terms of the amount of lithium atoms. 5.0 mmol (as first complexing agent) of TMEDA is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 7.5 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

200 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 20 minutes. After the said time, the conversion rate of 1, 3-CHD measured by gas chromatography is 49.5 mol%.

Subsequently, 400 g of isoprene (Ip) is injected into the high pressure vessel, and the polymerization is further performed at 40 ° C. for 6 hours.

When Ip is added to the polymerization reaction system of 1,3-CHD, the interruption of the polymerization reaction of 1,3-CHD occurs because the polymerization reaction of Ip proceeds prior to the polymerization reaction of 1,3-CHD. When almost all of the added Ip monomers are consumed, the polymerization of 1,3-CHD begins again. As a result, a CHD-Ip-CHD triblock copolymer is obtained.

The resulting polymerization reaction mixture is diluted with 1000 g of cyclohexane and heated to 70 ° C. The diluted polymerization reaction mixture is pressurized and delivered to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 62,000. The Mw / Mn ratio is 1.44. 1,2-bond / 1,4-bond molar ratio is 48/52. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 151 ° C.

The tensile strength (75) of the obtained triblock copolymer was 19.5 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 695%.

Example 40

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 11.25 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

300 g of 1,3-CHD is mixed with 300 g of Ip. The obtained mixture is poured into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 6 hours.

In the polymerization reaction system in which 1,3-CHD and Ip coexist, the polymerization reaction of Ip proceeds prior to the polymerization reaction of 1,3-CHD. When almost all of the added Ip monomer is consumed, the polymerization of 1,3-CHD begins. The conversion of 1,3-CHD measured by gas chromatography was 98.3%. As a result, an Ip-CHD diblock copolymer is obtained.

The resulting polymerization reaction mixture is heated to 70 ° C. and pressurized to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 40,100. The Mw / Mn ratio is 1.49. The 1,2-bond / 1,4-bond molar ratio is 51/49. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 153 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 12.5 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 28%. The flexural strength (FS) is 18.7 MPa and the flexural modulus (FM) is 815 MPa.

Izod impact strength is not broken.

Example 41

The polymerization reaction is substantially carried out in the same manner as in Example 38, but a monomer mixture of 480 g of 1,3-CHD and 120 g of Ip is used. After 6 hours of polymerization, the conversion of 1,3-CHD measured by gas chromatography was 96.6 mol%.

Since the polymerization reaction system contains a large amount of 1,3-CHD compared to Ip, the polymerization reaction of 1,3-CHD is also performed by Begin at the initial polymerization stage. As a result, a copolymer containing a moiety where Ip and 1,3-CHD are optionally copolymerized is obtained.

The resulting polymerization reaction mixture is heated to 70 ° C. and pressurized to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained copolymer is 41,200. The Mw / Mn ratio is 1.41. 1,2-bond / 1,4-bond molar ratio is 52/48. The glass transition temperature (TS) of the CHD polymer block of the copolymer measured by the DSC method is 154 ° C.

The tensile strength (TS) of the obtained copolymer was 47.5 MPa (1 MPa = 10.20 kg · f / cm )to be. Tensile Elongation (TE) is 5%. The flexural strength (FS) is 92.9 MPa and the flexural modulus (FM) is 3210 MPa.

The heat deflection temperature (HCT, 1.82 MPa) is 128 ° C.

Izod impact strength is 78.2 J / m.

Example 42

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 1500 g 10% by weight cyclohexane solution of the polymer obtained in Example 38 is added to a high pressure vessel. A catalyst solution is added to the obtained polymer solution, which is converted to the amount of titanium atoms based on the weight of the polymer and added to the cyclohexane (TC / DIBAL-H molar ratio: 1/6) as a hydrogenation catalyst in an amount of 290 ppm. It is prepared by adding titanogen dichloride (TC) and diisobutyl aluminum hydride (DIBAL-H).

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was carried out at 35 kg / cm for 6 hours. Performed under hydrogen pressure of G.

After completion of the reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-Ip-CHD triblock copolymer.

The hydrogenation degree of the isoprene (Ip) polymer block determined by H-NMR is 100% and the hydrogenation degree of the CHD polymer block is 96%.

The number average molecular weight is 42,400. The Mw / Mn ratio is 1.28. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 233 ° C.

The tensile strength (TS) of the obtained copolymer was 30.8 MPa (1 MPa = 10.20 kg · f / cm )to be. Tensile elongation (TE) is 357%. The flexural strength (FS) is 29.0 MPa and the flexural modulus (FM) is 3,050 MPa.

Izod impact strength is not broken.

Example 43

The hydrogenation reaction was substantially carried out in the same manner as in Example 42, but the polymer obtained in Example 39 was used.

After completion of the hydrogenation reaction, the solvent is removed by conventional methods to obtain a hydrogenated CHD-Ip-CHD triblock copolymer.

The degree of hydrogenation of the isoprene (Ip) polymer block determined by H-NMR is 100 mol% and that of the CHD polymer block is 92%.

The number average molecular weight is 62,700. The Mw / Mn ratio is 1.39. The glass transition temperature (Tg) of the hydrogenated CHD polymer block of the copolymer measured according to the DSC method is 232 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 24.3 MPa (1 MPa = 10.20 kg · f / cm 2) to be. Tensile elongation (TE) is 706%.

Example 44

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,000 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 1,000 g 10% by weight cyclohexane solution of the polymer obtained in Example 38 is added to a high pressure vessel. To the polymer solution obtained is added 10 g of solid catalyst, which comprises 5% by weight of palladium (Pd) supported by barium sulfate (BaSO).

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was allowed to proceed for 55 kg / cm for 6 hours. Performed under hydrogen pressure of G.

After completion of the reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-Ip-CHD triblock copolymer.

For both isoprene (IP) polymer blocks and CHD polymer blocks, The degree of hydrogenation determined by H-NMR is 100%.

The number average molecular weight is 40,900. The Mw / Mn ratio is 1.33. The glass transition temperature (Tg) of the hydrogenated CHD polymer block of the copolymer measured by the DSC method is 232 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 30.2 MPa (1 MPa = 10.20 kg · f / cm )to be. Tensile elongation (TE) is 320%. The flexural strength (FS) is 28.2 MPa and the flexural modulus (FM) is 3150 MPa.

Izod impact strength is not broken.

Example 45

The hydrogenation reaction was substantially carried out in the same manner as in Example 44, but the polymer obtained in Example 39 was used.

After completion of the reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-Ip-CHD triblock copolymer.

For both isoprene (Ip) polymer blocks and CHD polymer blocks, The degree of hydrogenation determined by H-NMR is 100%.

The number average molecular weight is 61,900. The Mw / Mn ratio is 1.46. The glass transition temperature (Tg) of the hydrogenated CHD polymer block of the copolymer measured by the DSC method is 230 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 25.9 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 650%.

