JPH09100314A - Curable resin and composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin having high thermal and mechanical properties and excellent in durability, chemical resistance, and compatibility with other resins by incorporating a polymer having cyclic structural units and reactive groups. SOLUTION: This resin comprises at least one polymer represented by the formula. In the formula, A to F each is a monomer unit as a component of the polymer backbone and may be arranged in any sequence, and (a) to (f) are the amounts (wt.%) of the monomer units A to F, respectively, based on the total amount of the monomer units A to F. The number-average mol.wt. in terms of standard PS of the polymer is 1,000-5,000,000. 'A' is a unit derived from a cyclic olefin monomer, B is one derived from a cyclic conjugated diene monomer, C is one derived from a chain conjugated diene monomer, D is one derived from a vinylaromatic monomer, E is one derived from a polar monomer, and F is an ethylene or α-olefin monomer unit. Q1 to Q6 each is a reactive group. 'A' to F satisfy the relationships a+b+c+d+e+f=100, 0<=(a, b)<=100, 0<=(c, d, e, f)<100, and a+b≠0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel curable resin composed of a polymer containing a cyclic molecular structural unit and having a reactive group, and a resin composition containing the resin. More specifically, the present invention provides a curable resin comprising a polymer having a cyclic molecular structural unit derived from a cyclic conjugated diene monomer and having a specific number of reactive groups, and the resin. A resin composition containing the same. Those resins and resin compositions have high thermal and mechanical properties, and also have excellent durability, chemical resistance, and compatibility with other resins,
Automotive field, civil engineering field, electrical and electronic field, textile field,
It can be advantageously used in the medical field, resin product field and the like.

[0002]

2. Description of the Related Art In recent years, polymer chemistry has made progress through several innovations in order to meet the demands of diversifying markets. In particular, in the research of polymer materials for industrial materials, a great deal of research has been conducted to develop better thermal and mechanical properties, and various types of materials have been proposed. Then, a curable resin which can improve thermal and mechanical properties by merely reacting a functional group which is originally contained or is contained by modification has been attracting attention and is used in various fields. Although the curable resin has been developed from the past, as described above, the base polymer is formed by reacting a functional group originally contained at the terminal or inside or modified by containing it to form a crosslinked structure. Since the purpose is to improve the performance of the produced polymer obtained from, the focus of development is UV crosslinking, electron beam crosslinking, ionic crosslinking, wet crosslinking (curing), and other chemical crosslinking (eg transesterification, hydrazone). The modification of the base polymer itself has not received much attention because it is a modification with a functional group for a reaction (crosslinking) such as oxidization, hydrazidation, oximation, or ammonium conversion. However, the market is diversified, and thermal and mechanical performance superior to conventional ones is required.
Chemical resistance, weather resistance, compatibility with other resins, etc. are required, and development of a completely new curable resin has been desired.

For example, in the field of electronic devices for communication, consumer use, industrial use, etc., there is a remarkable tendency toward miniaturization and high density of mounting methods, and accordingly, more excellent heat resistance in terms of materials. , Dimensional stability, electrical characteristics and flame retardancy are being demanded. For example, as a printed wiring board, a copper-clad laminate based on a curable functionalized polyphenylene ether resin has been used. Although these have excellent electrical properties and mechanical properties, they cannot be said to have sufficient heat resistance and chemical resistance when they are used as printed circuit board materials. Further, also in the field of construction and civil engineering, the purpose is to improve the strength of a sealing agent or concrete (mortar) using a polypropylene glycol-modified silicone-based curable resin as seen in Japanese Patent Publication No. Sho 61-18582. As such, polymer concrete (mortar) using unsaturated polyester, epoxy, vinyl ester, polyurethane, or phenolic curable resin as a binder has been developed.

In the sealing agent field, however, each of the commercially available polysulfide-based, urethane-based and silicone-based sealing agents has a problem. For example, it is said that the polysulfide type has a slow curing speed and poor tackiness, insufficient heat resistance, weather resistance, and fatigue resistance, and the polyurethane type has poor glass adhesion in addition to the problems of the polysulfide type. In addition, the curing speed, heat resistance, and silicone type (polyorganosiloxane type)
Although it has good weather resistance and fatigue resistance, it is difficult to overcoat the paint and lacks mold resistance. Therefore, improvement of these has been desired. As a method for overcoming these problems, for example, Japanese Patent Publication No. Sho 61-18582 proposes a curable resin obtained by modifying silicone with a high molecular weight polypropylene glycol, but still has an adhesive property to glass. However, the current situation is that there are problems with durability and applications are limited. Similarly, in the field of polymer concrete (mortar), there are problems of chemical resistance, durability and mechanical properties. These problems also exist in the industrial field of using curable resins, that is, in the fields of paints, adhesives, printing, electric / electronic materials, etc., and improvement in performance is desired.

As one of the most effective means for solving this problem, a cyclic conjugated diene-based monomer having a large steric hindrance, unlike a monomer having a relatively small steric hindrance such as butadiene and isoprene, is used. By homopolymerization or copolymerization, and further hydrogenation, a cyclic olefin structural unit is formed in the polymer chain of the conjugated diene polymer, and the structure of the polymer chain of the cyclic conjugated diene polymer is improved, Advanced thermal
BACKGROUND ART Research activities have been actively conducted to obtain polymer materials having mechanical properties and excellent in durability (heat resistance, weather resistance) and chemical resistance. However, in the prior art, although a catalyst system showing a polymerization activity which is relatively satisfactory for a monomer having a relatively small steric hindrance such as butadiene and isoprene, a monomer having a large steric hindrance, that is, a cyclic conjugated diene is proposed. A catalyst system having a sufficiently satisfactory polymerization activity has not yet been found for the system monomer. In other words, in the prior art, it is difficult to homopolymerize the cyclic conjugated diene monomer, and not only a high molecular weight polymer cannot be obtained, but also optimization of thermal and mechanical properties to meet various market demands. Even when attempting copolymerization with another monomer for the purpose of carrying out, it is possible to obtain only a low-molecular-weight substance of the order of an oligomer, and further to impart durability (heat resistance, weather resistance) and mechanical properties. It can be said that, at present, there is no knowledge of a polymer having a substituted cyclic olefin structure, which is important.

[0006] Am. Chem. Soc. , 81 , 4
No. 48 (1959) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene, which is a cyclic conjugated diene monomer, using a composite catalyst comprising titanium tetrachloride and triisobutylaluminum, and a polymerization method thereof. It has been disclosed. The polymerization method described here is
Not only requires a large amount of polymerization catalyst and a long reaction time, but also the molecular weight of the obtained polymer is extremely low,
No industrial value. Furthermore, there is no teaching or suggestion as to how to introduce the substituted cyclic olefin structural units and the possibility of modification. J. Polym. Sci. , Pt. A, 2 , 32
77 (1964) discloses a method for polymerizing a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene by various methods such as radical, cation, anion, and coordination polymerization. In any of the polymerization methods described herein, the molecular weight of the obtained polymer is extremely low in any case, and has no industrial value.
Furthermore, there is no teaching or suggestion as to how to introduce the substituted cyclic olefin structural units and the possibility of modification. British Patent Application No. 1,042,625 discloses a method for polymerizing a cyclohexadiene homopolymer by polymerizing 1,3-cyclohexadiene using a large amount of an organolithium compound as a catalyst. The polymerization method disclosed herein requires the use of as much as 1 to 2% by weight of a catalyst with respect to the monomer, which is not only economically disadvantageous but also has a very low molecular weight. Will be. On the other hand, in this polymerization method, it is difficult to remove a large amount of catalyst residue remaining in the polymer, and the polymer obtained by this polymerization method has no commercial value. Furthermore, there is no teaching or suggestion as to how to introduce the substituted cyclic olefin structural units and the possibility of modification.

[0007] Polym. Sci. , Pt. A,
3 , 1553 (1965) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using an organolithium compound as a catalyst. The polymer obtained here had a limit of number average molecular weight of 20,000, although the polymerization reaction was continued for 5 weeks. Furthermore, there is no teaching or suggestion as to how to introduce the substituted cyclic olefin structural units and the possibility of modification. Poly
m. Prepr. (Amer. Chem. Soc., D
iv. Polym. Chem. ) 12 , 402 (197)
In 1), when 1,3-cyclohexadiene is polymerized using an organolithium compound as a catalyst, the limit of the number average molecular weight of the cyclohexadiene homopolymer is 10,000.
It is disclosed that it is ˜15,000, and it is taught that the transfer reaction accompanied by the extraction of lithium cation and the elimination reaction of lithium hydride occur simultaneously with the polymerization reaction. Furthermore, there is no teaching or suggestion as to how to introduce the substituted cyclic olefin structural units and the possibility of modification. Die Makromekula
re Chemie. , 163 , 13 (1973) discloses a cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using a large amount of an organolithium compound as a catalyst. The oligomeric polymer obtained here has a number average molecular weight of only 6,500. Furthermore, there is no teaching or suggestion as to how to introduce the substituted cyclic olefin structural units and the possibility of modification.

[0008] Polym. Sci. , Polym.
Chem. Ed. , 20 , 901 (1982)
A cyclohexadiene homopolymer obtained by polymerizing 1,3-cyclohexadiene using an organic sodium compound as a catalyst is disclosed. The organic sodium compound used here is sodium naphthalene, and a dianion formed from a radical anion is actually a polymerization starting point. That is, the number average molecular weight of the cyclohexadiene homopolymer reported here is 38 apparently.
700, but the number average molecular weight is practically 19,350
The molecular chains of 2 grew only in two directions from the polymerization initiation point. Further, the polymerization method disclosed herein is a reaction at an extremely low temperature and has no industrial value. Furthermore,
There is no teaching or suggestion as to how to introduce the substituted cyclic olefin structural units and the possibility of modification. Makromol. C
hem. , 191 , 2743 (1990), describes a method of polymerizing 1,3-cyclohexadiene using polystyryllithium as a polymerization initiator. In the polymerization method described here, it is taught that transfer reaction accompanied by abstraction of lithium cation and elimination reaction of lithium hydride occur at the same time as the polymerization reaction, and the polymerization reaction is started by using polystyryllithium as an initiator. Despite the fact that it was carried out, it was reported that the styrene-cyclohexadiene block polymer was not obtained at room temperature, and only the low molecular weight cyclohexadiene homopolymer was obtained. Furthermore, there is no teaching or suggestion as to how to introduce the substituted cyclic olefin structural units and the possibility of modification. That is,
In the prior art, a conjugated diene-based polymer having an excellent reaction active group that is sufficiently satisfactory as an industrial material has not been obtained yet.

[0009]

In view of the above circumstances, the present invention has a high degree of thermal and mechanical properties, durability, chemical resistance and compatibility with other resins. It is intended to provide an excellent and novel curable composition. Under such circumstances, the present inventors have previously found that the polymer main chain is composed of at least one cyclic conjugated diene monomer unit, or at least one cyclic conjugated diene monomer. Unit and at least one other monomer unit copolymerizable therewith, having a high number average molecular weight, and having thermal properties such as melting point, glass transition temperature and heat distortion temperature, and tensile elastic modulus and flexural elastic modulus. The inventors have conducted extensive studies to develop a novel cyclic conjugated diene polymer having excellent mechanical properties such as, and a method for producing the same. As a result, in the production of a polymer of the type described above, it is possible to achieve a desired high degree of polymerization and block copolymerize a cyclic conjugated diene-based monomer and at least one other monomer copolymerizable therewith. Novel polymerization catalyst having catalytic activity for effectively and efficiently performing living anionic polymerization. Thereby,
Succeeded in synthesizing a novel cyclic conjugated diene polymer that has never been reported before, and derived from a cyclic conjugated diene monomer in some or all of the multiple monomer units that make up the polymer chain Has established a technique for introducing the above-mentioned monomer unit in an arbitrary ratio and form (WO94 / 28038). Further, as a result of research, the present inventors have developed a technique for providing a polymer containing a saturated cyclic molecular structural unit further derived from this cyclic conjugated diene polymer (WO94 / 29359).

As a result of further studies, the present inventors have found that a polymer containing a cyclic molecular structural unit derived from the above-mentioned cyclic conjugated diene-based monomer (cyclic conjugated diene-based or carbon-carbon double bond thereof). The cyclic olefin-based monomer unit-containing polymer obtained by partially or completely saturating the compound has high thermal and mechanical properties by containing a specific limited number of reactive groups. The present invention has been completed based on the finding that a curable resin having excellent durability, chemical resistance, and compatibility with other resins can be obtained. Therefore, one object of the present invention is to provide a novel curable resin having high thermal and mechanical properties, and having excellent durability, chemical resistance, and compatibility with other resins. To do. Another object of the present invention is to provide a composition comprising the above-mentioned novel curable resin and at least one other resin.

[0011]

The above and other objects, features and advantages of the present invention will become apparent from the following detailed description and claims taken in conjunction with the accompanying drawings. According to one aspect of the present invention, there is provided a curable resin comprising at least one polymer having a polymer chain represented by the following formula.

[0012]

Embedded image

[Formula (1) represents the composition formula of the polymer. A
~ F represents a monomer unit constituting the polymer main chain, A ~ F
Can be arranged in any order. a to f represent the respective wt% of the monomer units AF with respect to the total weight of the monomer units AF. The standard polystyrene equivalent number average molecular weight of the polymer is in the range of 1,000 to 5,000,000.

(A): One or more monomer units selected from cyclic olefin monomer units having no reactive group. (B): One or more monomer units selected from cyclic conjugated diene monomer units having no reactive group. (C): One or more monomer units selected from chain conjugated diene monomer units having no reactive group. (D): One or more monomer units selected from vinyl aromatic monomer units having no reactive group. (E): One or more monomer units selected from polar monomer units having no reactive group. (F): One or more monomer units selected from ethylene and α-olefin monomer units having no reactive group. A to F satisfy the following relationships. a + b + c + d + e + f = 100, 0 ≦ a, b ≦ 10
0,0 ≦ c, d, e, f <100, a + b ≠ 0.

Q _{1 to} Q ₆ are reactive groups directly bonded to A to F and may be the same or different.
The total number (J) of Q _{1 to} Q ₆ contained in the polymer molecule is
1 ≦ (J) ≦ 4. According to another aspect of the present invention, there is provided a resin composition comprising the resin (X) described above and at least one resin (Y) other than (X), wherein (X) and ( There is provided a curable resin composition in which 0.01 wt% ≦ Y ≦ 99.9 wt% with respect to the total weight of Y). According to still another aspect of the present invention, the resin (X), (X) described above.
A resin composition comprising a resin (Y) other than, and a compound (Z) selected from one or more cross-linking agents, wherein the total weight of (X), (Y) and (Z) is 0
wt% ≦ Y <100 wt%, 0 wt% <Z <100 wt
% Curable resin composition is provided. Next, in order to facilitate understanding of the present invention, basic features and aspects of the present invention will be listed. 1. A curable resin whose polymer chain is composed of at least one polymer represented by the following formula (1).

[0016]

Embedded image

[Formula (1) represents the composition formula of the polymer. A
~ F represents a monomer unit constituting the polymer main chain, A ~ F
Can be arranged in any order. a to f represent the respective wt% of the monomer units AF with respect to the total weight of the monomer units AF. The standard polystyrene equivalent number average molecular weight of the polymer is in the range of 1,000 to 5,000,000. (A): One or more monomer units selected from a cyclic olefin monomer unit having no reactive group. (B): One or more monomer units selected from cyclic conjugated diene monomer units having no reactive group. (C): One or more monomer units selected from chain conjugated diene monomer units having no reactive group. (D): One or more monomer units selected from vinyl aromatic monomer units having no reactive group. (E): One or more monomer units selected from polar monomer units having no reactive group. (F): One or more monomer units selected from ethylene and α-olefin monomer units having no reactive group.

A to F satisfy the following relationships. a + b + c + d + e + f = 100, 0 ≦ a, b ≦ 10
0,0 ≦ c, d, e, f <100, a + b ≠ 0. Q _{1 to} Q ₆ are reactive groups directly bonded to A to F, and may be the same or different. The total number (J) of Q _{1 to} Q ₆ contained in the polymer molecule is 1 ≦ (J) ≦
4. ] 2. Each of the reactive groups Q _{1 to} Q ₆ in the formula (1) is
Independently, C _{4 to} C ₂₀ cyclodienyl group, thiol group, carboxyl group, acid anhydride-containing group, hydrazinocarbonyl group, amino group, hydroxyl group, epoxy group, imino group,
Isocyanato group, sulfonic acid group, ester group, silyl group, siloxy group, vinyl group, methylol group, oxazoline group, silanol group, silyl ether group, silyl ester group, ether group, epoxy group, carbonyl group, formyloxy group, imide group , An acetoxy group, an alkoxysilane group, an oxazoline group, or a C _{1 to} C ₂₀ alkyl group having any of these bonded thereto, a C _{2 to} C ₂₀ unsaturated aliphatic hydrocarbon group, and a C _{3 to} C ₂₀ cycloalkyl group. group, an aryl group of _{C 5 ~C 20, C 4 ~C} 20 cyclodienyl group, or a curable resin according to item (1) is an organic compound residue containing one of these.