Example 46

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol (as first complexing agent) of TMEDA is added to the resulting cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 11.25 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

300 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 20 minutes. After this time, the conversion of 1,3-CHD measured by gas chromatography was 50.1%.

Subsequently, 300 g of styrene (51) is injected into a high pressure vessel, and the polymerization is further performed at 40 ° C. for 5 hours.

When St is added to the polymerization reaction system of 1,3-CHD, the interruption of the polymerization reaction of 1,3-CHD occurs because the polymerization reaction of St proceeds prior to the polymerization reaction of 1,3-CHD. When almost all of the added St monomer is consumed, the polymerization of 1,3-CHD begins again. As a result, a CHD-St-CHD triblock copolymer is obtained.

The resulting polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the triblock copolymer obtained is 40,600. The Mw / Mn ratio is 1.21. 1,2-bond / 1,4-bond molar ratio is 56/44. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 162 ° C.

The flexural strength (FS) of the obtained triblock copolymer was 33.5 MPa (1 MPa = 10.20 kg · f / cm Flexural modulus (FM) is 2,980 MPa.

The heat distortion temperature (HDT, 1.82 MPa) is 88 ° C.

Example 47

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 10.0 mmol in terms of the amount of lithium atoms. 5.0 mmol (as first complexing agent) of TMEDA is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 7.5 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

100 g of 1,3-CHD is injected into a high pressure vessel, and the polymerization reaction is carried out at 40 ° C. for 2 hours to obtain a CHD single polymer (polymer 1).

Subsequently, 400 g of styrene (St) is injected into a high pressure vessel, and the polymerization reaction is further performed at 40 ° C. for 3 hours to obtain a CHD-St diblock copolymer (polymer 2).

In addition, 100 g of 1,3-CHD is injected into a high pressure vessel, and the polymerization reaction is further performed at 40 ° C. for 5 hours to obtain a CHD-St—CHD triblock copolymer (polymer 3).

The resulting polymerization reaction mixture is heated to 70 ° C. and pressurized to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weights of the obtained polymers 1, 2 and 3 are 10,300, 49,800 and 60,700. Each Mw / Mn ratio is 1.04, 1.10 and 1.25. The molar ratio of 1,2-bond / 1,4-bond of Polymer 3 is 53/47. The glass transition temperature (Tg) of the CHD polymer block of polymer 3 measured by the DSC method is 156 ° C.

The tensile strength (TS) of the obtained polymer 3 was 18.9 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 2%. The flexural strength (FS) is 46.2 MPa and the flexural modulus (FM) is 3232 MPa.

The heat distortion temperature (HDT, 1.82 MPa) of polymer 3 is 78 ° C.

Example 48

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 11.25 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

300 g of 1,3-CHD is mixed with 300 g of St. The resulting mixture is poured into a vessel and the polymerization reaction is carried out at 40 ° C. for 6 hours.

In the polymerization reaction system in which 1,3-CHD and St coexist, the polymerization reaction of St proceeds prior to the polymerization reaction of 1,3-CHD. When almost all of the added St monomer is consumed, the polymerization reaction of 1,3-CHD begins. The conversion rate of 1,3-CHD measured by gas chromatography was 98.3 mol%. As a result, a St-CHD diblock copolymer is obtained.

The resulting polymerization reaction mixture is heated to 70 ° C. and pressurized to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 40,080. The Mw / Mn ratio is 1.23. 1,2-bond / 1,4-bond molar ratio is 57/43. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 161 ° C.

The flexural strength (FS) of the obtained diblock copolymer was 18.5 MPa (1 MPa = 10.20 kg · f / cm ) And flexural modulus (FM) is 5,430 MPa.

Heat distortion temperature (HDT, 1.82 MPa) is 72 ° C.

Example 49

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 11.25 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

Mix together 200 g of 1,3-CHD, 200 g of Ip and 200 g of St. The resulting mixture is poured into a vessel and the polymerization reaction is carried out at 40 ° C. for 6 hours.

In the polymerization reaction system in which Ip and St coexist, the polymerization reaction of St advances ahead of the polymerization reaction of 1,3-CHD and the polymerization reaction of Ip. When almost all of the St monomers present are consumed, the polymerization of Ip starts because the polymerization of Ip proceeds in preference to the polymerization of 1,3-HD.

When almost all of the Ip monomers are consumed, the polymerization of 1,3-CHD begins. The conversion of 1,3-CHD as measured by gas chromatography is 99.5 mol%. As a result, a St-Ip-CHD triblock copolymer is obtained.

The resulting polymerization reaction mixture is heated to 70 ° C. and pressurized to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the triblock copolymer obtained is 40,200. The Mw / Mn ratio is 1.21. 1,2-bond / 1,4-bond molar ratio is 53/47. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 156 ° C.

The tensile strength (75) of the obtained triblock copolymer was 22.4 (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 4%. The flexural strength (FS) is 45.0 MPa and the flexural modulus (FM) is 1,470 MPa.

Example 50

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

1,500 g of 10% by weight cyclohexane solution of the polymer obtained in Example 46 is added to a high pressure vessel. A catalyst solution is added to the obtained polymer solution, which is titano to cyclohexane (TC / DIBAL-H molar ratio: 1/6) as a hydrogenation catalyst in an amount of 290 ppm in terms of titanium atoms based on the polymer weight. Prepared by the addition of sen dichloride (TC) and diisobutyl aluminum hydride.

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was carried out at 35 kg / cm for 10 hours. Performed under hydrogen pressure of G.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-St-CHD triblock copolymer.

The hydrogenation degree of the CHD polymer block of the copolymer determined by H-NMR is 96 mol%.

The number average molecular weight is 40,400. The Mw / Mn ratio is 1.20. The glass transition temperature (Tg) of the hydrogenated CHD polymer block of the copolymer measured by the DSC method is 232 ° C.

The flexural strength of the copolymer (FS) is 38,8 MPa (1 MPa = 10.20 kg ) And the flexural modulus (FM) is 4,060 MPa.

The heat distortion temperature (HDT, 1.82 MPa) is 90 ° C.

Example 51

The hydrogenation reaction was carried out substantially in the same manner as in Example 50, but the polymer obtained in Example 48 was used.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated St-CHD diblock copolymer.

The hydrogenation degree of the CHD polymer block of the copolymer determined by H-NMR is 96 mol%. The St polymer block is not hydrogenated.

The number average molecular weight is 40,400. The Mw / Mn ratio is 1.19. The glass transition temperature (Tg) of the hydrogenated CHD polymer block of the copolymer measured by the DSC method is 234%.

The flexural strength of the copolymer (FS) is 22.8 MPa (1 MPa = 10.20 kg ) And the flexural modulus (FM) is 5,810 MPa.

The heat distortion temperature (HDT, 1.82 MPa) is 82 ° C.

Example 52

A well dried 4 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,000 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

1,000 g of a 10 wt% cyclohexane solution of the polymer obtained in Example 46 is added to a high pressure vessel. 50 g of solid catalyst is added to the obtained polymer solution, which contains 5% by weight of palladium (Pd) supported by barium sulfate (BaSO).

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was allowed to proceed for 55 kg / cm for 6 hours. Performed under hydrogen pressure of G.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-St-CHD triblock copolymer.

For both CHD polymer blocks and St polymer blocks, The degree of hydrogenation determined by H-NMR is 100 mol%.

The number average molecular weight is 41,600. The Mw / Mn ratio is 1.29. The glass transition temperatures (Tg) of the hydrogenated CHD polymer blocks and hydrogenated styrene polymer blocks, respectively, measured by the DSC method, are 232 ° C and 147 ° C.

The flexural strength of the copolymer (FS) is 42.8 MPa (1 MPa = 10.20 kgf / cm ) And the flexural modulus (FM) is 5,025 MPa.

The heat distortion temperature (HDT, 1.82 MPa) is 129 ° C.

Example 53

The hydrogenation reaction was substantially carried out in the same manner as in Example 52, but the polymer obtained in Example 48 was used.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated St-CHD diblock copolymer.

For both CHD polymer block and St polymer block, The degree of hydrogenation determined by H-NMR is 100%.

The number average molecular weight is 41,000. The Mw / Mn ratio is 1.26. The glass transition temperatures (Tg) of the hydrogenated CHD polymer blocks and hydrogenated styrene polymer blocks measured by the DSC method are 229 ° C and 149 ° C.

The flexural strength (FS) of the copolymer was 28.1 MPa (1 MPa = 10.20 kg · f / cm ) And the flexural modulus (FM) is 6,100 MPa.

The heat distortion temperature (HDT, 1.82 MPa) is 128 ° C.

Example 54

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. 1 g of the polymer obtained in Example 46 and 50 ml of trichlorobenzene are injected into a Schlenk tube. In an atmosphere of dried argon gas, the resulting mixture is heated to 140 ° C. under stirring to dissolve the polymer in trichlorobenzene.

To the resulting polymer solution, tetrachloro-1,4-benzoquinone (p-chloranyl) is added in an amount of 4 equivalents to the equivalent of cyclohexane units in the polymer. The dehydrogenation reaction is carried out at 140 ° C. for 20 hours. After completion of the reaction, the solvent is removed by conventional methods to obtain a pale yellow dehydrogenated polymer in elastic form. The UV spectrum of the obtained dehydrogenated polymer is measured. Certainly, the dehydrogenated cyclic conjugated diene polymer converts 76% of the cyclohexane units in the polymer obtained in Example 46 into benzene rings.

Example 55

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. Example 48 and 1 g of the polymer and 50 ml of trichlorobenzene obtained are injected into a Schlenk tube. In an atmosphere of dried argon gas, the resulting mixture is heated to 140 ° C. under stirring to dissolve the polymer in trichlorobenzene.

To the obtained polymer solution, tetrachloro-1,4-benzoquinone (p-chloranyl) is added in an amount of 4 equivalents to the equivalent of hexane units in the polymer. The dehydrogenation reaction is carried out at 140 ° C. for 20 hours. After completion of the reaction, the solvent is removed by conventional methods to obtain a pale yellow dehydrogenated polymer. The UV spectrum of the obtained dehydrogenated polymer is measured. Certainly, the dehydrogenated cyclic conjugated diene polymer converts 82% of the cyclohexane units in the polymer obtained in Example 48 to a benzene ring.

Example 56

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,700 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure container in the amount of 30.0 mmol in terms of the amount of lithium atoms. 15.0 mmol (as first complexing agent) of TMEDA is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 22.5 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

45 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 1 hour.

Subsequently, a solution of 700 g of 30% by weight of butadiene (Bd) in cyclohexane (210 g of Bd) was poured into a high pressure vessel, and the polymerization reaction was further performed at 40 ° C. for 1 hour to thereby prepare a CHD-Bd diblock copolymer Form.

45 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing a CHD-Bd diblock copolymer, and the polymerization reaction was further performed at 40 ° C. for 3 hours, thereby obtaining a CHD-Bd-CHD triblock copolymer. Form.

The resulting polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 10,100. The Mw / Mn ratio is 1.08. 1,2-bond / 1,4-bond molar ratio is 46/54.

Example 57

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,333 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 10.0 mmol in terms of the amount of lithium atoms. 5.0 mmol (as first complexing agent) of TMEDA is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 7.5 mmol (as a second complexing agent) of EMEDA is added to the obtained condensate.

100 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 2 hours to form a CHD homopolymer.

Subsequently, a solution of 667 g of 30% by weight of butadiene (Bd) in cyclohexane (Bd 200 g) was poured into a high pressure vessel, and the polymerization reaction was further performed at 40 ° C. for 2 hours to prepare a CHD-Bd diblock copolymer. Form.

100 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing the CHD-Bd diblock copolymer, and the polymerization reaction was further performed at 40 DEG C for 5 hours to obtain the CHD-Bd-CHD triblock copolymer. Form.

The resulting polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 40,100. The Mw / Mn ratio is 1.15. The 1,2-bond / 1,4-bond molar ratio is 51/49. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 158 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 14.2 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 133%. The flexural strength FS is 15.6 MPa, and the flexural modulus FM is 2,957 MPa.

Izod impact strength is not broken.

Example 58

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,467 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 10.0 mmol in terms of the amount of lithium atoms. 5.0 mmol (as first complexing agent) of TMEDA is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 7.5 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

100 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 40 ° C. for 2 hours to form a CHD homopolymer.

Subsequently, 1,333 g of 30 wt% butadiene (Bd) solution in cyclohexane (Bd 400 g) was poured into a high pressure vessel, and the polymerization reaction was further performed at 40 ° C. for 2 hours to form a CHD-Bd diblock copolymer. To form.

100 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing the CHD-Bd diblock copolymer, and the polymerization reaction was further performed at 40 DEG C for 5 hours to obtain the CHD-Bd-CHD triblock copolymer. Form.

After raising the temperature of the high pressure vessel to 70 ° C., the obtained polymerization reaction mixture is pressurized and transferred to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried by conventional methods. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 61,200. The Mw / Mn ratio is 1.17. The 1,2-bond / 1,4-bond molar ratio is 51/49. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 157 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 19.5 MPa (1 MPa = 10,20 kg · f / cm ) to be. Tensile elongation (TE) is 810%.

Izod impact strength is not broken.

Example 59

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

1,500 g of 10 wt% cyclohexane solution of the polymer obtained in Example 57 is added to a high pressure vessel. A catalyst solution is added to the obtained polymer solution, which is titanosene dichloride (TC) and diisobutyl aluminum hydride (TC) as a hydrogenation catalyst in an amount of 290 ppm in terms of titanium atoms based on the polymer weight. It is prepared by adding DIBAL-H) (TC / DIBAL-H molar ratio: 1/6).