3. Q ₁ of the reactive group in the formula (1)
Each of Q ₆ is independently a functional group selected from a silyl group, a silyl ether group, a siloxy group, a silanol group or a silyl ester group, an organic compound residue containing the same, a vinyl group or an organic group containing the same. 3. The curable resin according to item 2 above, which is a compound residue, or an epoxy group or an organic compound residue containing the same. 4. At least one polymer represented by the formula (1) is
a = 100, The curable resin in any one of the preceding clauses 1-3 characterized by the above-mentioned. 5. At least one polymer represented by the formula (1) is
a + b = 100 and 0 <b, The curable resin in any one of the preceding clauses 1-3 characterized by the above-mentioned. 6. At least one polymer represented by the formula (1) is
a + c = 100 and 0 <c, The curable resin in any one of the preceding clauses 1-3 characterized by the above-mentioned. 7. At least one polymer represented by the formula (1) is
0.001 ≦ a + b <100 and 0.01 ≦ a <100
The curable resin according to any one of items 1 to 3 above. 8. At least one polymer represented by the formula (1) is
The curable resin according to any one of items 1 to 3 above, wherein a + b + c = 100 and at least one condition of 0 <b and 0 <c is satisfied.

9. At least one polymer represented by the formula (1) satisfies 0.01 ≦ a + b + c <100 and satisfies at least one condition of 0.1 ≦ a <100, 0 ≦ b and 0 <c. The curable resin according to any one of items 1 to 3 above. 10. At least one polymer represented by the formula (1) has b = 0 and c = 0, and the above-mentioned items 1 to 3 are characterized.
The curable resin according to any one of 1. 11. The curable resin according to any one of items 1 to 10, wherein the at least one polymer represented by the formula (1) is a block copolymer having a block unit containing at least one monomer unit A. 12. A sealing agent comprising the curable resin according to any one of items 1 to 11 above. 13. An adhesive comprising the curable resin according to any one of items 1 to 11 above. 14． A coating material comprising the curable resin according to any one of items 1 to 11 above. 15. An admixture for cement, comprising the curable resin according to any one of items 1 to 11 above. 16. The resin (X) according to any one of the above items 1 to 11,
A resin composition comprising a resin (Y) other than (X), and 0.01w based on the total weight of (X) and (Y).
A curable resin composition in which t% ≦ Y ≦ 99.9 wt%. 17． The resin (X) according to any one of the above items 1 to 11,
A resin composition comprising a resin (Y) other than (X) and one or more cross-linking agents (Z), which is 0 wt% based on the total weight of (X), (Y) and (Z). % ≦ Y <100w
A curable resin composition having t% and 0 wt% <Z <100 wt%. 18. A sealing agent comprising the resin composition according to the above 16 or 17. 19. An adhesive comprising the resin composition according to the above 16 or 17. 20. A paint comprising the resin composition according to the above 16 or 17. 21. An admixture for cement, comprising the resin composition according to the above 16 or 17.

In the present invention, each monomer unit constituting the polymer is named according to the name of the monomer from which the monomer unit is derived. Therefore, for example, the “cyclic conjugated diene-based monomer unit” means a constitutional unit of a polymer produced as a result of polymerizing a monomeric cyclic conjugated diene, and its structure is two carbons of cycloalkene. Is a molecular structure with a binding site. Further, the "cyclic olefin-based monomer unit" means a constitutional unit of a polymer produced as a result of polymerizing a cyclic olefin which is a monomer, and its structure has two carbons of a cycloalkane as a bonding site. It has a molecular structure. As a polymer containing a cyclic molecular structural unit having a representative reactive group in the present invention, a molecular structural unit derived from only a cyclic conjugated diene monomer or a cyclic conjugated diene monomer and a copolymerizable therewith A polymer containing a molecular structural unit derived from such a monomer as a repeating unit and having a reactive group can be exemplified. More specifically, a molecular structure unit derived from a cyclic conjugated diene-based monomer or a cyclic conjugated diene-based monomer and a monomer copolymerizable therewith, containing as a repeating unit of the polymer chain, A polymer having a reactive group can be exemplified.

More specifically, a homopolymer of a cyclic conjugated diene monomer, a copolymer of two or more cyclic conjugated diene monomers, a cyclic conjugated diene monomer, and a copolymerizable therewith Examples thereof include copolymers with other monomers, and polymers having a reaction active group in the polymer. As the most preferable cyclic molecular structural unit-containing polymer having a reactive group, the molecular structural unit derived from the cyclic conjugated diene-based monomer contained in the polymer chain is a molecular structural unit containing a cyclohexene ring. A polymer containing a reaction active group in the polymer can be exemplified. The curable resin of the present invention may contain two or more of these polymers at the same time. The cyclic olefin-based monomer unit in the present invention is one or two or more kinds of monomer units selected from cyclic olefin-based monomer units composed of carbon-carbon bonds. The monomer unit selected from the preferable cyclic olefin-based monomer is one or more kinds selected from a 5- to 8-membered cyclic olefin-based monomer unit constituted by a carbon-carbon bond. Is a monomer unit. Particularly preferred cyclic olefin-based monomer units are 6-membered cyclic olefin-based monomer units constituted by carbon-carbon bonds. Specific examples of the cyclic olefin-based monomer unit include cyclopentane, cyclohexane, and cyclooctane derivatives. A particularly preferred cyclic olefin-based monomer unit is a cyclohexane derivative. In the polymer having a saturated cyclic molecule used in the present invention, a preferred cyclic olefin-based monomer unit as a repeating unit constituting a polymer chain is a molecular structural unit represented by the following formula (3), and most preferred The molecular structural unit is a molecular structural unit represented by the following formula (5).

[0023]

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[N represents an integer of 1 to 4. R1 each independently represent a hydrogen atom, a halogen atom, C ₁ -C ₂₀ alkyl groups, unsaturated aliphatic hydrocarbon group of C ₂ -C _20, aryl group of C ₅ -C _20, cycloalkyl of C ₃ -C ₂₀ alkyl group, C ₄ -C ₂₀
Or a 5- to 10-membered heterodicyclic group containing at least one nitrogen, oxygen or sulfur as a hetero atom, wherein R ^2's each independently represent a hydrogen atom, a halogen atom, C _{1 to} C ₂₀ Alkyl group, C _{2 to} C ₂₀ unsaturated aliphatic hydrocarbon group, C _{5 to} C ₂₀ aryl group, C _{3 to} C ₂₀ cycloalkyl group, C _{4 to} C ₂₀ cyclodienyl group, or 5 to 10 A heterocyclic group which is a membered ring and contains at least one nitrogen, oxygen or sulfur as a hetero atom, or R
² are each independently two R ²

[0025]

Embedded image

(R ³ has the same meaning as R ¹ and m is 1 to 1
Is a whole number of 0). ]

[0027]

Embedded image

[Each R ² has the same meaning as defined in the formula (3). The content of the cyclic olefin-based monomer unit in the polymer used in the present invention is not particularly limited because it is set variously depending on its intended use, but it is generally 0.001 to 1
It is in the range of 00 wt%, preferably 0.01 to 100
It is in the range of wt%, and particularly preferably 0.1 to 100 w
t%.

When the polymer used in the present invention is used in an application / field requiring high thermal / mechanical properties or functionality, the content of the cyclic olefin monomer unit is 1 to 100 wt. %, Preferably 2 to
It is particularly preferable that it is in the range of 100 wt%, and 5 to 1
Most preferably, it is in the range of 00 wt%. Examples of the cyclic olefin-based monomer from which the cyclic olefin-based monomer unit is derived include cyclopentene, cyclohexene, cyclooctene and derivatives thereof. The polymer used in the present invention may be obtained by any production method, and is particularly preferable as long as it has the cyclic olefin structural unit and / or the cyclic conjugated diene monomer unit of the present invention. It is not subject to any other restrictions.
More specifically, the cyclic olefin-based monomer unit in the polymer used in the present invention is within the scope of the present invention.
It may be introduced into the polymer chain by any method without particular limitation.

Further, a cyclic conjugated diene polymer, for example,
It is also possible to polymerize 1,3-cyclopentadiene, 1,3-cyclohexadiene and 1,3-cyclooctadiene and hydrogenate a part of the carbon-carbon double bond to form a cyclic olefin-based monomer unit. It is not particularly limited. The cyclic conjugated diene monomer unit in the present invention means carbon-
One or two or more monomer units selected from cyclic conjugated diene monomer units, which are composed of carbon bonds. The cyclic conjugated diene-based monomer from which the cyclic conjugated diene-based monomer unit is derived is a 5- or more-membered cyclic conjugated diene composed of carbon-carbon bonds. A preferred cyclic conjugated diene-based monomer is a 5- to 8-membered cyclic conjugated diene composed of carbon-carbon bonds. A particularly preferred cyclic conjugated diene-based monomer is a 6-membered cyclic conjugated diene composed of carbon-carbon bonds. Specifically, 1,
Examples thereof include 3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene and derivatives thereof. Examples of preferable cyclic conjugated diene-based monomers include 1,3-cyclohexadiene and 1,3-cyclohexadiene derivatives. The most preferred cyclic conjugated diene-based monomer is 1,3-cyclohexadiene.

The molecular weight of the cyclic molecule structural unit-containing polymer having a reaction-active group used in the present invention is generally in the range of 1,000 to 5,000,000 in number average molecular weight, and the optimum molecular weight range depends on the application. For example, when used as an industrial material such as structural parts,
The number average molecular weight is in the range of 10,000 to 5,000,000, and in view of industrial productivity, the number average molecular weight is preferably 15,000 to 5,000,000.
The range is 0, preferably 20,000 to 3,000,000, and more preferably 25,000 to 2,000.
More preferably, it is in the range of 30,000,
The range of 00 to 1,000,000 is particularly preferable. Most preferred is 40,000 to 500,000
It is in the range of 0. Also, like the field of construction and civil engineering, plasticity,
When adhesiveness and compatibility with inorganic components are required, the number average molecular weight is preferably in the range of 1,000 to 50,000. When the number average molecular weight is 1,000 or less, it becomes a remarkably brittle solid or viscous liquid and its value as an industrial material becomes extremely low. Number average molecular weight of 5,000,000
When it is 0 or more, the polymerization time becomes long and the melt viscosity becomes remarkably high, resulting in undesirable results in industrial production. The number average molecular weight (M
n) is the number average molecular weight in terms of standard polystyrene measured by GPC (gel permeation chromatography) method. In addition, M which is an index of molecular weight distribution
The w / Mn value is in the range of 1.01 to 10, preferably 1.03 to 7.0, and particularly preferably 1.0.
It is in the range of 5 to 5.0.

As the other monomer copolymerizable with the cyclic conjugated diene-based monomer in the present invention, a conventionally known monomer that can be polymerized by anionic polymerization can be exemplified. For example, 1,3-butadiene, isoprene, 2,
Chain conjugated diene-based monomers such as 3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p -Tert-Butylstyrene, 1,3-dimethylstyrene, vinyl aromatic monomers such as divinylbenzene, vinylnaphthalene, diphenylethylene and vinylpyridine, polar vinyl monomers such as acrylonitrile or ethylene oxide, propylene oxide, cyclic Examples thereof include polar monomers such as lactones, cyclic lactams and cyclic siloxanes, and ethylene and α-olefin monomers. These monomers may be used alone or in combination of two or more as necessary. In addition, the mode of copolymerization of the cyclic molecule structural unit-containing polymer having a reactive group used in the present invention can be variously selected as necessary. For example, diblock, triblock, tetrablock, multiblock,
Examples thereof include block copolymer such as radial block, graft copolymerization, taper copolymerization, random copolymerization and alternating copolymerization. In the cyclic molecular structural unit-containing polymer having a reactive group used in the present invention, the molecular structural unit composed of another copolymerizable monomer,
The molecular structural unit derived from hydrogenation after completion of the polymerization reaction is not particularly limited.

The content of the molecular structural unit derived from the cyclic conjugated diene monomer in the cyclic molecular structural unit-containing polymer having a reactive group used in the present invention is set variously depending on its intended use. Therefore, it is not particularly limited, but it is generally in the range of 0.1 to 100 wt%, preferably in the range of 0.5 to 100 wt%, and particularly preferably in the range of 1 to 100 wt%. Furthermore, the cyclic molecular structural unit-containing polymer having a reactive group in the present invention has a polymer terminal with a conventionally known bifunctional or higher functional cup for the purpose of adjusting the molecular weight or obtaining a star-shaped polymer, if necessary. Ring agent (for example, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, Bonding with silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, esters, etc.) is also not particularly limited. When the cyclic molecular structural unit-containing polymer having a reactive group in the present invention is a cyclic conjugated molecular structural unit-containing block copolymer having a reactive active group containing a block unit in the polymer chain, as the block unit Is a block unit composed of a molecular structural unit derived from a cyclic conjugated diene-based monomer, a cyclic structural diene-based monomer and a molecular structural unit derived from another monomer copolymerizable therewith Block unit, and further a block unit composed of a molecular structural unit derived from another monomer copolymerizable with the cyclic conjugated diene-based monomer can be designed, and various blocks can be designed as necessary. A block copolymer containing a conjugated molecular structural unit having a reaction-active group according to the purpose can be obtained by designing and polymerizing the unit and binding the units.

When the block unit of the present invention contains a molecular structural unit derived from a cyclic conjugated diene monomer in a part or all of the block unit, at least 10 units are contained in the block unit.
It is preferable that the molecular structural units derived from the cyclic conjugated diene-based monomer of the molecule are continuously bonded, more preferably 20 or more molecular structural units are continuously bonded, and 30 molecules It is particularly preferable that the above-mentioned molecular structural units are continuously bonded in order to improve thermal / mechanical properties. When the block copolymer containing a cyclic conjugated molecular structural unit having a reactive group in the present invention is synthesized, it is composed of a molecular structural unit derived from one or two or more cyclic conjugated diene-based monomers. Block unit, 1
Block unit composed of one or two or more cyclic conjugated diene-based monomers and a molecular structural unit derived from one or more other monomers copolymerizable therewith, and further a cyclic conjugate It is possible to exemplify a method of polymerizing and binding a block unit composed of a molecular structural unit derived from one or more kinds of other monomers copolymerizable with a diene monomer, depending on the purpose. it can. For example, a block unit containing a molecular structural unit derived from a cyclic conjugated diene monomer, or a block unit derived from a cyclic conjugated diene monomer is preliminarily polymerized, and one end of the polymer or A method of polymerizing one or two or more other monomers copolymerizable therewith from both ends. One kind or two or more kinds of other monomers copolymerizable with the cyclic conjugated diene-based monomer are preliminarily polymerized, and the cyclic conjugated diene-based monomer and the necessary monomer are added from one end or both ends of the polymer. A method of polymerizing one or two or more other monomers copolymerizable with the cyclic conjugated diene-based monomer according to the above.

A block unit containing a molecular structural unit derived from a cyclic conjugated diene monomer or a block unit derived from a cyclic conjugated diene monomer is polymerized,
Then, a block unit containing a molecular structural unit derived from a cyclic conjugated diene-based monomer or a cyclic conjugated diene-based single monomer is prepared by polymerizing one or more other monomers copolymerizable therewith. A method of sequentially polymerizing block units derived from a polymer. A block unit containing a molecular structural unit derived from the cyclic conjugated diene-based monomer by previously polymerizing one or more other monomers copolymerizable with the cyclic conjugated diene-based monomer. Alternatively, a method of polymerizing a block unit derived from a cyclic conjugated diene-based monomer, and sequentially polymerizing one or more other monomers copolymerizable with the cyclic conjugated diene-based monomer . A block unit containing a molecular structural unit derived from a cyclic conjugated diene-based monomer or a block unit derived from a cyclic conjugated diene-based monomer is polymerized and is then copolymerizable with one or two kinds. The above-mentioned other monomers are polymerized, and the polymer terminal is a conventionally known bifunctional or higher functional coupling agent (for example, trichlorosilane, methyldichlorosilane, dimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromo). Silane, methyltribromosilane, titanocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, esters, etc.). A block unit containing a molecular structural unit derived from a cyclic conjugated diene-based monomer or a block unit derived from a cyclic conjugated diene-based monomer is preliminarily polymerized, and a terminal modifier (ethylene oxide, ethylene oxide, Propylene oxide, cyclohexene oxide, carbon dioxide gas, acid chloride, etc.) to introduce a functional group and to bond it with another polymer having a functional group to bond with it.