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was carried out at 35 kg / cm for 10 hours. Performed under hydrogen pressure of .G.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-St-CHD triblock copolymer.

CHD polymer block and Bd polymer block Each degree of hydrogenation determined by H-NMR is 92 mol% and 98 mol%.

The number average molecular weight of the copolymer is 41,200. The Mw / Mn ratio is 1.17. The glass transition temperature (Tg) of the CHD polymer block measured by the DSC method is 232 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 19.6 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 153%. The flexural strength (FS) is 17.0 MPa and the flexural modulus (FM) is 3,254 MPa.

Izod impact strength is not broken.

Example 60

The hydrogenation reaction was substantially carried out in the same manner as in Example 59, but the polymer obtained in Example 58 was used.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-Bd-CHD triblock copolymer.

CHD polymer block and Bd polymer block The degree of hydrogenation determined by H-NMR is 98 mol% and 100 mol%, respectively.

The number average molecular weight is 60,900. The Mw / Mn ratio is 1.11. The glass transition temperature (Tg) of the CHD polymer block measured by the DSC method is 227 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 24.3 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 850%.

Example 61

A well dried 4 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,000 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 1,000 g 10% by weight cyclohexane solution of the polymer obtained in Example 57 is added to a high pressure vessel. 10 g of solid catalyst is added to the obtained polymer solution, which contains 5% by weight of palladium (PD) supported by alumina (AlO).

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 160 ° C., the hydrogenation reaction was allowed to proceed for 55 kg / cm for 6 hours. Performed under hydrogen pressure of G.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-Bd-CHD triblock copolymer.

For CHD polymer block and Bd polymer block, The degree of hydrolysis determined by H-NMR is 100 mol%.

The number average molecular weight of the copolymer is 40,700. The Mw / Mn ratio is 1.16. The glass transition temperature (Tg) of the CHD polymer block measured by the DSC method is 232 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 21.4 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 147%. The flexural strength (FS) is 19.2 MPa and the flexural modulus (FM) is 3350 MPa.

Izod impact strength is not broken.

Example 62

The hydrogenation reaction was substantially carried out in the same manner as in Example 61, but the polymer obtained in Example 58 was used.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-Bd-CHD triblock copolymer.

For CHD polymer block and Bd polymer block, The degree of hydrogenation determined by H-NMR is 100 mol%.

The number average molecular weight is 62,300. The Mw / Mn ratio is 1.15. The glass transition temperature (Tg) of the hydrogenated CHD polymer block measured by the DSC method is 229 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 25.2 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 810%.

Example 63

A well dried 4 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 1500 g 10% by weight cyclohexane solution of the polymer obtained in Example 56 is added to a high pressure vessel. A catalyst solution is added to the obtained polymer solution, which solution is converted into an amount of titanium atoms based on the weight of the polymer to titano in cyclohexane (TC / n-BuLi molar ratio: 1/1) as a hydrogenation catalyst in an amount of 100 ppm. It is prepared by adding sendichloride (TC) and n-BuLi.

Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 75 ° C., the hydrogenation reaction was carried out for 30 minutes at 8 kg / cm Performed under hydrogen pressure of G.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-Bd-CHD triblock copolymer.

The degree of hydrogenation of the CHD polymer block and the Bd polymer block determined by H-NMR is 100 mol%.

The number average molecular weight is 10,200. The Mw / Mn ratio is 1.09.

Example 64

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,947 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

The polymerization catalyst (complex) obtained in Example 1 is added to the high pressure vessel in an amount of 5.0 mmol in terms of the amount of lithium atoms.

While maintaining the temperature of the high pressure vessel at 30 ° C., 3.75 mmol of TMEDA (second complexing agent) is added to the high pressure vessel.

60 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out at 30 ° C. for 4 hours to form a CHD single polymer.

A 30% by weight solution of 933 g of butadiene (Bd) in cyclohexane (Bd 280 g) was added to the obtained polymerization reaction mixture, and the polymerization reaction was further performed at 45 ° C. for 1 hour to obtain a CHD-Bd diblock copolymer. Form.

60 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing the CHD-Bd diblock copolymer, and the polymerization reaction was further performed at 30 ° C. for 4 hours to thereby prepare the CHD-Bd-CHD triblock copolymer. Form.

The resulting polymerization reaction mixture is delivered by pressurization to another 5 liter high pressure vessel equipped with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The catalyst solution was added to the obtained polymer solution, and the solution was converted into the amount of titanium atoms based on the weight of the polymer to 250 ppm in cyclohexane (TC / n-BuLi molar ratio: 1/1) as a hydrogenation catalyst. Prepared by adding titanocene dichloride (TC) and n-BuLi. Replace the high pressure vessel with hydrogen gas. After raising the temperature of the high pressure vessel to 75 ° C., the hydrogenation reaction was carried out for 10 minutes at 10 kg / cm. Performed under hydrogen pressure of G.

After the completion of the hydrogenation reaction, the high pressure vessel is cooled to room temperature and the pressure of the high pressure vessel is lowered to atmospheric pressure. Substituted with high pressure vessel theory hydrogen gas, and methanol was added to the obtained reaction mixture to treat n-BuLi.

Irganox B2l5 (0037HX) (manufactured by CIBA GEIGY, Switzerland) as a stabilizer is added to the reaction mixture, and then the solvent is removed by conventional methods to obtain the hydrogenated CHD-Bd-CHD triblock copolymer in elastic form.

The hydrogenation degree of the CHD polymer block determined by H-NMR is 0 mol%. For the 1,2-vinyl bond, 1,4-cis bond and 1,4-trans bond of the Bd polymer block, The degree of hydrogenation determined by H-NMR is 100 mol%. 1,2-bond / 1,4-bond molar ratio is 48/52. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 153 ° C.

The number average molecular weight of the obtained triblock copolymer is 79,600. The Mw / Mn ratio is 1.09.

The tensile strength (TS) of the obtained triblock copolymer was 17.8 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 850%.

Example 65

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,947 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

The polymerization catalyst (complex) obtained in Example 1 is added to the high pressure vessel in the amount of 10.0 mmol in terms of the amount of lithium atoms.

While maintaining the temperature of the high pressure vessel at 30 ° C., 7.5 mmol of TMEDA (second complexing agent) is added to the high pressure vessel.

120 g of 1,3-CHD high pressure vessel is injected and the polymerization reaction is carried out at 30 ° C. for 4 hours to form a CHD homopolymer.

Subsequently, a 30 wt% solution of 933 g of butadiene (Bd) in cyclohexane (Bd 280 g) is injected into a high pressure vessel and the polymerization reaction is further performed at 45 ° C. for 1 hour to form a CHD-Bd diblock copolymer. .

To the obtained polymerization solution was added silicon tetrachloride (SiCl) in an amount of 2.5 mmol, and then the coupling reaction was carried out at 60 ° C. for 30 minutes.