A block unit containing a molecular structural unit derived from a cyclic conjugated diene monomer or a block unit derived from a cyclic conjugated diene monomer is polymerized,
Then, one or more kinds of other monomers copolymerizable with this are polymerized, and a terminal modifier (ethylene oxide, propylene oxide, cyclohexene oxide, carbon dioxide, acid chloride, etc.) is reacted with the polymer terminal. A functional group is introduced by the method of (1), and the functional group is bonded to another polymer having a functional group to be bonded thereto. A method of forming a tapered block copolymer by simultaneously polymerizing a cyclic conjugated diene-based monomer and one or more other monomers having different polymerization rates and copolymerizable with each other. A method in which a cyclic conjugated diene-based monomer and one or more kinds of other monomers copolymerizable with the cyclic conjugated diene-based monomer are charged in different composition ratios, and polymerization is performed simultaneously. A cyclic conjugated diene-based monomer is polymerized first, and at any conversion rate, one or two or more other copolymerizable monomers having different polymerization rates are copolymerized to form a block copolymer. Methods, etc., and various block copolymers can be prepared as needed.

The block unit derived from one or more cyclic conjugated diene-based monomers is a molecule derived from one or more other monomers copolymerizable therewith. Inclusion of a structural unit is not particularly limited. Further, in the polymer chain which is a molecular structural unit derived from one or more kinds of other monomers copolymerizable with one or more kinds of cyclic conjugated diene-based monomers, Alternatively, it is not particularly limited to contain a molecular structural unit derived from two or more kinds of cyclic conjugated diene monomers. The most preferable molecular structural unit or block unit derived from one or more cyclic conjugated diene-based monomers in the present invention is a molecular structural unit containing a cyclohexene ring, or a structural unit containing the same or composed thereof. It is a block unit. In the cyclic conjugated diene-based polymer used in the most preferable method for producing a polymer containing a cyclic molecular structural unit having a reactive group of the present invention, a cyclic conjugate contained in a part or all of repeating units constituting a polymer chain A preferred molecular structural unit derived from a diene-based monomer is a molecular structural unit represented by the following formula (4),
The most preferable molecular structural unit is a molecular structural unit represented by the following formula (6).

[0038]

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[Each R ¹ and R ² has the same meaning as defined in the formula (3). However, the carbon-carbon double bond of the formula (4) is not hydrogenated]

[0040]

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[Each R ² has the same meaning as defined in the formula (3). However, the carbon-carbon double bond of the formula (6) is not hydrogenated. The block copolymer containing a cyclic conjugated molecular structural unit having a reactive group in the present invention, and the block copolymer containing a saturated cyclic molecule obtained by carrying out an addition reaction thereto have a thermoplastic elastomer or impact resistance. In the case of the special transparent resin, the special transparent resin has at least two constrained phases (block units) and at least one rubber phase (block units), and both blocks must be microphase-separated.

The polymer chain having such a structure exhibits elastomer elasticity because the constrained phase acts as a physical cross-linking point at a temperature of Tg or less. Since the polymer chains flow above the Tg of the constrained phase, injection molding and recycling can be performed. The cyclic molecular structural unit-containing polymer having a reactive group in the present invention is mainly composed of a cyclic conjugated diene monomer unit or a derivative thereof if the most preferable polymerization method disclosed in the present invention, that is, living anionic polymerization is adopted. At least two block units (hereinafter referred to as X blocks) which are composed of a cyclic conjugated diene monomer and a vinyl aromatic monomer, mainly a chain conjugated diene monomer unit or its At least one polymer block unit (hereinafter Y block) composed of a derivative
It is possible to obtain a block copolymer containing a conjugated molecular structural unit having a reaction-active group that each has, and by subjecting this to an addition reaction such as hydrogenation, a block copolymer having a saturated cyclic molecule can be obtained. For example, as a thermoplastic elastomer or a special transparent resin having impact resistance, a linear block copolymer represented by the following formula (7) and a radial block copolymer represented by the following formula (8) are produced. The polymer containing cyclic molecular structural units having these reactive groups and the polymer obtained by this addition reaction can exhibit rubber elasticity. (X-Y) _l , X- (Y-X) _m , Y- (X-Y) _n (7) [l and n represent 2 or more and m represents an integer of 1 or more. ] [(Y-X) _{n] m} Z, [(X-Y) _{n] m} Z, [(Y-X) _n -Y] _m Z, [(X-Y) _n -X] _m Z (8 ) [M represents an integer of 2 or more and n represents an integer of 1 or more. Z is, for example, dimethyldichlorosilane, methylene chloride, silicon tetrachloride,
It represents a residue of a polyfunctional coupling agent such as tin tetrachloride or epoxidized soybean oil, or a residue of an initiator such as a polyfunctional organic group IA metal compound. ] When a carbon-carbon unsaturated bond remains in the polymer having a saturated cyclic molecule of the present invention, this is determined according to the purpose and use,
It is also possible to obtain a hydrogenated polymer by hydrogenating in an arbitrary range and ratio (hydrogenation rate).

The cyclic conjugated diene-based polymer used in the most preferred method for producing a polymer containing a cyclic molecular structural unit having a reaction active group of the present invention may be obtained by any conventionally known polymerization method. Although not particularly limited as long as it is within the range of 1, the most preferable polymerization method of the polymer having a molecular structure unit having a reactive group of the present invention is an organometallic compound containing a metal of Group IA of the periodic table disclosed by the present invention. A complex compound is formed by reacting amines with a complexing agent as a complexing agent, and living anion polymerization is performed by using this as a polymerization catalyst to obtain a cyclic conjugated diene polymer having an arbitrary molecular weight and polymer structure. It is a polymerization method. In the polymerization method used in the present invention, the group IA metals that can be used as the polymerization catalyst are lithium, sodium, potassium, rubidium, cesium and francium, and examples of preferable group IA metals are lithium, sodium and potassium. Which is particularly preferred I
Lithium can be illustrated as a group A metal. The complex compound which is the polymerization catalyst of the polymerization method used in the present invention is a complex compound formed by reacting the organometallic compound containing a Group IA metal with amines. As a particularly preferable complex compound, a complex compound formed by reacting an amine with an organic lithium compound, an organic sodium compound or an organic potassium compound can be exemplified.

As the most preferable complex compound, a complex compound formed by reacting an organolithium compound with amines can be exemplified. The organolithium compound preferably used for the polymerization catalyst used in the present invention is a compound containing one or more lithium atoms, which is bonded to an organic molecule or organic polymer containing at least one carbon atom. Is. Here, the organic molecule is C
Alkyl group of ₁ -C _20, unsaturated aliphatic hydrocarbon group of C ₂ -C _20, aryl group of C ₅ -C _20, cycloalkyl group of C ₃ -C _20, in cyclodienyl group C ₄ -C ₂₀ is there. Specific examples of the organic lithium compound include methyllithium, ethyllithium, n-propyllithium, iso-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium,
Hexyllithium, allyllithium, cyclohexyllithium, phenyllithium, hexamethylenedilithium, cyclopentadienyllithium, indenyllithium, butadienyldilithium, isoprenyldilithium, etc., or polybutadienyllithium, polyisoprenyllithium. Examples thereof include known oligomeric or polymeric organic lithium containing a lithium atom in a part of a polymer chain such as polystyryllithium.
The type of the preferred organolithium compound is not particularly limited as long as it forms a stable complex state (compound), but typical organolithium compounds include methyllithium, ethyllithium, n-propyllithium, i.
so-propyllithium, n-butyllithium, sec
Examples include -butyllithium, tert-butyllithium, and cyclohexyllithium.

The most preferable organolithium compound that can be industrially adopted is n-butyllithium (n-BuLi). The organometallic compound containing a Group IA metal employed in the polymerization method used in the present invention may be one kind or a mixture of two or more kinds, if necessary. In the polymerization catalyst in the polymerization method used in the present invention,
The complexing agent reacted with the organometallic compound containing a Group IA metal to form a complex compound is one kind or two or more kinds of amines. More specifically, a polar group R ¹ R ² N-group (R ¹ , which is capable of forming a complex by coordinating to an organometallic compound containing a Group IA metal, is present). R ² represents an alkyl group, an aryl group or a hydrogen atom, which may be the same or different.) And an organic amine compound or an organic polymer amine compound containing one or more of them. You can Of these amines, the most preferred amines are tertiary (tertiary) amine compounds. Preferred tertiary (tertiary) amine compounds in the present invention include trimethylamine, triethylamine, dimethylaniline, diethylaniline, tetramethyldiaminomethane, tetramethylethylenediamine, tetramethyl-1,3-propanediamine, tetramethyl-1,3. -Butanediamine, tetramethyl-1,4-butanediamine, tetramethyl-1,6
-Hexanediamine, tetramethyl-1,4-phenylenediamine, tetramethyl-1,8-naphthalenediamine, tetramethylbenzidine, tetraethylethylenediamine, tetraethyl-1,3-propanediamine, tetramethyldiethylenetriamine, tetraethyldiethylenetriamine, pentamethyldiethylenetriamine ,
Pentaethyldiethylenetriamine, diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,4,0] -7-undecene, 1, 4,8,11-
Tetramethyl-1,4,8,11-tetraazacyclotetradecane, tetrakis (dimethylamino) ethylene,
Examples include tetraethyl-2-butene-1,4-diamine and hexamethylphosphoric triamide.

In the present invention, more preferred amines are aliphatic amines, and particularly preferred amines are aliphatic diamines. Particularly preferred aliphatic diamines include:
Tetramethylmethylenediamine (TMMDA), tetraethylmethylenediamine (TEMDA), tetramethylethylenediamine (TMEDA), tetraethylethylenediamine (TEEDA), tetramethylpropylenediamine (TMPDA), tetraethylpropylenediamine (TEPDA), tetramethylbutylenediamine (T
MBDA), tetraethyl butylene diamine (TEBD
A), tetramethylpentanediamine, tetraethylpentanediamine, tetramethylhexanediamine (TM
HDA), tetraethylhexanediamine (TEHD)
A), diazabicyclo [2,2,2] octane (DAB
ACO) can be illustrated. The most preferable aliphatic diamine compound that can be industrially adopted is an aliphatic diamine that reacts with an organolithium compound to form a stable complex compound, and the number of carbon atoms existing between nitrogen atoms is 1
## STR6 ## are preferred, those with 1 to 3 carbon atoms are particularly preferred, and aliphatic diamines with 2 carbon atoms are most preferred. Tetramethylethylenediamine (TMEDA) can be illustrated as the most preferable aliphatic diamine. The amines used as these complexing agents are
It is also possible to use one kind or a mixture of two or more kinds as necessary.

The preferred combination of the organometallic compound and amines used in the polymerization method of the present invention is a combination that forms a stable complex under room temperature conditions.
A particularly preferred combination is n-butyllithium (n-
BuLi) and tetramethylmethylenediamine (TMMD
A), tetramethylethylenediamine (TMEDA),
It is a combination selected from tetramethylpropylenediamine (TMPDA) and diazabicyclo [2,2,2] octane (DABACO). The most preferred combination is n-butyllithium (n-BuLi) and tetramethylethylenediamine (TMEDA), and the white or colorless crystalline complex compound formed therefrom is stable under room temperature conditions, Most preferred as a polymerization catalyst in the above polymerization method. In the polymerization method of the present invention, a complex compound is formed by reacting an organometallic compound containing a metal of Group IA of the periodic table with amines as a complexing agent before the polymerization reaction, and this is used as a polymerization catalyst. . The method for synthesizing the polymerization catalyst used in the present invention is not particularly limited, and conventionally known techniques can be applied as necessary. For example, a method in which an organometallic compound is dissolved in an organic solvent under a dry inert gas atmosphere and a solution of amines is added thereto. Alternatively, a method in which amines are dissolved in an organic solvent under a dry inert gas atmosphere and a solution of an organometallic compound is added thereto can be exemplified, and the method is appropriately selected as necessary. The organic solvent used here is preferably selected appropriately according to the kind and amount of the organic metal and the kind and amount of the amine compound, and is preferably used after sufficiently degassing and drying. In addition, the temperature condition for reacting the organometallic compound and the amines is generally -100.
It can be appropriately selected within the range of up to 100 ° C. Helium, nitrogen, and argon are preferable as the dry inert gas, and nitrogen or argon is preferably used industrially.

Amine as a complexing agent is added to an organometallic compound containing a Group IA metal, which is a polymerization catalyst of the most preferable polymerization method for obtaining a polymer containing a cyclic molecular structural unit having a reactive group of the present invention. In the case of reacting to form a complex compound, when the amine compound molecule to be blended and the Group IA metal atom in the organometallic compound are Amol and Bmol, respectively, the blending ratio of these is generally A / B = 1000/1 To 1/1000, preferably A / B = 500/1 to 1/500, more preferably A / B = 100/1 to 1/100, and The range of B = 50/1 to 1/50 is particularly preferable, and the range of A / B = 20/1 to 1/20 forms a stable complex compound at a high yield and has a molecular weight distribution. Narrow ring of It is most preferable for efficiently producing the conjugated diene-based polymer. Amine compound molecule and I
When the compounding ratio of the group A metal atom is outside the range of the present invention, not only is it economically disadvantageous, but the complex compound as the polymerization catalyst becomes unstable, and the transfer reaction or the group IA metal hydride simultaneously occurs in the polymerization reaction. This will lead to undesirable results such as side reactions such as the elimination reaction of.

In the polymerization method of the present invention, an organometallic compound containing a metal of Group IA of the periodic table is reacted with amines as a complexing agent to form a complex, and then unreacted before the polymerization reaction. Removal of the organometallic compound containing a metal of Group IA of the Periodic Table is a particularly preferred method in the present invention. If the unreacted organometallic compound remains, side reactions such as transfer reaction or elimination reaction of Group IA metal hydride occur concurrently with the polymerization reaction, and the molecular weight distribution of the cyclic conjugated diene polymer is broadened, or the polymer This will have unfavorable consequences such as the block not being completely formed. The polymerization method in the polymerization method of the present invention is not particularly limited, and gas phase polymerization, bulk polymerization, solution polymerization or the like can be appropriately selected and adopted. As the polymerization reaction process, for example, a batch type, a semi-batch type, a continuous type or the like can be appropriately selected and used. As the polymerization solvent that can be used in the case of solution polymerization,
Butane, n-pentane, n-hexane, n-heptane,
Aliphatic hydrocarbons such as n-octane, iso-octane, n-nonane, n-decane, such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane, cyclooctane, decalin, norbornane Alicyclic hydrocarbon, benzene, toluene, xylene, ethylbenzene,
Examples thereof include aromatic hydrocarbons such as cumene and ethers such as diethyl ether and tetrahydrofuran.

These polymerization solvents may be used alone or in a mixture of two or more if necessary. Preferred polymerization solvents are aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents, and most preferred polymerization solvents are aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, or mixed solvents thereof. It is. The most preferable polymerization solvent in the production method of the present invention is normal hexane or cyclohexane, or a mixed solvent thereof. The amount of the polymerization catalyst used in the method of polymerizing the cyclic conjugated diene polymer cannot be particularly limited because it varies depending on the purpose. 10 ^-6 mol to ¹ × 10 ^-1 mo
1 range, preferably 5 × 10 ⁻⁶ mol to 5 × 1
It can be carried out in the range of 0 ^-2 mol. The polymerization temperature in the method of polymerizing the cyclic conjugated diene polymer is set to be variously different as necessary, but generally -10.
0 to 150 ° C, preferably -80 to 120 ° C, particularly preferably -30 to 110 ° C, most preferably 0 to 100 ° C.
It can be carried out within the range. From an industrial point of view, it is advantageous to carry out the treatment at room temperature to 90 ° C.

The time required for the polymerization reaction is not particularly limited because it varies depending on the purpose or the polymerization conditions, but it is usually within 48 hours, particularly preferably in the range of 1 to 10 hours. To be done. The atmosphere in the polymerization reaction system is preferably an inert gas such as nitrogen, argon or helium, particularly a sufficiently dried inert gas. The pressure of the polymerization reaction system is not particularly limited as long as it is within the pressure range sufficient to maintain the monomer and solvent in the liquid phase within the above-mentioned polymerization temperature range. Further, it is necessary to take care that impurities such as water, oxygen, carbon dioxide, etc., which inactivate the polymerization catalyst and the active terminal, do not enter into the polymerization system. In the method for polymerizing the polymer containing a molecular structural unit having a reaction active group of the present invention, the polymerization catalyst used may be one kind or a mixture of two or more kinds, if necessary. In the polymerization method, after the polymerization reaction reaches a predetermined polymerization rate, if necessary, a known terminal modifier (halogen gas, carbon dioxide gas, carbon monoxide, alkylene oxide, alkylene sulfide, isocyanate compound, imino compound, aldehyde) Compounds, ketones and thioketone compounds, esters, lactones, amide-containing compounds, urea compounds, acid anhydrides) or terminal branching agents (polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyanhalides, polyesters, polyhalides, Metal halides, etc., coupling agents (trichlorosilane, methyldichlorosilane, dimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, methyltribromosilane, titanocene dichloride, di Conocene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride, epoxidized soybean oil, esters, etc.), and further a polymerization terminator, a polymerization stabilizer, or Addition of stabilizers such as heat stabilizers, antioxidants, and ultraviolet absorbers is not particularly limited.

As a stabilizer such as a heat stabilizer, an antioxidant and an ultraviolet absorber, a conventionally known stabilizer can be used as it is. For example, phenol type, organic phosphate type,
It is possible to employ various heat stabilizers such as organic phosphite-based, organic amine-based, organic sulfur-based, antioxidants, and ultraviolet absorbers. The addition amount of the heat stabilizer, the antioxidant, the ultraviolet absorber and the like is generally 0.001 to 10 parts by weight based on 100 parts by weight of the cyclic conjugated diene polymer. As the polymerization terminator, known polymerization terminators that deactivate the polymerization active species of the polymerization catalyst of the present invention can be adopted. Water and carbon number 1 are preferred.
Examples thereof include alcohols, ketones, polyhydric alcohols (ethylene glycol, propylene glycol, glycerin, etc.) of 10 to 10, phenols, carboxylic acids, halogenated hydrocarbons and the like. The addition amount of the polymerization terminator is generally 0. 0 with respect to 100 parts by weight of the cyclic conjugated diene polymer.
Used in the range of 001 to 10 parts by weight. The polymerization terminator may be added before adding a stabilizer such as a heat stabilizer, an antioxidant, or an ultraviolet absorber, or may be added simultaneously with a stabilizer such as a heat stabilizer, an antioxidant, or an ultraviolet absorber. May be.
Further, it may be deactivated by bringing molecular hydrogen into contact with the active end of the polymer.

The most preferred method for producing the polymer of the present invention is to carry out a polymerization reaction to synthesize a cyclic conjugated diene polymer,
Then, hydrogenation is carried out if necessary, and a hydrocarbon residue having a reaction active group is added. More specifically, the polymerization reaction of the cyclic conjugated diene polymer achieves a predetermined polymerization rate (hydrogenation is carried out if necessary), and an addition reaction for adding a hydrocarbon residue having a reactive group is carried out. By carrying out the method, a polymer having a hydrocarbon residue having a reaction active group is produced. For example, a method in which the polymerization reaction is stopped by deactivating the polymerization catalyst, and the addition reaction is carried out batchwise in the same reactor in which the polymerization reaction was carried out. A method in which the polymerization reaction is stopped by deactivating the polymerization catalyst, the polymer solution is transferred to a reactor separate from the polymerization reaction, and the addition reaction is performed in a separate reactor in a semi-batch manner. It is possible to exemplify a method of continuously producing a polymer by continuously performing a polymerization reaction and an addition reaction in a tube reactor. These methods can be appropriately selected and adopted according to the purpose and need.

The reactive groups in the present invention are 1) UV
Irradiation 2) Electron beam irradiation 3) Reaction with inorganic substances 4) Reaction with water 5) Other chemical reactions (transesterification, hydrazone formation, hydrazide formation, oxime formation, ammonium salt formation, etc.)
It is a functional group capable of forming a crosslinked structure by reacting with itself or the crosslinking agent (Z) or other coexisting components present under the conditions such as. Specifically, for example, cyclodienyl group of C ₄ -C _20, a thiol group, a carboxyl group, an acid anhydride-containing group, hydrazinocarbonyl group, amino group, hydroxyl group, epoxy group, imino group, isocyanate group, a sulfonic acid group , Ester group, silyl group, siloxy group, vinyl group, methylol group, oxazoline group, silanol group, silyl ether group, silyl ester group, ether group (epoxy group etc.),
A carbonyl group, a formyloxy group, an imide group, an acetoxy group, an alkoxysilane group, an oxazoline group, or a C ₁ -C ₂₀ alkyl group to which any of these is bonded, C ₂ -C
₂₀ unsaturated aliphatic hydrocarbon groups, C _{3 to} C ₂₀ cycloalkyl groups, C _{5 to} C ₂₀ aryl groups, C _{4 to} C ₂₀ cyclodienyl groups, or organic compound residues containing any of these Etc. can be mentioned. More preferably, silyl group, siloxy group, silanol group, silyl ether group,
A silyl ester group, an epoxy group, a vinyl group, or a C ₁ -C ₂₀ alkyl group having any of these bonded thereto, C ₂ -C
₂₀ unsaturated aliphatic hydrocarbon groups, C _{3 to} C ₂₀ cycloalkyl groups, C _{5 to} C ₂₀ aryl groups, C _{4 to} C ₂₀ cyclodienyl groups, or organic compound residues containing any of these Etc. can be mentioned.

The reaction-active group-containing polymer of the present invention is achieved by adding the reaction-active group by a conventionally known reaction using a conventionally known reaction reagent. For example,
Oxidation reaction, hydration reaction, amination reaction, epoxidation reaction,
Halohydrination reaction, silylation reaction, carbonylation reaction (oxidative and reductive), dehydration reaction, dehydrohalogenation reaction, iminization reaction, radical addition reaction (radical, anion, cation), acetalization reaction, carboxylation reaction It is possible to employ one kind or two or more kinds of reactions selected from among them in an appropriate combination. Examples of the reactive agent for introducing the above reactive group include the following.

(I) Unsaturated carboxylic acid and its derivative Specifically, acrylic acid, methacrylic acid, maleic acid,
Itaconic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, mesaconic acid, sorbic acid maleic acid,
Itaconic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, mesaconic acid, sorbic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.2.1] hept-5-ene 2,3 dicarboxylic acid ( Nadic acid R), methyl-endocis-bicyclo [2.2.1] hept-5-ene 2,3 dicarboxylic acid (methyl nadic acid ^R ), (meth) acrylic acid metal salt, methyl (meth) acrylate, (meth) Ethyl acrylate, dimethyl maleate, diethyl maleate, dimethyl succinate, diethyl succinate, dimethyl fumarate, diethyl fumarate, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, succinic anhydride, itaconic anhydride, Citraconic anhydride, fumaric anhydride, hymic acid anhydride, crotonic acid anhydride, mesacon anhydride Acid, sorbic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleimide, succinimide, phthalimide, (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth) acrylic acid iodide, maleic acid chloride, itaconic acid Chloride, citraconic acid chloride, fumaric acid chloride, hymic acid chloride, crotonic acid chloride, mesaconic acid chloride, sorbic acid chloride, maleic acid bromide, itaconic acid bromide, citraconic acid bromide, fumaric acid bromide, hymic acid bromide, crotonic acid bromide, Mesaconic acid bromide, sorbic acid bromide,
Tetrahydrophthalic acid bromide, methyltetrahydrophthalic acid bromide, maleic acid iodide, itaconic acid iodide, citraconic acid iodide, fumaric acid iodide, hymic acid iodide, crotonic acid iodide, mesaconic acid iodide, sorbic acid iodide, tetrahydrophthalic acid iodide, methyl tetrahydrophthalic acid iodide Phthalic acid iodide maleimide, succinimide, phthalimide, (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth)
Unsaturated carboxylic acids such as acrylic acid iodide and their esters, acid anhydrides, metal salts, amides, imides and acid halides can be mentioned. It is also possible to carry out carbonylation using carbon monoxide, carbon dioxide, carboxylation or esterification in the presence of alcohol, amidation in the presence of amine, and dehydration by dehydration under various conditions using a catalyst.

(Ii) Epoxy-containing compound Specifically, it is an unsaturated epoxy compound having one or more unsaturated bonds and one or more epoxy groups in the molecule.

[0058]

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[In the formula, R ⁴ represents an organic compound residue having an unsaturated bond. ] Unsaturated glycidyl esters represented by, and

[0060]

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[Wherein, R ⁴ represents an organic compound residue having an unsaturated bond, and X ¹ represents —CH ₂ —O— or

[0062]

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Represents an ether residue represented by ] Unsaturated glycidyl ethers represented by, and

[0064]

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[In the formula, R5 represents hydrogen or an alkyl group, and represents an organic compound residue having an R6 unsaturated bond. ] The alkenyl epoxys represented by these can be illustrated. More specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, mesaconic acid, sorbic acid maleic acid, itaconic acid, citraconic acid, fumaric acid, hymic acid, Crotonic acid, mesaconic acid, sorbic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.2.1] hept-5-ene 2,3 dicarboxylic acid (nadic acid R), methyl-endocis-bicyclo [2.2] .1] Mono- and diglycidyl esters of unsaturated carboxylic acids such as hept-5-ene 2,3 dicarboxylic acid (methyl nadic acid ^R ), mono-, di- and triglycidyl esters of butenetricarboxylic acid, styrene-p-glycidyl Ether, 3,4-epoxy-1-
Butene, 3,4-epoxy-3 methyl-1-butene,
3,4-epoxy-1-pentene, 3,4-epoxy-
Examples thereof include 3-methyl-1-pentene and 5,6-epoxy-1-hexene. Further, the epoxy group can be bonded using oxygen, hydrogen peroxide, chlorine water or the like.

(Iii) Organosilicon Compound Specifically, it is an organosilicon compound having one or more saturated bond, unsaturated bond and any other functional group in the molecule. More ^{specifically, R 7 R 8 SiY 1 Y} 2, R 7 X 2 SiY 1 Y 2, R 7 SiY 1 Y 2 Y 3, SiY 1 Y 2 Y 3 Y 4, X 2 SiY 1 Y 2 Y 3 , X ² X ³ SiY ¹ Y ² , or X ³ X ³ X ⁴ SiY ¹ [wherein, R ⁷ and R ⁸ each independently represent an unsaturated organic compound group. Further, X ² , X ³ and X ⁴ each independently represent a residue selected from hydrogen, halogen and a saturated organic compound group. Furthermore, Y ¹ , Y ² and Y ³ each independently represent a functional group other than the unsaturated organic compound. Specific examples of R ⁷ and R ⁸ include vinyl, (meth) acrylic, butenyl, hexenyl, cyclohexenyl, cyclopentadienyl, octenyl, and the like.
Of these, a terminal olefinically unsaturated bond is particularly preferable. On the other hand, as another preferred example, CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ -CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ —O— having a terminal unsaturated acid ester bond. _{(CH 2) 3 - CH 2} = C (CH 3) COO (CH 2) 3 OCH 2 CH (OH) C
An unsaturated organic compound group such as H ₂ O (CH ₂ ) ₃ − may be mentioned. Among these unsaturated organic compound groups, the vinyl group is particularly preferable.

Specific examples of X ² , X ³ and X ^{4 in} the above organosilicon compound are selected from hydrogen, halogen, and C _{1 to} C ₂₀ hydrocarbon groups, or halogen-substituted hydrocarbon groups. Residues can be mentioned. Furthermore, Y ¹ , Y ² and Y in the above organosilicon compound
³ represents a functional group other than an unsaturated hydrocarbon group, each independently an alkoxy group such as methoxy, ethoxy, butoxy, and methylethoxy, or alkyl (aryl)
Alkoxy, formyloxy, acetoxy, acyloxy group or _{-ON = C (CH 3) 2} , -ON = CHCH 2 C 2 H 5, and _{-ON = C (C 6 H 5} ) 2 or the like of the oxime group, such as propionoxy Alternatively, an amino group such as —NH ₂ , —NHCH ₃ , and —NHC ₂ H ₅ —NH (C ₆ H ₅ ), a substituted amino group, a substituted aminoaryl group, and the like can be given.

Of these, particularly preferred is the general formula R
⁷ SiY ¹ is an organic silicon compound represented by Y ² Y ^3, as industrially most preferred organosilicon compounds used, vinyltrimethoxysilane, vinyltriethoxysilane,
Such as vinyltris (methoxyethoxy) silane and other vinyltrisalkoxysilanes, γ- (meth) acroyloxypropyltrialkoxysilane, vinylethyldiethoxysilane, vinylphenyldimethoxysilane, trichlorosilane, dimethylchlorosilane, methyldichlorosilane, etc. Alkoxysilanes such as halogenated silanes, trimethoxysilane, triethoxysilane, methyldiethoxysilane methyldimethoxysilane and phenyldimethoxysilane, acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane, bis (dimethylketoxysilane) Examples thereof include ketoxymate silanes such as mate) methylsilane and bis (cyclohexylketoximate) methylsilane, and products obtained by polymerizing these silanes. In the method for introducing a reaction active group into a polymer containing a cyclic molecular structural unit having a reaction active group of the present invention, the amount of the reaction reagent added is such that the kind of the reaction reagent or the reaction active group is imparted to the polymer containing a cyclic molecular structural unit. The number of reactive groups (J) varies depending on the reaction conditions at the time and the target addition amount.
Is appropriately adjusted so that is within the range of 1 ≦ J ≦ 4. In addition,
The above reaction reagents may be used alone or in combination of two or more.

As a method for introducing a reactive group into the polymer containing a cyclic molecular structural unit using a reactive agent according to the present invention, any conventionally known technique is not particularly limited, but preferable introduction is preferable. As the method, the cyclic molecular structural unit-containing polymer and the reaction reagent are dissolved in a suitable solvent and reacted in the presence of a radical initiator, the cyclic molecular structural unit-containing polymer and the reaction reagent. And a method of blending a radical initiator and reacting in a molten state,
Alternatively, a method in which the cyclic molecular structural unit-containing polymer and the reaction reagent are blended, and the cyclic molecular structural unit-containing polymer is swollen by using a suitable solvent as necessary, heated, and reacted by electron beam / ultraviolet irradiation. Etc. can be illustrated.
Examples of the radical initiator according to the present invention include organic peroxides and azo compounds that generate radicals upon thermal decomposition. Particularly preferably, the temperature at which the half-life time of the thermal decomposition reaction is 1 minute is 120. An organic peroxide having a temperature of (° C.) or higher, specifically, benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-
2.5-di (tert-butylperoxy) hexane, 2,
5-dimethyl-2,5-di (tert-butylperoxy)
Hexine 3, 1.3-bis (tert-butylperoxyisopropyl) benzene, 1.4-bis (tert-
Butyl peroxyisopropyl) benzene, di-tert-
Butyroperoxide, cumene hydroperoxide,
Examples thereof include tert-butyl perbenzoate.

[0070] Also, "CATALYSIS OF ORGANIC REACTIONS"
William R Moser (1981) Marcel clekker Inc / New Yor
k basel, "Homogeneous Catalyst" BJ Luberoff (196
8) American chemical Society Publications "Synthesis reactions using organometallic compounds (top) (bottom)" Takeo Saegusa, Yoshihiko Ito, Makoto Kumada (1975) of olefins or halides using metal catalysts as seen in Maruzen Publishing Utilizing a modification reaction, the cyclic molecular structural unit-containing polymer is dissolved in a suitable solvent, carbon monoxide alone in the presence of a metal catalyst or a method of performing carbonylation modification in the presence of an oxidizing agent,
A method of carrying out a carboxylation modification by reacting the polymer with carbon dioxide in the presence of a catalyst, a method of carrying out an esterification modification by allowing an alcohol to coexist in these reaction systems, and amidation modification by changing an alcohol to an amine. Examples thereof include a method of carrying out the method and a method of modifying the acid anhydride by dehydration. Further, it is also possible to carry out a modification such as carboxylation, esterification, amidation or imidation by the same reaction using a modified product (for example, a halide) of the polymer. Having a reactive group which is one of the polymers of the present invention,
And, a preferred method for producing a cyclic molecular structural unit-containing polymer having a saturated cyclic molecule is an addition reaction to a carbon-carbon double bond of a cyclic conjugated diene-based polymer, and a carbon-carbon double bond is obtained by carrying out the reaction. This is an addition reaction in which the bond is saturated to form a carbon-carbon single bond, and the carbon-carbon double bond may be present in either a cyclic conjugated diene monomer or a chain conjugated diene monomer. Specifically, in addition to the above reaction, a usual addition reaction is used. For example, water, an amino acid, a carboxylic acid group, a hydrosilyl group, chlorine water, and a reagent having active hydrogen such as a derivative thereof in the presence of a catalyst or A method of reacting in the absence of denaturation and denaturing can be mentioned.
As a catalyst for modification with water, an amino group, a carboxylic acid group, and chlorine water, an ordinary acid can be used, and an inorganic solid catalyst such as zeolite, an ion exchange resin such as a fluorinated sulfonic acid resin, an inorganic Examples thereof include a systemic mineral acid, a homogeneous catalyst such as trifluoromethanesulfonic acid, and a Lewis acid catalyst such as silica and alumina. The reaction method may be any of normal pressure, increased pressure, and reduced pressure, and can be changed depending on the type of reactor or reaction reagent. The reaction temperature is from room temperature to about 300 ° C. and may be appropriately selected depending on the situation. More specifically, the polymer of the present invention may be dissolved in a suitable solvent, a catalyst may be added thereto, and water, amine, carboxylic acid, chlorine water, etc. which generate a reactive group may be added and heated.