Irganox B2l5 (0037HX) (manufactured by CIBA GEIGY, Switzerland) is added as a stabilizer to the obtained polymer solution, and then the solvent is removed by a conventional method to obtain the hydrogenated CHD-Bd-CHD triblock copolymer in elastic form. 1,2-bond / 1,4-bond molar ratio is 50/50. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured by the DSC method is 155 ° C.

The number average molecular weight of the obtained triblock copolymer is 112,000. The Mw / Mn ratio is 2.08.

The tensile strength (TS) of the obtained triblock copolymer was 16.8 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 600%.

Example 66

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. 1 g of the polymer obtained in Example 64 and 50 ml of trichlorobenzene are injected into a Schlenk tube. In an atmosphere of dried argon gas, the resulting mixture is heated to 140 ° C. under stirring to dissolve the polymer in trichlorobenzene.

To the resulting polymer solution, tetrachloro-1,4-benzoquinone (p-chloranyl) is added in an amount of 4 equivalents to the equivalent of cyclohexane units in the polymer. Dehydrogenation is carried out at 140 ° C. for 20 hours. After completion of the reaction, the solvent is removed in a conventional manner to obtain a pale yellow dehydrogenated polymer in elastic form.

The UV spectrum of the obtained dehydrogenated polymer is measured. Certainly, the dehydrogenated cyclic conjugated diene polymer converts 89% of the cyclohexane units in the polymer obtained in Example 64 into a benzene ring.

Example 67

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 2,400 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

n-BuLi is added to the high pressure vessel in an amount of 15.0 mmol in terms of the amount of lithium atoms. 7.5 mmol of TMEDA (as first complexing agent) is added to the obtained cyclohexane solution of n-BuLi, and the resulting mixture is stirred at room temperature for 10 minutes.

The temperature of the high pressure vessel is raised to 40 ° C. and then 11.25 mmol (as second complexing agent) of EMEDA is added to the mixture obtained above.

The high pressure vessel is replaced with ethylene (Et) gas. 40 kg / cm at 40 ° C. for 1 hour Under ethylene pressure of G.

The ethylene gas is then discharged and replaced with dried nitrogen gas. 300 g of 1,3-CHD is injected into a high pressure vessel, and the polymerization reaction is further performed at 40 ° C for 7 hours to obtain an Et-CHD diblock copolymer. After this time, the conversion of 1,3-CHD measured by gas chromatography was 98.2 mol%.

The high pressure vessel is raised to 70 ° C. and the resulting polymerization reaction mixture is then transferred to a 5 liter high pressure vessel with an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The ethylene content of the obtained diblock copolymer determined by H-NMR is 15% by weight.

The number average molecular weight is 23,400. The Mw / Mn ratio is 1.62. 1,2-bond / 1,4-bond molar ratio is 53/47. The glass transition temperature (Tg) of the CHD polymer block measured by the DSC method is 157 ° C.

Example 68

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. Inject 18.0 g of cyclohexane and 2.0 g of n-hexane into a Schlenk tube. While maintaining the temperature of the solution obtained at room temperature, the polymerization catalyst (complex) obtained in Example 1 is added to the high pressure vessel in the amount of 0.07 mmol in terms of the amount of lithium atoms.

Subsequently, a 1.0M solution of TMEDA in cyclohexane (as first complexing agent) is added to a high pressure vessel to obtain a Li / EMEDA with a molar ratio of 4/5 (n-BuLi) and the reaction is carried out at room temperature for 10 minutes. . 1.50 g of 1,3-CHD is injected into a high pressure vessel and the polymerization reaction is carried out for 3 hours at room temperature under an atmosphere of dried argon gas to form a CHD homopolymer.

The obtained polymer solution is cooled to −10 ° C. and 1.50 g of methyl methacrylate (MMA) is added to the polymer solution. The polymerization reaction is further performed at −10 ° C. for 3 hours to obtain a CHD-MMA diblock copolymer.

To the obtained polymerization reaction mixture, a 10% by weight BHF [bis (t-butyl) -4-methylphenol] solution in methanol is added to terminate the polymerization reaction. Then, a large amount of mixed solution of methanol and hydrochloric acid are added to the polymerization reaction mixture containing the CHD-MMA diblock copolymer to separate the diblock copolymer. The separated diblock copolymer is washed with methanol and then dried in vacuo at 80 ° C. to yield 81% by weight of a white CHD-MMA diblock copolymer.

The number average molecular weight of the obtained CHD-MMA diblock copolymer is 34,500. The Mw / Mn ratio is 1.72. 1,2-bond / 1,4-bond molar ratio is 54/46. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured according to the DSC method is 154 ° C.

Example 69

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. Inject 18.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of the solution obtained at room temperature, a 1.6M solution of n-BuLi in n-hexane is added to cyclohexane in an amount of 0.10 mmol in terms of the amount of lithium atoms. The resulting mixture is stirred for 10 minutes.

Subsequently, a 1.0 M solution of TMEDA in cyclohexane (as first complexing agent) is added to the mixture to obtain a molar ratio of 4/2 (n-BuLi) Li / EMEDA and the reaction is carried out at room temperature for 10 minutes. do. The obtained reaction mixture is heated and maintained at 40 ° C. to obtain a complex solution.

To the complex solution obtained was added 0.075 mmol (as the second complexing agent) to the complex solution, 1.0 M solution of TMEDA in cyclohexane (as the second complexing agent) was added to form a Li / TMEDA molar ratio of 4/5. A cyclohexane solution of the complex TMEDA is obtained.

In an atmosphere of dried argon gas, 2.0 g of 1,3-CHD is added to the obtained complex-TMEDA mixture solution and the polymerization solution is carried out at 40 ° C. for 4 hours to form a CHD homopolymer.

2.0 g of methyl methacrylate (MMA) is added to the obtained polymerization reaction mixture, and the polymerization reaction is further performed in an atmosphere of argon gas dried at 40 ° C. for 2.5 hours to obtain a CHD-MMA diblock copolymer.

To the obtained polymerization reaction mixture, 10% by weight of a BHF [bis (t-butyl) -4-methylphenol] solution in methanol is added to terminate the polymerization reaction. Then, a large amount of mixed solution of methanol and hydrochloric acid are added to the polymerization reaction mixture containing the CHD-MMA diblock copolymer to separate the diblock copolymer. The separated diblock copolymer is washed with methanol and then dried in vacuo at 60 ° C. to yield 98% by weight of a white CHD-MMA diblock copolymer.

The number average molecular weight of the obtained CHD-MMA diblock copolymer is 38,700. The Mw / Mn ratio is 1.89. 1,2-bond / 1,4-bond molar ratio is 52/48. The glass transition temperature (Tg) of the CHD polymer block of the copolymer measured according to the DSC method is 155 ° C.

Example 70

The hydrogenation reaction was carried out substantially in the same manner as in Example 52, but the polymer obtained in Example 47 was used.