When introducing a silyl group, the reaction can be carried out under the same conditions as described above, but it is necessary to use a noble metal, especially a platinum-based catalyst, as a catalyst. The preferred catalyst is
Chloroplatinic acid, [PtCl ₂ (C ₂ H ₄ ) ₂ ], [PtCl
₂ (py) (C ₂ H ₄ )], [PtCl ₂ (PEt ₃ ) ₂ ],
[Pt (PPh ₃ ) ₂ (C ₂ H ₄ )], [Pt (PPh ₃ ) ₂ (C ₂ H ₄ )]
h _{3) 4],} it can be mentioned _{[Pt (C 2 H 4) 2} Si 2 (O) (CH 3) 4 ] (py represents pyridine). More specifically, the polymer of the present invention is dissolved in a suitable solvent, placed in an autoclave, charged with a platinum catalyst and a silylation reagent (eg, methyldichlorosilane), and heated to about 130 ° C.
By stirring for about an hour, the desired reactive group can be introduced. Further, a cyclic or chain olefin, a halide, a carbonyl compound, an epoxy compound, a silane compound or the like is further reacted with the polymer having these reactive groups in the presence or absence of a catalyst to introduce a reactive group. It is also possible to do so. The number (J) of reaction-active groups in the present invention can be shown by the number satisfying 1 ≦ (J) ≦ 4 in one molecule of the polymer. That is, (J) means the number of moles in 1 mole of the polymer. The number of reactive groups in one molecule is 1
When the amount is less, the curing becomes insufficient, and when the amount of the reactive groups is more than 4, the curing rate is remarkably increased and control is difficult, and the moldability of the resin after curing is lost, so that it is not suitable as an industrial material. , Not worth the use. In the addition reaction of the present invention, in order to separate and recover the polymer of the present invention from the polymer solution, a conventionally known technique that is usually used when recovering a polymer from a polymer solution of a known polymer is used. Can be adopted. For example, a steam coagulation method of directly contacting the reaction solution with steam, a reprecipitation method of adding a poor solvent for the polymer to the reaction solution to precipitate the polymer, a method of heating the reaction solution in a container to distill off the solvent Examples of the method include pelletizing while distilling off the solvent with a vented extruder, and an optimal method can be adopted depending on the properties of the cyclic conjugated diene polymer and the solvent used.

The polymer having a saturated cyclic molecule of the present invention is
Depending on its purpose and application, it can be used as a single material or as a composite material of other polymer material (including cyclic conjugated diene polymer), inorganic material, inorganic reinforced material / organic reinforced material. . The resin other than (X) which is the component (Y) in the resin composition of the present invention can be selected from conventionally known organic polymers as necessary,
There is no particular limitation on the type and amount. For example, nylon 4, nylon 6, nylon 8, nylon 9, nylon 1
0, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, nylon 636, nylon 1212, nylon 4T (T: terephthalic acid), nylon 4I
(I: isophthalic acid), nylon 6T, nylon 6I,
Nylon 12T, Nylon 12I, Nylon MXD6
(MXD: metaxylylenediamine) and other semi-aromatic polyamides, copolymers thereof, polyamide polymers such as blends, polybutylene terephthalate (PBT), polyethylene terephthalate (PET),
Polycarbonate (PC), Polyarylate (PAR)
Polyester polymer such as polypropylene, polypropylene (P
P), polyethylene (PE), ethylene-propylene rubber (EPR), polystyrene (PSt) and other olefin polymers, polybutadiene (PBd), polyisoprene (PIp), styrene-butadiene rubber (SBR),
Or conjugated diene-based polymers such as hydrides thereof,
Thiol-based polymers such as polyphenylene sulfide (PPS), ether-based polymers such as polyacetal (POM) and polyphenylene ether (PPE), or acrylic resins, ABS resins, AS resins, polysulfones (PSF), polyether ketones (PEK) , Polyamideimide (PAI) and the like. These organic polymers may be one kind or a mixture / copolymer of two or more kinds as necessary.

Further, as the inorganic reinforcing material, glass fiber, glass wool, carbon fiber, talc, mica, wollastonite, kaolin, montmorillonite, titanium whiskers, rock wool, etc., as the organic reinforcing material, aramid, polyimide, liquid crystal polyester ( L
CP), polybenzimidazole, polybenzothiazole, and the like. Furthermore, examples of the inorganic material include cement, sand, stone, and the like, and metals such as iron and aluminum can also be used together. The amount of (X) and (Y) constituting the resin composition of the present invention is 0.01 wt% ≦ Y ≦ 9 based on the total weight of (X) and (Y).
9.9 wt%, preferably ~. The cross-linking agent used as the Z component of the present invention is (1) an amino resin obtained by addition-condensing formaldehyde or alcohol to an amino compound such as melamine, benzoguanamine or urea, particularly a completely alkylated melamine resin or a partially alkylated melamine resin. (2) Resol type resin obtained by reacting phenol with aldehyde in the presence of alkali, (3) polyisocyanate,
Isocyanates such as blocked isocyanates,
(4) Primary, secondary, tertiary amines, (5) polycarboxylic acids, acid anhydrides, (6) epoxy compounds, (7) alcohols, (8) vinyl compounds, (9) methylacrylamide glycolate Methyl ether, (10) acetoacetoxyethyl methacrylate, (11) hydroxy carbamate and the like can be mentioned. Further, assuming wet curing, water (humidity) and the like can be considered as the crosslinking agent.

Examples of the amino resin described in (1) include melamine formaldehyde resin, hexamethoxymethylmelamine, butylated melamine, methylated melamine, benzoguanamine, formoguanamine, acetoguanamine, and other triazine compounds, tetraalkoxymethyl glycouril, urea. Etc. Examples of the phenol resin described in (2) include mono-, di-, and trimethylolphenol, condensates thereof, and butyl ether compounds thereof. The isocyanates mentioned in (3) include 2,4- / 2,
6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, poly- (4,4'-diphenylmethane diisocyanate), m- / p-xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, phenol block isocyanate, ε-caprolactam blocked isocyanate, methyl ethyl ketoxime blocked isocyanate, active methylene compound blocked isocyanate, water-soluble blocked isocyanate and the like can be mentioned. The amines mentioned in (4) include polymethylene diamine,
Diethylenetriamine, bishexamethylenetriamine, polyetherdiamine, dimethylaminopropylamine, diethylaminopropylamine, 1,3-diaminocyclohexane, branched amine, amine having spiro ring, amine having piperazine ring, diaminodiphenylmethane, diaminodiphenylsulfone, 4,4'-
Bis (o-toluidine), m-phenylenediamine, N
-Methylpiperazine, morpholine, triethanolamine, dialkylaminoethanol, 1,4-diazacyclo (2,2,2) octane, benzyldimethylamine,
2,5-dimethyl-2,5-hexanediamine and the like can be mentioned.

The acid anhydrides mentioned in (5) include phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, maleic anhydride / styrene copolymer. And ethylene glycol bistrimellitate, m-carboxyphenyl-3,4-anhydride phenyldimethylsilane and the like. (6) Epoxy resin refers to a bisphenol A type epoxy resin in a narrow sense, but a phenolic epoxy in a broad sense,
It refers to many epoxy group-containing compounds such as glycidyl methacrylate copolymer, glycidyl ester of carboxylic acid, and alicyclic epoxy. For example, triglycidyl isocyanurate, 3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate, epoxidized melamine resin and the like can be mentioned. (7) Examples of alcohols include polyether polyol, polybutadiene glycol, polycaprolactone polyol, and tris (2-hydroxyethyl) isocyanurate. (8) Vinyl compounds include polyvinyl compounds such as divinylbenzene, polyallyl compounds such as diallyl phthalate, triallyl trimellitate and diethylene glycol bisallylcarbonate, various glycols such as ethylene glycol diacrylate, and polyols such as trimethylol propane. And a reaction product of (meth) acrylic acid, a reaction product of polyepoxide and (meth) acrylic acid, polyallyl glycidyl ether, triallyl isocyanurate, triallyl cyanurate, and the like.

The combination of the cyclic conjugated diene polymer after the introduction of the reactive group used in the present invention and the cross-linking agent is not particularly limited, and one kind or two or more kinds of the polymer and the cross-linking agent may be used in combination. It is also possible to mix and use it at an arbitrary ratio. (X) which constitutes the resin composition of the present invention,
The ratio of (Y) and (Z) is (X), (Y) and (Z).
0 wt% <X <100 wt%, 0
wt% ≦ Y <100 wt%, 0 wt% <Z <100 wt
%, Preferably ~. (X) component, (Y) component,
The order of mixing the three components of the component (Z) is not particularly limited. The method of blending the three components of the component (X), the component (Y), and the component (Z) is not particularly limited, and a method of solution mixing or a method of heating and melting can be used. The solvent used for the solution mixture may be a single or selected from halogen-substituted hydrocarbons such as dichloromethane, chloroform, trichloroethylene, and dichlorobenzene, halogen-substituted aromatic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene. A mixed solvent may be used.
The above resin composition dissolved in these solvents can be formed into a film by a casting method. As a shaping method other than the casting method, a usual method by heating and melting can be mentioned, and methods such as injection molding, transfer molding, extrusion molding and press molding can be used. The temperature at the time of heating and melting is selected in the range of not less than the glass transition temperature of the resin composition and not more than the curing start temperature. The method for curing the curable cyclic conjugated diene polymer resin composition of the present invention is arbitrary, and a method using heat, light, electron beam or the like can be adopted.

A radical initiator may be contained as a catalyst for the purpose of lowering the temperature during curing and promoting the crosslinking reaction. The preferred amount of the initiator is 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the sum of the components (X) and (Y) and (Z). Is the range. Typical examples of the radical initiator include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, t-butylcumyl peroxide, α, α′-bis. (T-Butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxoisophthalate, t-butyl Peroxybenzoate, 2, 2
-Bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyl Peroxides such as triphenylsilyl peroxide include, but are not limited to. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator. The temperature for curing by heating varies depending on the presence or absence of the initiator and its type, but the temperature is 100 ° C to 450 ° C, more preferably 15 ° C.
It is selected in the range of 0 ° C to 400 ° C. The time is about 30 seconds to 5 hours, more preferably about 1 minute to 3 hours. The degree of this curing reaction can be traced by a differential scanning calorimeter or infrared absorption spectroscopy.

In curing the composition of the present invention, a catalyst may or may not be used, but when it is used, alkyl titanate, organosilicon titanate, tin octylate, dibutyltin laurate, dibutyltin are used. Malate,
Known silanol condensation catalysts such as carboxylic acid salts such as dibutyltin phthalate and amine salts can be used. The catalyst is preferably used in an amount of 0 to 10% based on the polymer of the present invention. The curable cyclic conjugated diene polymer composition of the present invention may be used by blending an amount of a filler or an additive in a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. it can. The filler may be in the form of fiber or powder, glass fiber, aramid fiber, carbon fiber, boron fiber, ceramic fiber, asbestos fiber, carbon black, silica, alumina, talc, mica, glass beads, glass A hollow sphere etc. can be mentioned. The additives include antioxidants, heat stabilizers, antistatic agents, stabilizers such as UV absorbers, lubricants,
Nucleating agent, plasticizer, pigment, dye, colorant, anti-slip agent,
An anti-blocking agent, a release agent, another polymer material, a flame retardant, a flame retardant aid, etc. can be added. More specifically, fume silica, precipitated silica, silicic acid anhydride, hydrous silicic acid, carbon black and other reinforcing materials, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay clay, talc, titanium oxide, bentonite, organic bentonite, second oxide Fillers such as iron and zinc oxide can be used. These fillers can be selectively used depending on the physical properties required for the cured product. For example, when a high strength body is desired, fume silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, calcined clay, etc. are effective. And can be used in the range of 1 to 100 parts with respect to 100 parts of the polymer. When a high elongation product is desired, polymer 10 such as titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide is used.
2 to 100 parts may be used for 0 parts. You may use these fillers individually or in mixture of 2 or more types.

The polymer of the present invention can be used by mixing with a plasticizer. The usable plasticizer can be basically used if it is generally used, for example, dioctyl phthalate, dibutyl phthalate, butynyl phthalate and other phthalates, dioctyl adipate, isodecyl succinate, Dibasic acid esters such as dibutyl sebacate, diethylene glycol dibenzoate, glycol esters such as pentaerythritol ester, butyl oleate, fatty acid esters such as methyl acetylricinoleate, tricresyl phosphate,
One or more of phosphoric acid esters such as trioctyl phosphate and octyl diphenyl phosphate, epoxidized soybean oil, epoxy plasticizers such as benzyl epoxy stearate, chlorinated paraffin, and the like can be used in combination, and the amount thereof is used. It can be used in the range of 0 to 100 parts based on 100 parts of the polymer. The curable composition of the present invention can be either a one-part composition or a two-part composition, and when used as a two-part composition, it is filled with a component consisting of the polymer, filler and plasticizer of the present invention. It may be divided into an agent, a plasticizer, a condensation catalyst and a cross-linking agent and mixed at the time of use. When used as a one-pack composition, the polymer, filler, plasticizer, and condensation catalyst of the present invention may be thoroughly dehydrated and dried, mixed and stored in the absence of water. The curable cyclic conjugated diene-based polymer composition of the present invention,
Excellent industrial materials include plastics, thermoplastic elastomers, fibers, sheets, films, machine parts, food containers, packaging materials, tires, belts, insulating agents, adhesives, paints,
Not only can it be used as a modifier for other resins, but it can also be used as a base polymer for the field of construction and civil engineering, an admixture for cement, a resin for sealants, and a sealant for buildings, ships, automobiles, roads, etc. Also, it can be used alone or as a sealing composition or adhesive composition for glass, porcelain, wood, metal, resin by using a primer. Furthermore, it can be expected as a food packaging material or a cast rubber material. Further, it is also suitably used in fields of application that require functionality such as functional polymers, polymer catalysts, and separation membranes.

[0080]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, Production Examples and Reference Examples, but the present invention is not limited to these Examples. Production Example 1 <Preparation of Polymerization Catalyst> A known amount of tetramethylethylenediamine (TMEDA) was dissolved in a mixed solvent of cyclohexane / normal hexane = 9/1 (volume ratio) under a dry argon atmosphere. This solution was cooled and held at -10 ° C, and a predetermined amount of n-BuLi normal hexane was prepared so that TMEDA / n-butyllithium (n-BuLi) = 1/4 (mol ratio) in a dry argon atmosphere. The solution was added slowly to the polymerization catalyst TMEDA / n-B.
A uLi complex was obtained. <Polymerization Reaction-Cyclohexadiene Homopolymer> The inside of a 100 ml Schlenk tube that had been sufficiently dried according to a conventional method was replaced with dry argon. 3.00 g of 1,3-cyclohexadiene and 20.0 g of cyclohexane were injected into the Schlenk tube. Keeping the temperature of the solution at 30 ° C.,
A polymerization catalyst (complex compound) composed of -BuLi / TMEDA was added in an amount of 0.07 mmol in terms of lithium atom, and a polymerization reaction was performed for 4 hours in a dry argon atmosphere.

After completion of the polymerization reaction, a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol] was added to stop the reaction, and the polymer was further mixed with a large amount of methanol / hydrochloric acid mixed solvent. Was separated, washed with methanol, and vacuum dried at 80 ° C. to obtain a white polymer with a yield of 100%. The obtained cyclohexadiene homopolymer had a number average molecular weight (Mn) ^*) of 44,500 and a molecular weight distribution (Mw / Mn) of 1.07.
*) The polymer was dissolved in TBC (1,2,4-trichlorobenzene), and G. P. It is displayed as a standard polystyrene conversion value measured by the C (gel permeation chromatography) method.

Production Example 2 <Cyclohexadiene Homopolymer> The reaction was performed in the same manner as in Production Example 1 except that the reaction time was 1 hour, and the yield was 100% and Mn = 9200 and Mw / Mn = 1.03. A polymer was obtained. Production Example 3 <Cyclohexadiene / butadiene diblock copolymer> The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. Cyclohexane (2800 g) and 1,3-cyclohexadiene (60 g) were charged into an autoclave, and the polymerization catalyst (complex compound) obtained by the above method was added in terms of atoms to obtain 10.48 mmol of the polymerization catalyst in terms of lithium atoms.
Polymerization was carried out at 0 ° C. for 4 hours (step 1: cyclohexadiene homopolymer). Next, 280 g of butadiene was further added to this polymerization solution, and a polymerization reaction was performed at 60 ° C. for 30 minutes (step 2: cyclohexadiene / butadiene block copolymer). After completion of the polymerization reaction, heptanol was added to the autoclave to stop the polymerization reaction.
[Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. as a stabilizer was added to the polymer solution, and the solvent was desolvated according to a conventional method to obtain a viscous cyclohexadiene-butadiene diblock polymer. The number average molecular weight (Mn) of the obtained cyclohexadiene-butadiene diblock polymer was 47,500, and the molecular weight distribution (Mw / Mn) ^*) was 1.10 (polystyrene-equivalent molecular weight).