After completion of the hydrogenation reaction, the solvent is removed in a conventional manner to obtain a hydrogenated CHD-St-CHD triblock copolymer.

For both CHD polymer blocks and St polymer blocks, The degree of hydrogenation determined by N-NMR is 100 mol%.

The number average molecular weight is 41,000. The Mw / Mn ratio is 1.28. The glass transition temperatures (Tg) of the hydrogenated CHD polymer block and the hydrogenated styrene polymer block measured according to the DSC method are 230 ° C and 149 ° C.

Flexural strength (FS) is 50.1 MPa (1 MPa = 10.20 kgf / cm ) And flexural modulus (FM) is 6,200 MPa.

Heat distortion temperature (HDT, 1.82 MPa) is 130 ° C.

Example 71

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,947 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

60 g of 1,3-CHD and 3.0 mmol of TMEDA (as the second complexing agent) are injected into the high pressure vessel and the temperature of the high pressure vessel is raised to 40 ° C.

Subsequently, the polymerization catalyst (complex) obtained in substantially the same manner as in Example 1 was added to a high pressure vessel in an amount of 4.0 mmol in terms of the amount of lithium atoms, and the polymerization reaction was carried out at 40 ° C. for 2 hours to give CHD To form a homopolymer.

Subsequently, a 30 wt% 933 g solution of butadiene (Bd) in cyclohexane (Bd 280 g) is injected into a high pressure vessel and the polymerization reaction is further performed at 40 ° C. for 2 hours to form a CHD-Bd diblock copolymer. .

60 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing the CHD-Bd diblock copolymer, and the polymerization reaction was further performed at 40 ° C. for 5 hours to thereby prepare the CHD-Bd-CHD triblock copolymer. Get

The polymerization reaction mixture obtained by heating the obtained polymerization reaction mixture to 70 ° C. is pressurized to a 5 liter high pressure vessel having an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 98,900. The Mw / Mn ratio is 1.04. 1,2-bond / 1,4-bond molar ratio is 50/50. The glass transition temperature (Tg) of the CHD polymer block measured by the DSC method is 156 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 19.2 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 910%.

Example 72

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,947 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at room temperature.

60 g of 1,3-CHD and 4.875 mmol (as the second complexing agent) are injected into the high pressure vessel and the temperature of the high pressure vessel is raised to 40 ° C.

Subsequently, the polymerization catalyst (complex) obtained in substantially the same manner as in Example 1 was added to a high pressure vessel in the amount of 6.5 mmol in terms of the amount of lithium atoms, and the polymerization reaction was carried out at 40 ° C. for 2 hours to give CHD To form a homopolymer.

Subsequently, a 30 wt% 933 g solution of butadiene (Bd) in cyclohexane (Bd 280 g) is injected into a high pressure vessel and the polymerization reaction is further performed at 40 ° C. for 2 hours to form a CHD-Bd diblock copolymer. .

60 g of 1,3-CHD was added to the obtained polymerization reaction mixture containing the CHD-Bd diblock copolymer, and the polymerization reaction was further performed at 40 ° C. for 5 hours to thereby prepare the CHD-Bd-CHD triblock copolymer. Get

The obtained polymerization reaction mixture is raised to 70 ° C. to transfer the polymerization reaction mixture obtained by pressurization into a 5 liter high pressure vessel having an electromagnetic induction stirrer, which is well dried in a conventional manner. Dehydrated n-heptanol is added to the polymerization reaction mixture in the same molar amount relative to the amount of lithium atoms present in the polymerization reaction mixture to terminate the polymerization reaction.

The number average molecular weight of the obtained triblock copolymer is 62,000. The Mw / Mn ratio is 1.06. 1,2-bond / 1,4-bond molar ratio is 49/51. The glass transition temperature (Tg) of the CHD polymer block measured by the DSC method is 154 ° C.

The tensile strength (TS) of the obtained triblock copolymer was 17.2 MPa (1 MPa = 10.20 kg · f / cm ) to be. Tensile elongation (TE) is 800%.

Example 73

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. Inject 27.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, the amount of 0.3 mmol obtained by converting the complex of Li / TMEDA molar ratio 4/1 (of n-BuLi) obtained in substantially the same manner as in Example 1 to the amount of lithium atoms It is added to cyclohexane and dissolved to obtain a complex solution. The complex solution is maintained at 40 ° C.

To the complex solution obtained above to add 0.30 mmol (as the second complexing agent) to the complex solution, 1.0M solution of TMEDA in cyclohexane (as the second complexing agent) was added to give a Li / TMEDA molar ratio of 4 /. A cyclohexane solution of the complex-TMEDA mixture having 5 is obtained.

In an atmosphere of dried argon gas, 3.0 g of 1,3-CHD is added to the obtained complex-TMEDA mixture solution, and the polymerization reaction is carried out at 40 ° C. for 2 hours to obtain a CHD homopolymer.

To the obtained polymerization reaction mixture, a 10% by weight BHF [bis (t-butyl) -4-methylphenol] solution in methanol is added to terminate the polymerization reaction. Next, a large amount of mixed solution of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C. to obtain 100% by weight of white polymer.

The obtained CHD single polymer has a number average molecular weight as high as 10,200.

The 1,2-bond / 1,4-bond molar ratio is 47/53. The glass transition temperature (Tg) of the obtained polymer, measured according to the DSC method, is 154 ° C.

Example 74

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. Inject 27.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, the amount of 0.3 mmol, in terms of the amount of lithium atoms, of the complex of Li / TMEDA molar ratio 2/2 (of n-BuLi) obtained in substantially the same manner as in Example 1 It is added to cyclohexane and dissolved to obtain a complex solution. The complex solution is maintained at 40 ° C.

To a complex solution obtained above to add 0.075 mmol of TMEDA (as the second complexing agent) to the complex solution, 1.0M solution of TMEDA in cyclohexane (as the second complexing agent) was added to give a Li / TMEDA molar ratio of 4 /. A cyclohexane solution of the complex-TMEDA mixture having 5 is obtained.

In an atmosphere of dried argon gas, 3.0 g of 1,3-CHD is added to the obtained complex-TMEDA mixture solution, and the polymerization reaction is carried out at 40 ° C. for 2 hours to obtain a CHD homopolymer.

To the obtained polymerization reaction mixture, a 10% by weight BHF [bis (t-butyl) -4-methylphenol] solution in methanol is added to terminate the polymerization reaction. Next, a large amount of mixed solution of methanol and hydrochloric acid is added to the polymerization reaction mixture containing the target polymer to separate the target polymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C. to yield 100% by weight of white polymer.

The obtained CHD homopolymer has a number average molecular weight as high as 9,870.

1,2-bond / 1,4-bond molar ratio is 49/51. The glass transition temperature (Tg) of the obtained polymer, measured according to the DSC method, is 154 ° C.