Production Example 4 <Cyclohexadiene / butadiene diblock copolymer> In the same manner as in Production Example 3, 2800 g of cyclohexane,
Polymerization catalyst (complex compound) obtained by the above method by charging 60 g of 1,3-cyclohexadiene into an autoclave
Is converted to atoms and the polymerization catalyst is converted to lithium atoms. 1
0.48 mmol was added and polymerization was carried out at 30 ° C. for 0.5 hours (step 1: cyclohexadiene homopolymer). Then, the polymerization solution was further mixed with butadiene 28
0 g was added and a polymerization reaction was carried out at 60 ° C. for 10 minutes (st
ep2: cyclohexadiene / butadiene block copolymer). After completion of the polymerization reaction, heptanol was added to the autoclave to stop the polymerization reaction. The same treatment as in Production Example 3 was carried out to obtain a cyclohexadiene / butadiene diblock copolymer having Mn = 5700 and Mw / Mn = 1.05.

Production Example 5 <Cyclohexadiene / butadiene triblock copolymer> A cyclohexadiene / butadiene diblock polymer was polymerized in the same manner as in Production Example 3, and then 1,3-cyclohexadiene was further added to this polymerization solution. 60 g is added and a polymerization reaction is carried out at 30 ° C. for 2 hours (step 3: cyclohexadiene / butadiene / cyclohexadient block polymer). After the completion of the polymerization reaction, a cyclohexadiene showing rubber elasticity was obtained through the same operation as in Production Example 3.
A butadiene / cyclohexadi-entry block polymer was obtained. The number average molecular weight (Mn) of the obtained cyclohexadiene-butadiene triblock polymer was 97,000.
0, the molecular weight distribution (Mw / Mn) ^*) was 1.05 (polystyrene-equivalent molecular weight).

Production Example 6 <Cyclohexadiene / butadiene triblock copolymer> A cyclohexadiene / butadiene diblock polymer was polymerized in the same manner as in Production Example 5, and then 1,3-cyclohexadiene was further added to the polymerization solution. Add 60 g and carry out polymerization reaction at 30 ° C for 0.5 hours (step
3: cyclohexadiene butadiene cyclohexadientry block polymer). After completion of the polymerization reaction, the same operations as in Production Example 5 were carried out to obtain a cyclohexadiene / butadiene / cyclohexadi entry block polymer.
The number average molecular weight (Mn) of the obtained cyclohexadiene-butadiene triblock polymer was 10,000, and the molecular weight distribution (Mw / Mn) ^*) was 1.01 (polystyrene-equivalent molecular weight).

Production Example 7 <Cyclohexadiene / styrene diblock copolymer> The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. Cyclohexane 2800 g, 1,3-cyclohexadiene 6
0 g was charged into an autoclave, and 10.48 mmol of the polymerization catalyst (complex compound) obtained by the above method was converted into an atom, and the polymerization catalyst was added in an amount of 10.48 mmol in terms of a lithium atom.
Polymerization was performed at 4 ° C. for 4 hours (step 1: cyclohexadiene homopolymer). Next, 280 g of styrene was further added to this polymerization solution, and a polymerization reaction was carried out at 70 ° C. for 20 minutes (step 2: cyclohexadiene / styrene diblock copolymer). After completion of the polymerization reaction, heptanol was added to the autoclave to stop the polymerization reaction. [Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. as a stabilizer was added to the polymer solution, and the solvent was desolvated according to a conventional method to obtain a cyclohexadiene / styrene diblock polymer. The resulting cyclohexadiene / styrene diblock polymer had a number average molecular weight (Mn) of 49,000 and a molecular weight distribution (Mw / M
n) ^*) was 1.12 (polystyrene-equivalent molecular weight).

Example 1 <Synthesis of trimethoxysilane-modified polycyclohexadiene> 0.75 parts by weight of trichlorosilane and 0.03 chloroplatinic acid based on 100 parts by weight of the cyclohexadiene homopolymer obtained in Production Example 1. By adding parts by weight (isopropanol solution: hereinafter abbreviated as IPA) to 200 cm ³ of toluene under a dry nitrogen atmosphere, the temperature is raised stepwise to 100 ° C. and reacted for 4 hours to obtain 4.5 mmol of silicon.
A polymer containing (J = 2) was obtained. The amount of silicon was estimated by extracting a part of the solution, removing unreacted trichlorosilane, and then titrating the amount of chloro groups with a 1N sodium hydroxide aqueous solution. Next, 200 cm ³ of methanol was added to this toluene solution, and the mixture was reacted under reflux of methanol to obtain trimethoxysilane-modified polycyclohexadiene (Si-PCHD1).

[0088]Example 2 <Trimethoxysilane modified polycyclohexadiene
Composition> Using the polymer obtained in Production Example 2, trichlorosilane
The same procedure as in Example 1 was repeated except that 3.6 g of orchid was used.
And containing 22 mmol (J = 2) of silicon.
Methoxysilane-modified polycyclohexadiene (Si-P
CHD2) was obtained. Example 3 <Allyl glycidyl ether modified polycyclohexadiene
Synthesis of cyclones> Cyclohexadiene homo obtained in Production Example 1
Allyl glycidyl ether for 100 parts by weight of polymer
0.61 parts by weight of 1,2,4-toluene in a dry nitrogen atmosphere.
Lichlorobenzene (TBC) 200 cm^ThreeAdd in
Heat to 120 ° C. and stir to dissolve completely. This solution
Diluted with 50% dioctyl phthalate of benzoyl peroxide
Product (Nyper BO: manufactured by NOF CORPORATION, Japan).
5 mmol was gradually added, and then 120 under nitrogen atmosphere.
The reaction was carried out at 0 ° C for 2 hours. Acetone / TBC after reaction
After repeated reprecipitation with
The corresponding allyl glycidyl ether was removed, and the
Allyl containing 5 mmol (J = 2.2) of poxy group
Glycidyl ether modified polycyclohexadiene (EP
-PCHD) was obtained. The amount of epoxy group is determined by this polymer
Was dissolved in TBC and then a catalytic amount of sodium methoxide
The ring-opening reaction is performed with methanol in the presence of hydroxy
It was measured by quantifying the ru group by the acetic anhydride method.

Example 4 <Synthesis of maleic anhydride-modified polycyclohexadiene> Cyclohexadiene homopolymer 10 obtained in Production Example 1
120 parts by weight of maleic anhydride to 0 parts by weight of 1,2,4-trichlorobenzene (TB
C) Add to 200 cm ³ and heat to 120 ° C. and stir to completely dissolve. Add 5 parts of benzoyl peroxide to this solution.
24 mmol of 0% dioctyl phthalate diluted product (Nyper BO, manufactured by NOF CORPORATION) was gradually added,
Then, the mixture was reacted at 120 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, reprecipitation was repeated with acetone / TBC, and then unreacted maleic anhydride was removed by heating under reduced pressure, and 2,6-ditertiarybutyl-4-methylphenol was used as a stabilizer to prepare cyclohexadiene homo. 0.5 parts by weight per 100 parts by weight of the polymer modified product was added by melt-kneading at 230 ° C. ^**) . **) For melt-kneading, a twin-screw extruder (2D20SH) is connected to a Labo Plastomill (30C150) manufactured by Toyo Seiki Co., Ltd. in Japan, and melt-extruded in a strand form at 230 to 280 ° C. and a rotation speed of 50 rpm. Pelletized using a cutter. (Identification of Maleic Anhydride Group in Maleic Anhydride Modified Polycyclohexadiene (M-PCHD1)) The maleic anhydride addition amount measured by titration of maleic anhydride modified polycyclohexadiene with sodium methylate is 0.7 wt% ( J = 2.3). Example 5 <Synthesis of maleic anhydride-modified polycyclohexadiene> Cyclohexadiene homopolymer 10 obtained in Production Example 1
2.5 parts by weight of maleic anhydride and 90% by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane diluted with 0 parts by weight (Perhexa 25B: Japan, NOF Co., Ltd.) in an amount of 0.25 parts by weight, and 3000 ppm of Irganox B215 as a stabilizer is further added, and the mixture is reacted under melt-kneading at a temperature condition of 180 to 290 ° C. to give an addition amount of 0.55 wt% (J = 2. . 32) was obtained. The amount of maleic anhydride added and the identification of the obtained maleic anhydride-modified polycyclohexadiene (M-PCHD2) were the same as in Example 4.

Example 6 <Synthesis of glycidyl methacrylate modified polycyclohexadiene> In the modification of the cyclohexadiene homopolymer carried out in Example 5, glycidyl methacrylate was used as a modifying agent instead of maleic anhydride. In the same manner as in Example 5, the addition amount is 1% (J = 3.4).
Glycidyl methacrylate-modified polycyclohexadiene (G-PCHD) of 6) is obtained. The glycidyl group was analyzed in the same manner as in Example 3.

Example 7 <Synthesis of maleic anhydride-modified polycyclohexadiene> 100 parts by weight of the cyclohexadiene homopolymer obtained in Example 4 was mixed with γ-methacryloyloxy-propyltrimethoxysilane (KBM-503). : Manufactured by Shin-Etsu Chemical Co., Ltd., Japan, 2.5 parts by weight and 2,
A mixture of 0.5 parts by weight of a 90% diluted product of 5-dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa 25B: manufactured by NOF CORPORATION) was used as a stabilizer. Add 3000 ppm of Irganox B215 and let it react under melt-kneading at a temperature condition of 180 to 290 ° C. Polymer with an addition amount of 1% (J = 3.69) (Si—CH
D) was obtained. Example 8 <Modification of cyclohexadiene / butadiene diblock copolymer> 0.7 parts by weight of trichlorosilane and 0.03 of chloroplatinic acid were added to 100 parts by weight of the cyclohexadiene / butadiene diblock copolymer obtained in Production Example 3. 20 parts by weight (IPA solution) of toluene under a dry nitrogen atmosphere
It was added to 0 cm ³ and the temperature was raised stepwise to 100 ° C. and reacted for 4 hours, whereby 4.8 mmol of silicon (J =
2.3) A containing polymer was obtained. The amount of silicon was estimated by extracting a part of the solution, removing unreacted trichlorosilane, and then titrating the amount of chloro groups with a 1N aqueous sodium hydroxide solution. Next, 200 cm ³ of methanol was added to this toluene solution, and the mixture was reacted under reflux of methanol to obtain a trimethoxysilane-modified cyclohexadiene-butadiene diblock copolymer [Si-P (CHD-Bd) 1].

Example 9 <Modification of cyclohexadiene / butadiene diblock copolymer> Using the polymer obtained in Production Example 4, except that 5.8 g of trichlorosilane was used, a reaction was carried out in the same manner as in Example 8, Trimethoxysilane-modified cyclohexadiene-butadiene diblock copolymer containing 37 mmol (J = 2.1) of silicon [Si-P (CHD-B
d) 2] was obtained. Example 10 <Modification of cyclohexadiene / butadiene diblock copolymer> 0.58 parts by weight of allyl glycidyl ether was added to 100 parts by weight of the cyclohexadiene / butadiene diblock copolymer obtained in Production Example 3 under a dry nitrogen atmosphere. 1,2,4-Trichlorobenzene (TBC) 20
Add to 0 cm ³ and heat to 120 ° C. and stir to completely dissolve. To this solution, 0.5 mmol of a 50% dioctyl phthalate diluted product of benzoyl peroxide (Nyper BO: manufactured by NOF CORPORATION) was gradually added, and then reacted at 120 ° C. for 2 hours in a nitrogen atmosphere. It was After completion of the reaction, reprecipitation was repeated with acetone / TBC, and then unreacted allyl glycidyl ether was removed by heating under reduced pressure, and an epoxy group in the polymer was 4.8 mmol (J =
2.3) Containing allyl glycidyl ether-modified rhohexadiene / butadiene diblock copolymer [EP-
P (CHD-Bd) 1] was obtained. The epoxy group was quantified by dissolving this polymer in TBC, and then performing a ring-opening reaction with methanol in the presence of a catalytic amount of sodium methoxide.
It was measured by quantifying the hydroxyl group by the acetic anhydride method.

[0093]Example 11 <Cyclohexadiene / butadiene diblock copolymer
Modification> Cyclohexadiene obtained in Production Example 3
Based on 100 parts by weight of butadiene diblock copolymer
2.5 parts by weight of maleic anhydride and 2,5-dimethyl
9 of ru-2,5-di (t-butylperoxy) hexane
0% diluted product (Perhexa 25B: Nippon Oil & Fat)
(Manufactured by Co., Ltd.) in an amount of 0.2 parts by weight, and further as a stabilizer.
Add 3000 ppm of Irganox B215 and add 180
The reaction is performed under melt-kneading at a temperature of ~ 290 ° C, and the amount added
Of 0.7% (J = 3.38) modified with maleic anhydride
Rohexadiene / butadiene diblock copolymer [M
-P (CHD-Bd) 1] addition amount of maleic anhydride
The identification and identification are the same as in Example 4. Example 12 <Cyclohexadiene / butadiene diblock copolymer
Modification> Other than using the block copolymer of Production Example 4
In the same manner as in Example 10 except that maleic anhydride modified cyclo
Obtain hexadiene-butadiene diblock copolymer
Was. The amount of modification of this polymer is 2.6% (J = 1.51)
And this is designated as [MP (CHD-Bd) 2].Example 13 <Cyclohexadiene / butadiene diblock copolymer
Modification> Cyclohexadiene obtained in Production Example 3
In the modification of butadiene diblock copolymer, anhydrous
Modified glycidyl methacrylate instead of maleic acid
By the same operation as in Example 10 except that it is used as an agent
Addition amount of 0.63% (J = 2.11) methacrylate
Lysidyl-modified cyclohexadiene / butadiene diblock
Copolymer [GP (CHD-Bd)] is obtained.

Example 14 <Modification of cyclohexadiene / butadiene triblock copolymer> The cyclohexadiene / cyclohexanediene obtained in Production Example 5
0.35 part by weight of trichlorosilane and 0.1 part of chloroplatinic acid per 100 parts by weight of butadiene triblock copolymer.
2.4 parts of silicon was added by adding 03 parts by weight (IPA solution) to 200 cm ³ of toluene under a dry nitrogen atmosphere and gradually heating to 100 ° C. and reacting for 4 hours.
A polymer containing (J = 2.33) was obtained. The amount of silicon was estimated by extracting a part of the solution, removing unreacted trichlorosilane, and then titrating the amount of chloro groups with a 1N aqueous sodium hydroxide solution. Next, 200 cm ³ of methanol was added to this toluene solution, and the mixture was reacted under reflux of methanol to obtain a trimethoxysilane-modified cyclohexadiene-butadiene triblock copolymer [Si-P (CHD-Bd-CHD) 1]. It was Example 15 <Modification of cyclohexadiene / butadiene triblock copolymer> Using the polymer obtained in Production Example 6, a reaction was performed in the same manner as in Example 8 except that 3.3 g of trichlorosilane was used, and 25 mmol of silicon was used. (J = 2.5)
Contains trimethoxysilane-modified cyclohexadiene
Butadiene triblock copolymer [Si-P (CHD
-Bd-CHD) 2] was obtained. Example 16 <Modification of cyclohexadiene / butadiene triblock copolymer> Cyclohexadiene /
0.28 parts by weight of allyl glycidyl ether was added to 100 parts by weight of butadiene triblock copolymer under an atmosphere of dry nitrogen and 1,2,4-trichlorobenzene (TBC).
Add to 200 cm ³ and heat to 120 ° C. and stir to completely dissolve. Add 50% of benzoyl peroxide to this solution.
Dioctyl phthalate diluted product (Nyper BO: manufactured by NOF CORPORATION, Japan) was gradually added in an amount of 0.5 mmol, and then reacted in a nitrogen atmosphere at 120 ° C. for 2 hours. After the reaction was completed, after repeating reprecipitation with acetone / TBC,
Unreacted allyl glycidyl ether was removed by heating and decompressing, and 2.3 mmol (J
= 2.23) containing allyl glycidyl ether modified rhohexadiene butadiene triblock copolymer [EP-P (CHD-Bd-CHD) 1] was obtained. The epoxy group was quantified by dissolving the polymer in TBC, followed by ring-opening reaction with methanol in the presence of catalytic amount of sodium methoxide, and quantifying the hydroxyl group by acetic anhydride method.

Example 17 <Modification of cyclohexadiene / butadiene triblock copolymer> In modification of the cyclohexadiene / butadiene triblock copolymer obtained in Production Example 5, the addition amount was changed by the same operation as in Example 10. 0.2%
(J = 2.04) maleic anhydride-modified cyclohexadiene-butadiene triblock copolymer [MP
(CHD-Bd-CHD)] is obtained. Example 18 <Modification of cyclohexadiene / butadiene triblock copolymer> In modification of the cyclohexadiene / butadiene triblock copolymer obtained in Production Example 5, glycidyl methacrylate was used as a modifying agent instead of maleic anhydride. By the same operation as in Example 10 except that the glycidyl methacrylate-modified cyclohexadiene-butadiene triblock copolymer [GP (CHD-Bd-C) with an addition amount of 0.33% (J = 2.24) was used.
HD)] is obtained. Example 19 <Modification of cyclohexadiene / butadiene triblock copolymer> To 100 parts by weight of the cyclohexadiene / styrene diblock copolymer obtained in Production Example 7, 2.5 parts by weight of maleic anhydride and 2,5 9-dimethyl-2,5-di (t-butylperoxy) hexane
A 0% diluted product (Perhexa 25B: manufactured by NOF CORPORATION, Japan) was mixed in an amount of 0.2 parts by weight, and 3000 ppm of Irganox B215 was added as a stabilizer to obtain 180.
The reaction is carried out under melt-kneading at a temperature of 290 ° C to 290 ° C, and a maleic anhydride modified cyclohexadiene / styrene diblock copolymer [M-
The amount of maleic anhydride added and the identification of P (CHD-St)] are the same as in Example 4.

Production Example 8 <Hydrogenation of cyclohexadiene polymer> The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. Cyclohexane 2
Charge 800 g, 1,3-cyclohexadiene 60 g into an autoclave, and use the above-mentioned polymerization catalyst (complex compound) as an atomic conversion and the polymerization catalyst as a lithium atom conversion.
48 mmol was added and polymerization was carried out at 30 ° C. for 4 hours (cyclohexadiene homopolymer). After completion of the polymerization reaction, heptanol was added into the autoclave to stop the polymerization reaction. Co (acac) ₃ / TI was added to this polymer solution.
A hydrogenation catalyst consisting of BAL (triisobutylaluminum) = 1/6 was added to the polymer so as to be 50 ppm. The inside of the autoclave was replaced with hydrogen, the temperature was raised to 180 ° C., the hydrogen pressure was set to 35 kg / cm ² G, and the hydrogenation reaction was carried out for 4 hours. After the hydrogenation reaction, the autoclave was cooled to room temperature, the pressure was reduced to normal pressure, and then the inside was replaced with nitrogen. TIBAL was treated by adding methanol according to a conventional method. As a stabilizer in a polymer solution, manufactured by Ciba-Geigy, Switzerland [Irganox B215 (0037HX)]
Was added and the solvent was removed according to a conventional method to obtain a white powder of hydrogenated cyclohexadiene homopolymer. The hydrogenation rate of the cyclohexane ring calculated by ¹ H-NMR of the obtained polymer was 100%. Production Example 9 <Hydrogenation of cyclohexadiene / butadiene diblock copolymer> The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2720 g of cyclohexane and 150 g of 1,3-cyclohexadiene were charged into an autoclave, and the polymerization catalyst (complex compound) obtained in Production Example 1 was converted into an atom, and the polymerization catalyst was converted into a lithium atom of 15.36 mmol.
The mixture was added and polymerized at 30 ° C. for 6 hours (STEP 1: cyclohexadiene homopolymer). To this polymerization solution, 325 g of butadiene was added, and a polymerization reaction was carried out at 60 ° C. for 1 hour (STEP 2: cyclohexadiene / butadiene diblock copolymer). After completion of the polymerization reaction, this polymer solution was transferred into a 200 ml autoclave and titanocene dichloride (Cp ₂ TiCl ₂ / TIBAL = 1 /
A hydrogenation catalyst consisting of 6 is added to the polymer as a metal atom (Ti).
And 100 ppm are added, and a hydrogenation reaction is carried out in the same manner as in Production Example 8. The hydrogenation rate of the cyclohexane ring calculated by ¹ H-NMR of the obtained polymer was 0%,
The hydrogenation rates of 1,2-vinyl and 1,4-part of the butadiene part are 91.6% and 46.9%, respectively.

Production Example 10 <Hydrogenation of cyclohexadiene / butadiene triblock copolymer> In the same manner as in Production Example 9, after completion of the polymerization reaction, titanocene dichloride (Cp ₂ TiCl ₂ / TIB) was used.
A hydrogenation catalyst consisting of AL = 1/6 is added to the polymer in an amount of 100 ppm as a metal atom (Ti), and a hydrogenation reaction is carried out in the same manner as in Production Example 8. ¹ H-NM of the obtained polymer
Hydrogenation rate of cyclohexane ring calculated by R is 0%
The hydrogenation rates of 1,2-vinyl and 1,4-part of the butadiene part were 94% and 52%, respectively. Production Example 11 <Hydrogenation of cyclohexadiene / butadiene triblock copolymer> The amount of titanocene dichloride was 1000.
Hydrogenation was carried out in the same manner as in Production Example 10 except that the amount was 0 ppm. Cyclohexane ring calculated from ¹ H-NMR of the obtained polymer, 1,2-vinyl in the butadiene part, 1,
The hydrogenation rate of the 4-vinyl part was 100%. Production Example 12 <Hydrogenation of cyclohexadiene / styrene diblock copolymer> The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. Cyclohexane (2800 g) and 1,3-cyclohexadiene (120 g) were charged into an autoclave, and the polymerization catalyst (complex compound) obtained by the above method was added in terms of atom, and the polymerization catalyst was added in an amount of 13 mmol in terms of lithium atom.
Polymerization was carried out at 30 ° C. for 4 hours (step 1: cyclohexadiene homopolymer). Next, 280 g of styrene was further added to this polymerization solution, and a polymerization reaction was performed at 70 ° C. for 70 minutes (step 2: cyclohexadiene / styrene diblock copolymer). After completion of the polymerization reaction, heptanol was added to the autoclave to stop the polymerization reaction.
This polymer solution was transferred into a 200 ml autoclave, and Pd barium sulfate (BaSO ₄ ) supported type (5% P
d) A hydrogenation catalyst is added so as to be 200 wt% with respect to the polymer. Next, after replacing the inside of the autoclave with hydrogen and raising the temperature to 140 ° C., the hydrogen pressure is 50 kg / c.
The hydrogenation reaction is carried out for 5 hours as m ² . After completion of the hydrogenation reaction, after the hydrogenation reaction, the autoclave is cooled to room temperature,
After depressurizing to atmospheric pressure, the inside was replaced with nitrogen and used as a stabilizer by Ciba-Geigy [Irganox B215
(0037HX)] was added and the solvent was removed according to a conventional method to obtain a hydrogenated cyclohexadiene / styrene diblock polymer. The hydrogenation rate of the cyclohexane ring and the benzene ring calculated by ¹ H-NMR of the obtained polymer was 100%.

Example 20 The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. 2800 g of cyclohexane and 60 g of the modified polymer of Example 1 were charged into an autoclave, and Co (a) was added to the polymer solution.
cac) ₃ / TIBAL (triisobutylaluminum)
= 1/6 hydrogenation catalyst, 50 pp for polymer
m was added. The inside of the autoclave was replaced with hydrogen, the temperature was raised to 180 ° C., the hydrogen pressure was set to 35 kg / cm ² , and the hydrogenation reaction was carried out for 4 hours. After the hydrogenation reaction, the autoclave was cooled to room temperature, the pressure was reduced to normal pressure, and then the inside was replaced with nitrogen. Add methanol according to the usual method
IBAL was processed. The hydrogenation rate of the obtained polymer was 100% according to ¹ H-NMR. This hydrogenated polymer is referred to as (Si-HPCHE1: J = 2). Example 21 Hydrogenation was carried out under the same conditions as in Example 20 except that the polymer of Example 2 was used to obtain a polymer having a hydrogenation rate of 100%. This polymer was converted into (Si-HPCHE2: J =
2). Examples 22 to 25 Cp ₂ TiCl ₂ / TIBA was used as a hydrogenation catalyst using the polymers of Example 8, Example 9, Example 14, and Example 15.
Example 2 except that L = 1/6 was used at 10000 ppm
A hydrogenated polymer was obtained in the same manner as in 0. Each hydrogenated polymer was converted into [Si-P (CHE-EB) 1: J = 2.
2], [Si-P (CHE-EB) 2: J = 2.1],
[Si-P (CHE-EB-CHE) 1: J = 2.
3], [Si-P (CHE-EB-CHE) 2: J =
2.5].

Example 26 <Cyclohexadiene / methyl methacrylate diblock polymer> The inside of a 100 ml Schlenk tube which had been sufficiently dried by a conventional method was replaced with dry argon. 1,3-cyclohexadiene 1.50 g, cyclohexane 18.0
g and 2.0 g of normal hexane were injected into the Schlenk tube. The temperature of the solution is kept at 30 ° C., and the n-BuL
A polymerization catalyst (complex compound) composed of i / TMEDA was added in an amount of 0.07 mmol in terms of lithium atom, and a polymerization reaction was performed for 4 hours in a dry argon atmosphere. Next, this polymer solution is cooled to −10 ° C., 1.50 g of methyl methacrylate (MMA) is added, and a polymerization reaction is performed at −10 ° C. for 3 hours (cyclohexadiene / methyl methacrylate diblock polymer). ). After completion of the polymerization reaction, BHT [2,
6-bis (t-butyl) -4-methylphenol] 10
The reaction was stopped by adding a wt% methanol solution, and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid,
After washing with methanol, vacuum drying at 80 ° C, yield 81%
A white polymer was obtained. The obtained cyclohexadiene / methyl methacrylate diblock polymer had a number average molecular weight (Mn) ^*) of 34,500 and a molecular weight distribution (Mw / Mn) of 1.89.

Example 27 The polycyclohexane obtained in Production Example 8 was modified with maleic anhydride under the same conditions as in Example 4 (MP
CHE). The amount of added maleic anhydride measured by titration with sodium methylate of maleic anhydride hydrogenated cyclohexane homopolymer was 0.29 wt% (J =
1.4). Example 28 With respect to 100 parts by weight of polycyclohexane obtained in Production Example 8, 2.5 parts by weight of maleic anhydride and 2,5-
A 90% diluted product of dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa 25B: manufactured by NOF CORPORATION, Japan) was mixed in an amount of 0.5 part by weight, and Irganox was used as a stabilizer. Add 3000 ppm of B215 to 18
A polymer (J = 2.5) having an addition amount of 0.5% which was reacted under melt-kneading under a temperature condition of 0 to 290 ° C. was obtained. This is designated as (M-PCHE). Example 29 In the modification of polycyclohexane performed in Example 27, the addition amount was 0.8% (J = 2.77) glycidyl methacrylate modified polycyclohexane (G-PCH)
E) is obtained.

Example 30 To 100 parts by weight of polycyclohexane obtained in Production Example 8, 2.5 gamma-methacryloyloxy-propyltrimethoxysilane (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd., Japan) was used. Parts by weight and 2,5-dimethyl-2,
0.5 parts by weight of a 90% diluted product of 5-di (t-butylperoxy) hexane (Perhexa 25B: manufactured by NOF CORPORATION) was added, and 3000 ppm of Irganox B215 was added as a stabilizer. Then, the reaction is performed under melt kneading at a temperature condition of 180 to 290 ° C. (Si-PCHE:
J = 2.78). Example 31 Partially hydrogenated cyclohexadiene obtained in Production Example 9
To 100 parts by weight of butadiene diblock copolymer, 0.58 parts by weight of allyl glycidyl ether was added to 1,2,4-trichlorobenzene (TB) under a dry nitrogen atmosphere.
C) Add to 200 cm ³ and heat to 120 ° C. and stir to completely dissolve. Add 5 parts of benzoyl peroxide to this solution.
0.5 mmol of 0% dioctyl phthalate diluted product (Nyper BO: manufactured by NOF CORPORATION, Japan) was gradually added, and then reacted at 120 ° C. for 2 hours in a nitrogen atmosphere. After completion of the reaction, reprecipitation was repeated with acetone / TBC, and then unreacted allyl glycidyl ether was removed by heating under reduced pressure, and an epoxy group in the polymer was 4.9 m.
Allyl glycidyl ether modified partially hydrogenated cyclohexadiene / butadiene diblock copolymer [EP-P (CHD-EB) 1] containing 1 mol (J = 2.35)
I got In addition, this polymer was analyzed by TBC
After dissolution in, the ring-opening reaction was performed with methanol in the presence of a catalytic amount of sodium methoxide, and the hydroxyl group was measured by the acetic anhydride method.

Example 32 Partially hydrogenated cyclohexadiene obtained in Preparation Example 9
2.5 parts by weight of maleic anhydride and 9 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane per 100 parts by weight of butadiene diblock copolymer.
A 0% diluted product (Perhexa 25B: manufactured by NOF CORPORATION, Japan) was mixed in an amount of 0.2 parts by weight, and 3000 ppm of Irganox B215 was added as a stabilizer to obtain 180.
The reaction is carried out under melt kneading at a temperature of 290 ° C. The obtained addition amount of 0.43% (J = 2.08) maleic anhydride modified partially hydrogenated cyclohexadiene butadiene diblock copolymer anhydrous modified cyclohexadiene homopolymer [MP (CHD- The addition amount and identification of maleic anhydride in EB))] are the same as in Example 4. Example 33 Partially hydrogenated cyclohexadiene obtained in Production Example 9
Example 32 except that glycidyl methacrylate was used as the modifying agent instead of maleic anhydride in the modification of the butadiene diblock copolymer polycyclohexane.
By the same operation as above, the added amount is 0.58% (J = 1.9.
4) Glycidyl methacrylate-modified partially hydrogenated cyclohexadiene-butadiene diblock copolymer [G-
P (CHE-EB)] is obtained.

Example 34 In the modification of the partially hydrogenated cyclohexadiene butadiene triblock copolymer polycyclohexane obtained in Production Example 10, by the same method as in Example 31,
Allyl glycidyl ether modified partially hydrogenated cyclohexadiene-butadiene triblock copolymer [EP-P
(CHD-EB-CHD) 1: J = 2.12] is obtained. Example 35 In the modification of the partially hydrogenated cyclohexadiene / butadiene triblock copolymer polycyclohexane obtained in Production Example 10, the addition amount was 0.38% (J = 3.88) by the same operation as in Example 32. ) Maleic anhydride modified partially hydrogenated cyclohexadiene butadiene triblock copolymer [MP (CHD-EB-CH
D)] is obtained. Example 36 The same as Example 35 except that glycidyl methacrylate was used as a modifying agent in place of maleic anhydride in the modification of the partially hydrogenated cyclohexadiene / butadiene triblock copolymer obtained in Production Example 10. Glycidyl methacrylate modified partially hydrogenated cyclohexadiene butadiene triblock copolymer [GP (CHD) having an addition amount of 0.38% (J = 2.59) by operation.
-EB-CHD)] is obtained. Example 37 Using the hydrogenated cyclohexadiene-butadiene triblock copolymer obtained in Production Example 10, the addition amount was 0.13% (J = 1.3 by the same operation as in Example 5).
3) Water maleic acid modified hydrogenated cyclohexadiene
Butadiene triblock copolymer [MP (CHE-
EB-CHE)] is obtained.

Example 38 The same as Example 37 except that the hydrogenated cyclohexadiene / butadiene triblock copolymer obtained in Production Example 10 was used and glycidyl methacrylate was used as a modifier in place of maleic anhydride. Of 0.24% (J = 1.63) of glycidyl methacrylate modified partially hydrogenated cyclohexadiene butadiene triblock copolymer [GP (CHE-EB-CH
E)] is obtained. Examples 39 to 45 The curable resin composed of the cyclic conjugated diene polymer obtained in the above Production Examples 1 to 6 and Example 26 was electron beam cured by a cascade electron beam accelerator. Irradiation dose is 10 Mr
A cured product was obtained by irradiating an electron beam at room temperature in an ad, nitrogen atmosphere. At 23 ° C., the weight loss rate of the cured product before and after soaking in methanol, chloroform and 35% hydrochloric acid for 24 hours was measured and used as an index of chemical resistance. Table 1 shows the results. These resins are cured by electron beam irradiation, and the chemical resistance is remarkably improved as compared with the uncured product. Example 46 95 parts by weight of allyl glycidyl ether-modified polycyclohexadiene obtained in Example 3 and 5 parts by weight of ethylenediamine (hereinafter abbreviated as ED) as a cross-linking agent were dissolved in trichloroethylene to have a thickness of about 5 by a casting method. A film having a thickness of 100 μm was formed. The film forming property was excellent, and a film having a smooth surface was obtained. Eighteen of these were stacked, heated from room temperature to 200 ° C. by a vacuum press, held at 200 ° C. for 30 minutes, and then cooled to a thickness of about 1.
A 5 mm sheet-shaped cured product was obtained. At 23 ° C., the weight loss rate of the cured product before and after soaking in methanol, chloroform and 35% hydrochloric acid for 24 hours was measured and used as an index of chemical resistance. Table 2 shows the results.