Example 75

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

A 10 wt% 1,500 g cyclohexane solution of the polymer obtained in Example 71 is added to a high pressure vessel. A catalyst solution is added to the obtained polymer solution, which solution hydrogenates the titanocene dichloride (TC) and the complex obtained in Example 1 in an amount of 100 ppm in terms of titanium atoms based on the weight of the polymer. It is prepared by adding cyclohexane (Ti / Li molar ratio: 1/1) as a catalyst.

Substitute hydrogen gas in the high pressure vessel. After raising the temperature of the high pressure vessel to 75 ° C., the hydrogenation reaction was carried out for 10 minutes at 10 kg / cm. At a hydrogen pressure of G.

After the completion of the hydrogenation reaction, the high pressure vessel is cooled to room temperature and the pressure of the high pressure vessel is lowered to atmospheric pressure. Methanol is added to the obtained reaction mixture to treat n-BuLi.

A stabilizer [Irganox B2l5 (00371k)] (manufactured and sold by CIBA GEIGY, Switzerland) was added to the reaction mixture, and then the solvent was removed by conventional methods to remove hydrogenated CHD-Bd-CHD triblock copolymer in the form of an elastomer. Get

The degree of hydrogenation of the CHD polymer block is 0 mol%. For 1,2-vinyl bond, 1,4-cis bond and 1,4-trans bond of Bd polymer block, The degree of hydrogenation determined by H-NMR is 100 mol%.

Example 76

A well dried 5 liter high pressure pressure vessel equipped with an electromagnetic induction stirrer is replaced with dried nitrogen gas in a conventional manner.

In an atmosphere of dried nitrogen gas, 1,500 g of cyclohexane is injected into a high pressure vessel. The temperature of cyclohexane is maintained at 70 ° C.

The hydrogenation reaction is carried out substantially in the same manner as in Example 75, but the polymer obtained in Example 72 is used.

The hydrogenation degree of the CHD polymer block of the obtained hydrogenated polymer, determined by H-NMR, is 0 mol%. For 1,2-vinyl bond, 1,4-cis bond and 1,4-trans bond of Bd polymer block, The degree of hydrogenation determined by H-NMR is 100 mol%.

Example 77

The well dried 100 ml Schlenk tube is replaced with argon gas dried in a conventional manner. Inject 27.0 g of cyclohexane into a Schlenk tube. While maintaining the temperature of cyclohexane at room temperature, a 1.6M solution of n-BuLi in n-hexane is added to the cyclohexane in an amount of 0.15 mmol in terms of the amount of lithium atoms to obtain a solution. The temperature of the solution is kept at 40 ° C.

To the resulting solution was added a 0.1 M solution of TMEDA (as first complexing agent) in cyclohexane (as first complexing agent) in an amount that provides a Li / TMEDA molar ratio of 4/4 (of n-BuLi) and the reaction was carried out at 40 ° C. for 10 minutes. To obtain a complex solution.

To a complex solution obtained above to add 0.0375 mmol of TMEDA (as the second complexing agent) to the complex solution, 1.0M solution of TMEDA in cyclohexane (as the second complexing agent) was added to give a Li / TMEDA molar ratio of 4 /. A cyclohexane solution of the complex-TMEBA mixture having 5 is obtained.

In an atmosphere of dried argon gas, 3.0 g of 1,3-CHD was added to the obtained complex-TMEDA mixture solution and the polymerization was carried out at 40 ° C. for 4 hours. To the obtained polymerization reaction mixture, a 10% by weight BHF [bis (t-butyl) -4-methylphenol] solution in methanol is added to terminate the polymerization reaction. Subsequently, a large amount of the mixed solution of methanol and hydrochloric acid are added to the polymerization reaction mixture containing the CHD single polymer to separate the CHD homopolymer. The separated polymer is washed with methanol and then dried in vacuo at 80 ° C. to obtain 100% by weight CHD homopolymer.

1,2-bond / 1,4-bond molar ratio is 52/48.

[Industry availability]

The cyclic conjugated diene polymer of the present invention has a relatively high molecular weight distribution as well as a relatively high 1,2-bond / 1,4-bond molar ratio, which has excellent thermal properties, mechanical properties and excellent functionality. The cyclic conjugated diene polymer of the present invention may advantageously be used alone or in combination with inorganic materials and as other resin materials. In addition, if desired, the cyclic conjugated diene polymer of the present invention may impart various functionalities in carrying out at least one reaction among hydrogenation, halogenation, hydrohalogenation, alkynation, acylation, ring-opening reaction and dehydrogenation. Can be. The cyclic conjugated diene polymer of the present invention can be prepared by the novel process of the present invention in which living anionic polymerization of cyclic conjugated diene monomers or cyclic conjugated diene monomers and comonomers copolymerizable therewith is carried out in the presence of specific catalysts.

Claims (32)

Formula (I)

(Wherein A to E are monomer units constituting the main chain, monomer units A to E are arranged in a certain order, and a to e are each of monomer units A to E based on the total weight of monomer units A to E). Weight percent, wherein A is selected from the class constituting the cyclic conjugated diene monomer unit, B is selected from the class constituting the chain conjugated diene monomer unit, C is selected from the class constituting the vinyl aromatic monomer unit, D is selected from the class constituting the polar monomer unit, E is selected from the class constituting the ethylene monomer unit and the α-olefin monomer unit, wherein a to e satisfy the following relationship and a + b + c + d + e = 100, 0.1 ≦ a ≦ 100, 0 ≦ b100, 0 ≦ c100, 0 ≦ d100, and 0 ≦ e100; wherein the monomeric unit A is 1,2- bond and 1,4- bond in the main chain Are bonded at, and the molar ratio of 1,2-bond / 1,4-bond is from 40/60 to (90/10). And cyclic conjugated diene polymers having a number average molecular weight of 500 to 5,000,000. The cyclic conjugated diene polymer according to claim 1, which is a block copolymer. The cyclic conjugated diene polymer according to claim 1, wherein the glass transition temperature (Tg) is 150 ° C or higher. 3. The cyclic conjugated diene polymer according to claim 2, wherein the block copolymer contains a polymer block having a glass transition temperature (Tg) of 150 ° C or higher. 3. The cyclic conjugated diene polymer of claim 2, which is at least one tri-block copolymer. The cyclic conjugated diene polymer according to any one of claims 2 to 5, which is a block copolymer having a polymer block containing two or more monomer units A. The cyclic conjugated diene polymer according to any one of claims 2 to 5, which is a block copolymer having a polymer block constituting two or more monomer units A. The method according to any one of claims 2 to 4, comprising at least one polymer block constituting at least two monomer units A and at least one polymer block constituting one kind of monomer unit selected from B to E. A cyclic conjugated diene polymer, characterized in that it is at least a diblock copolymer. The polymer block Y according to any one of claims 2 to 4, which is composed mainly of one polymer block X containing at least one monomer unit A, and at least one monomer unit selected from B and E. A diblock copolymer comprising a cyclic conjugated diene polymer, wherein the weight ratio of X / Y is 1/99 to 99/1. The polymer of claim 5, wherein the polymer is at least a triblock copolymer comprising at least two blocks X containing at least one monomer unit A and at least one polymer block Y mainly composed of at least one monomer unit selected from B and E. 7. And the weight ratio of X / Y is 1/99 to 99/1. 6. The ring according to claim 5, which is a triblock copolymer comprising two blocks X containing at least one monomer unit A and one block Y mainly composed of at least one monomer unit selected from B and E. Conjugated diene polymer. The cyclic conjugated diene polymer according to claim 10, wherein the at least triblock copolymer has a structure represented by a formula selected from the group consisting of:

(Wherein X and Y are the same as above, p is an integer of 1 or more, and q is an integer of 2 or more). The cyclic conjugated diene polymer according to claim 1, wherein the monomer unit A is selected from the group constituting the monomer unit represented by the following formula (II):

(Wherein m is an integer of 1 to 4, each of R ¹ is independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ unsaturated aliphatic hydrocarbon group, a C ₆ -C ₂₀ aryl group, C _{A 3} -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ cyclodienyl group or a 5-10 membered heterocyclic group having at least one nitrogen, oxygen or sulfur atom as a hetero atom, each R ² independently represents a hydrogen atom, a halogen atom, C _l - C ₂₀ alkyl group, C ₂ - C ₂₀ unsaturated aliphatic hydrocarbon group, C ₆ - C ₂₀ aryl group, C ₃ - C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cycloalkyl group or a cyclopentadienyl least one nitrogen as a hetero atom, oxygen or Or a 5 to 10 membered heterocyclic group having a sulfur atom, or each R ² independently represents a bonding group or a group, and two R ² groups are represented by the formula

Wherein R ³ is the same as R ^1, and n is an integer of 1 to 10). The cyclic conjugated diene polymer according to claim 13, wherein the monomer unit A is selected from the group constituting the monomer unit represented by the following general formula (III);

Wherein each of R ² is the same as in formula (II). 14. A monomer according to claim 13, wherein said monomeric unit A is selected from the classes comprising 1,3-cyclopentadiene monomer units, 1,3-cyclohexadiene monomer units, 1,3-cyclooctadiene monomer units and derivatives thereof. A cyclic conjugated diene polymer characterized by one or more causes. 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. The cyclic conjugated diene polymer according to claim 14, wherein the monomer unit A is a 1,3-cyclohexadiene monomer unit. A polymer produced by carrying out at least one reaction of hydrogenation, halogenation, hydrohalogenation, alkylation, arylation, ring opening, and dehydrogenation of the cyclic conjugated diene polymer of claim 1. Formula (I)

(Where A to E are monomer units constituting the main chain in which the monomer units A to E are arranged in a certain order, and a to e are the weights of the monomer units A to E based on the total weight of the monomer units A to E, respectively). %, A is selected from the class constituting the cyclic conjugated diene monomer unit, B is selected from the class constituting the chain conjugated diene monomer unit, C is selected from the class constituting the vinyl aromatic monomer unit, and D is polar Selected from the class constituting the monomer unit, and E is selected from the class constituting the ethylene monomer unit and the α-olefin monomer unit, wherein A to E satisfy the following relationship, and a + b + c + d + e Preparation of cyclic conjugated diene polymer having a number average molecular weight of 500 to 5,000,000, comprising a main chain represented by = 100, 0.1≤a≤100, 0≤b100, 0≤c100, 0≤d100, and 0≤e100). As a method, comprising A process for preparing a cyclic conjugated diene polymer, comprising: providing a complex of at least one first complexing agent with at least one organometallic compound containing a metal belonging to group IA of the periodic table, wherein At least one cyclic conjugated diene monomer in the presence of a catalyst comprising a mixture, or at least one comonomer copolymerizable with the monomer and at least one cyclic conjugated diene monomer (chain conjugated diene monomer, vinyl aromatic monomer, polar monomer, ethylene monomer, and α -Selected from the class comprising the olefin monomers). 20. The at least one element of claim 19, wherein each of the first and second complexing agents is independently selected from the group consisting of oxygen (O), nitrogen (N), sulfur (S) and phosphorus (P). It is an organic compound containing. 20. The method of claim 19, wherein each of said first and second complexing agents is independently an organic compound selected from the group consisting of ethers, metal alkoxides, amines and thioethers. 20. The method of claim 19, wherein each of said first and second complexing agents is independently an ether or an amine. 20. The method of claim 19, wherein each of said first and second complexing agents is independently an amine. 20. The method of claim 19, wherein each of said first and second complexing agents is independently diamine. 20. The method of claim 19, wherein each of said first and second complexing agents is independently aliphatic diamine. 20. The method of claim 19, wherein each of said first and second complexing agents is independently a tertiary amine. The method of claim 24, wherein the diamine is selected from the group consisting of tetramethylethylenediamine (TMEDA) and diazabicyclo [2,2,2] -octane (DABCO). 20. The method of claim 19, wherein the organometallic compound containing a metal belonging to group IA of the periodic table is an organolithium compound. The organometallic compound according to claim 19, wherein the organometallic compound containing a metal belonging to group IA of the periodic table is selected from the group consisting of normal butyllithium (n-BuLi), secondary butyllithium (s-BuLi) and tertiary butyllithium (t-BuLi). It is an organolithium compound selected from the group which comprises, A said 1st complexing agent and a said 2nd complexing agent are each independently tetramethylethylenediamine (TMEDA) and diazabicyclo [2,2,2] -octane (DABCO). Selected from the group consisting of: 30. The method of any one of claims 19 to 29, wherein the first complexing agent is reacted with the organometallic compound containing a metal belonging to group IA of the periodic table to produce the complex. Characteristic Methods: A ₁ / B ₁ = 200/1 to 1/100 (wherein A ₁ represents the molar amount of the Group IA metal contained in the organometallic compound used in the reaction, and B ₁ is used for the reaction). Molar amount of the first complexing agent). 30. The complex according to any one of claims 19 to 29, wherein the complex contains the organometallic compound and the first complexing agent containing a metal belonging to the Group IA metal of the periodic table in a molar ratio represented by the following formula. Method: A ₂ / B ₂ = l / 0.25 to 1/1 (wherein A ₂ represents the molar amount of the Group IA metal contained in the organometallic compound constituting the complex, and B ₂ forms the complex The amount of the first complexing agent). 30. The method of claim 19, wherein in said catalyst, said organometallic compound, said first complexing agent and said second complexing agent are present in a molar ratio relationship represented by the following formula: A ₃ / B ₃ = 100/1 to 1/200 (wherein A ₃ represents the molar amount of the Group IA metal contained in the organometallic compound, and B ₃ represents the total molar amount of the first complexing agent and the second complexing agent). ).

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