Examples 47 to 52 Examples 4 to 6 and Examples 13, 18 and 29
Chemical resistance was determined in the same manner as in Example 46, except that the polymer obtained in (4) was used. Table 2 shows the results. Example 53 To 100 parts by weight of trimethoxysilane-modified cyclohexadiene obtained in Example 2, 20 parts by weight of chlorinated paraffin, 3 parts by weight of silicic acid anhydride and 2 parts by weight of dibutyltin malate were added and mixed well, and then mixed on a polyethylene film. Inject and
It was left at room temperature for 14 days to obtain a sheet-shaped cured body having a thickness of 2 mm. Methanol, chloroform, 35% at 23 ℃
After dipping in hydrochloric acid for 24 hours, the weight loss rate was measured and used as an index of chemical resistance. Table 3 shows the results. Examples 54 to 59 Chemical resistance was determined in the same manner as in Example 53 except that the polymers obtained in Examples 20 to 25 were used. Table 3 shows the results.

Comparative Examples 1 to 8 Using the cyclic conjugated diene polymers obtained in the above Production Examples 1 to 3 and 5 to 6 and 8 to 10 and the hydrides thereof, the same method as in the above Examples was used for chemical resistance. I investigated the sex. Table 4 shows the results. Comparative Example 9 Into a nitrogen-substituted 1 L autoclave with a stirrer was added 0.95 g of potassium hydroxide and 1.6 of 1,2-propanediol.
After adding 4 g and further adding 464 g of propylene oxide, the temperature was raised to 100 ° C. and the reaction was carried out for 15 hours.
0 polymer was obtained. To this solution, 11 g of metallic potassium was added and stirred at 80 ° C. for 2 hours, methylene chloride was added, and further reacted at 70 ° C. for 4 hours. Subsequently, 13 g of allyl chloride was added, and the reaction was carried out at 40 ° C. for 2 hours to obtain a molecular weight of 6
A polymer having an allyl ether group at the terminal of 900 was obtained. Next, this polymer was transferred to a reactor equipped with a stirrer, and 19.4 g of methyldichlorosilane and 13 ml of an isopropanol tetrahydrofuran solution of chloroplatinic acid (platinum chloride concentration = 6
(00 ppm) was added, the mixture was reacted at 90 ° C. for 3 hours, and methanol was further added to obtain a polymer having a methyldimethoxysilyl group. To 100 parts by weight of the obtained polymer, 20 parts by weight of chlorinated paraffin, 3 parts by weight of silicic acid anhydride, and 2 parts by weight of dibutyl tin malate were added and mixed well, poured on a polyethylene film, and allowed to stand at room temperature for 14 days to have a thickness of 2 mm. A sheet-shaped cured product of was obtained. This was immersed in methanol, chloroform, and 35% hydrochloric acid at 23 ° C. for 24 hours, and the weight loss rate was measured to be used as an index of chemical resistance. Table 4 shows the results.

Comparative Example 10 A maleic anhydride-modified cyclohexadiene butadiene diblock having an addition amount of 1.4% (J = 6.8) was prepared in the same manner as in Example 11 except that 5 parts by weight of maleic anhydride was used. A copolymer was obtained. A curable resin was synthesized from this polymer in the same manner as in Example 45, but the moldability was poor and a coating film could not be obtained. Comparative Example 11 A maleic anhydride-modified partially hydrogenated cyclohexadiene butadiene diblock copolymer having an addition of 1.4% (J = 14.3) was prepared in the same manner as in Example 17 except that 5 parts by weight of maleic anhydride was used. Got This polymer was used in Example 4
A curable resin was synthesized in the same manner as in Example 5, but the moldability was poor and a coating film could not be obtained. Comparative Example 12 A maleic anhydride-modified partially hydrogenated cyclohexadiene butadiene diblock copolymer having an addition of 1.0% (J = 9.9) was prepared in the same manner as in Example 35 except that 5 parts by weight of maleic anhydride was used. Got This polymer was used in Example 45.
A curable resin was synthesized in the same manner as, but the moldability was poor and a coating film could not be obtained.

Example 60 <Preparation of polymerization catalyst> A known amount of tetramethylethylenediamine (TMEDA) was dissolved in a mixed solvent of cyclohexane / normal hexane = 9/1 (volume ratio) under a dry argon atmosphere. This solution was cooled and held at -10 ° C, and a predetermined amount of n-BuLi normal hexane was prepared so that TMEDA / n-butyllithium (n-BuLi) = 1/4 (mol ratio) in a dry argon atmosphere. The solution was added slowly to the polymerization catalyst TMEDA / n-B.
A uLi complex was obtained. <Synthesis of base polymer> Sufficiently dried according to a conventional method 1
The inside of the 00 ml Schlenk tube was replaced with dry argon. 3.00 g of 1,3-cyclohexadiene and 20.0 g of cyclohexane were injected into the Schlenk tube. Keeping the temperature of the solution at 30 ° C., the n-BuLi / TMED
A polymerization catalyst (complex compound) consisting of A was added in an amount of 0.07 mmol in terms of lithium atom, and a polymerization reaction was carried out for 2 hours in a dry argon atmosphere. After the polymerization reaction, BHT
[2,6-Bis (t-butyl) -4-methylphenol] 10 wt% methanol solution was added to stop the reaction, and the polymer was separated with a large amount of a mixed solvent of methanol / hydrochloric acid and washed with methanol. After vacuum drying at 80 ° C., a cyclohexadiene homopolymer having a number average molecular weight (Mn) of 9200 and a molecular weight distribution (Mw / Mn) of 1.03 was obtained with a yield of 100%. Next, 0.75 parts by weight of methyldichlorosilane and 0.03 parts by weight of chloroplatinic acid were added to 100 parts by weight of this polymer under a dry nitrogen atmosphere with toluene 200c.
A polymer containing 22 mmol of silicon was obtained by adding to m ³ and gradually heating up to 100 ° C. and reacting for 4 hours. This amount of silicon corresponds to containing two silicons (J = 2) per polymer molecule. The amount of silicon was estimated by extracting a part of the solution, removing unreacted trichlorosilane, and then titrating the amount of chloro groups with a 1N aqueous sodium hydroxide solution. Next, 200 cm ³ of methanol was added to this toluene solution, and the mixture was reacted under reflux of methanol to give methyldimethoxysilane-modified polycyclohexadiene (Si-PCHD).
I got For the molecular weight and molecular weight distribution,
(1,2,4-trichlorobenzene) and dissolved in G.I.
It is expressed as a standard polystyrene conversion value measured by a PC (gel permeation chromatography) method.

<Hydrogenation of Base Polymer> The inside of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. Cyclohexane 2
800 g and Si-PCHD 60 g were charged into an autoclave, and Co (acac) ₃ / TIBAL was added to the polymer solution.
A hydrogenation catalyst consisting of (triisobutylaluminum) = 1/6 was added to the polymer at 50 ppm. The inside of the autoclave was replaced with hydrogen, the temperature was raised to 180 ° C., the hydrogen pressure was set to 35 kg / cm ² G, and the hydrogenation reaction was carried out for 4 hours. After the hydrogenation reaction, the autoclave was cooled to room temperature, the pressure was reduced to normal pressure, and then the inside was replaced with nitrogen.
TIBAL was treated by adding methanol according to a conventional method. [Irganox B215 (0037HX)] manufactured by Ciba-Geigy Co., Ltd. as a stabilizer was added to the polymer solution, and the solvent was desolvated by a conventional method to obtain methyldimethoxysilane-modified polycyclohexane (Si-PCHE1). The hydrogenation rate of the cyclohexane ring calculated by ¹ H-NMR of the obtained polymer was 100%. Example 61 Methyldimethoxysilane-modified polycyclohexane (Si-PCHE2: J = 2.
5) was obtained.

Example 62 The interior of a sufficiently dried 5 L high pressure autoclave equipped with an electromagnetic induction stirrer was replaced with dry nitrogen according to a conventional method. Cyclohexane 2800 g, 1,3-cyclohexadiene 60
10 g of the polymerization catalyst used in Example 1 was added to the autoclave in terms of lithium atom, and 10.48 mmol was added,
Polymerization was carried out at 30 ° C. for 30 minutes (step 1: cyclohexadiene homopolymer). Next, 280 g of butadiene was further added to this polymerization solution, and a polymerization reaction was performed at 60 ° C. for 10 minutes (step 2: cyclohexadiene / butadiene block copolymer). Next, 60 g of 1,3-cyclohexadiene is further added to this polymerization liquid, and a polymerization reaction is carried out at 30 ° C. for 0.5 hours (step 3: cyclohexadiene / butadiene / cyclohexadient block polymer). After completion of the polymerization reaction, heptanol was added to the autoclave to stop the polymerization reaction, and Mn = 1000
A cyclohexadiene butadiene cyclohexadi entry block polymer having an Mw / Mn of 1.01 was obtained. Next, with respect to 100 parts by weight of this polymer, 3.3 parts by weight of methyldichlorosilane and 0.03 part by weight of chloroplatinic acid were added to 200 cm ³ of toluene under a dry nitrogen atmosphere, and gradually added to 100 ° C. By raising the temperature and reacting for 4 hours, a polymer containing 20 mmol of silicon (J = 2) was obtained. This amount of silicon is 2 for one molecule of polymer.
Equivalent to containing individual pieces. Next, 200 cm ³ of methanol was added to this toluene solution, and the mixture was reacted under reflux of methanol to give a methyldimethoxysilane-modified cyclohexadiene-butadiene-cyclohexadiene block copolymer [Si-P (CHD-Bd-C
HD)] was obtained. Next, in the same autoclave as in Example 1, 2800 g of cyclohexane and 160 g of [Si-P (CHD-Bd-CHD)] were charged into the autoclave, and the polymer solution was added with Cp ₂ TiCl ₂ (titanocene dichloride) / TIBAL (tribal). Isobutyl aluminum)
= 1/6 of hydrogenation catalyst to polymer
It was added so as to be 0 ppm. The inside of the autoclave was replaced with hydrogen, the temperature was raised to 180 ° C, and the hydrogen pressure was 35 kg / c.
The hydrogenation reaction was carried out for 4 hours as m ² G. After the hydrogenation reaction, the autoclave was cooled to room temperature, the pressure was reduced to normal pressure, and then the inside was replaced with nitrogen. TIBAL was treated by adding methanol according to a conventional method. As a stabilizer in the polymer solution, manufactured by Ciba-Geigy, Switzerland [Irganox B2
15 (0037HX)] was added and the solvent was removed according to a conventional method to obtain methyldimethoxysilane-modified cyclohexane / hydrogenated butadiene / cyclohexane triblock copolymer [Si-P (CHE-EB-CHE)].
The hydrogenation rate of the cyclohexane ring and the butadiene portion of the obtained polymer calculated by ¹ H-NMR was 100%.

Example 63 To 100 parts by weight of the polymer obtained in Example 60, 20 parts by weight of chlorinated paraffin, 3 parts by weight of silicic acid anhydride and 2 parts by weight of dibutyl tin malate were added and mixed well, and the mixture was poured onto a polyethylene film. It was left at room temperature for 14 days to obtain a sheet-shaped cured body having a thickness of 2 mm. This was immersed in methanol, chloroform and 35% hydrochloric acid at 23 ° C. for 24 hours, and the weight loss rate was measured. Further, this test piece was put in a hot air dryer at 100 ° C. and its yellowing degree was measured. Table 5 shows the results. Examples 64 and 65 Chemical resistance was measured in the same manner as in Example 63 except that the polymers obtained in Examples 61 and 62 were used. Table 5 shows the results.

Production Example 13 <Cyclohexadiene / isoprene triblock copolymer> In the same manner as in Production Example 3, 2800 g of cyclohexane,
Polymerization catalyst (complex compound) obtained in Production Example 1 by charging 60 g of 1,3-cyclohexadiene into an autoclave
Is converted to atoms and the polymerization catalyst is converted to lithium atoms. 1
0.48 mmol was added and polymerization was carried out at 30 ° C. for 0.5 hour (step 1: cyclohexadiene homopolymer). Then, the isoprene 12 was added to the polymerization solution.
0 g was added and a polymerization reaction was carried out at 60 ° C. for 10 minutes (st
ep2: cyclohexadiene / isoprene diene block copolymer). Next, 60 g of 1,3-cyclohexadiene was further added to this polymerization solution, and a polymerization reaction was carried out at 30 ° C. for 0.5 hour (Step 3: cyclohexadiene / isoprene / cyclohexadient block polymer). After the completion of the polymerization reaction, heptanol was added to the autoclave to stop the polymerization reaction. The same treatment as in Production Example 3 was carried out to obtain a cyclohexadiene-isoprene triblock copolymer having Mn = 9800 and Mw / Mn = 1.02. Example 66 <Modification of cyclohexadiene-isoprene triblock copolymer> Using the polymer obtained in Production Example 13 and performing the reaction in the same manner as in Example 8 except that 3.5 g of trichlorosilane was used, 25 mmol of silicon ( J = 2.
5) Containing trimethoxysilane-modified cyclohexadiene-isoprene triblock copolymer [Si-P (C
HD-IP-CHD)] was obtained.

Example 67 Hydrogenation was carried out under the same conditions as in Example 20 except that the polymer of Example 66 was used to obtain a polymer having a hydrogenation rate of 100%. This polymer was converted into (Si-P (CHE-HI
PCHE) (: J = 2.5). Example 68 Evaluation was carried out in the same manner as in Example 53 using the polymer obtained in Example 67. As a result, the weight reduction rate in methanol: 0.09%, in chloroform 0.06%, 35
% Hydrochloric acid: 0.02%, indicating good chemical resistance.

[0114]Comparative Example 13 Hydroxylate in a 1 L autoclave with a stirrer that has been replaced with nitrogen.
0.95 g of potassium and 1.6 of 1,2-propanediol
4 g was added, and further 464 g of propylene oxide was added.
After that, the temperature is raised to 100 ° C. and the reaction is carried out for 15 hours.
0 polymer was obtained. Add 11 g of metallic potassium to this solution.
Stir at 80 ° C for 2 hours, add methylene chloride, and
The reaction was carried out at 70 ° C for 4 hours. Then 13g of allyl chloride
Molecular weight of 6 by adding and reacting at 40 ° C for 2 hours
A polymer having an allyl ether group at the end of 900 was obtained.
Was. Next, this polymer was transferred to a reactor equipped with a stirrer, and methyl
Chlorsilane 19.4g, chloroplatinic acid isopropanoate
13 ml of tetrahydrofuran solution (platinum chloride concentration = 6
(00 ppm) was added and reacted at 90 ° C. for 3 hours.
Addition of tanol to the poly (methyldimethoxysilyl) group
Got a remar. Chlorinated para was added to 100 parts by weight of this polymer.
20 parts by weight of fins, 3 parts by weight of silicic acid anhydride, dibutyl tin
Add 2 parts by weight of the rate and mix well, then add polyethylene fill
On the membrane and leave it at room temperature for 14 days.
A cured product was obtained. Methanol, chloro at 23 ℃
Measure the weight loss rate after immersing in 35% hydrochloric acid for 24 hours.
Specified. Put this test piece in a hot air dryer at 100 ° C.
Then, the degree of yellowing was measured. The results are shown in Table 5.

[0115]

[Table 1]

[0116]

[Table 2]

[0117]

[Table 3]

[0118]

[Table 4]

[0119]

[Table 5]

[0120]

EFFECT OF THE INVENTION The novel modified cyclic conjugated diene polymer according to the present invention is curable and has excellent thermal properties, and further, depending on the required thermal and mechanical properties. It is possible to copolymerize various monomers in any proportion and form, so plastics, thermoplastic elastomers, cross-links can be used alone or as a composite with other resin materials and inorganic materials depending on the purpose and application. Automotive parts, electric / electronic parts, useful industrial materials such as elastomers, fibers, sheets, films, tubes, tires, belts, insulators, organic glass, adhesives, food containers, packaging materials, and modifiers of other resins. It can be used for a wide range of applications such as parts, miscellaneous goods, food containers, packaging materials, medical instruments / parts, and civil engineering / construction fields.

[Brief description of the drawings]

1 is a ¹ H-NMR spectrum chart of trimethoxysilane-modified polycyclohexadiene obtained in Example 2 (in the figure, the position of each peak on the spectrum is indicated by a bar line). Point); and

FIG. 2 is a ¹ H—N of cyclohexadiene / isoprene triblock copolymer obtained in Example 67.
It is a MR spectrum chart figure (in the figure, the existing position of each peak on a spectrum is shown by the bar line).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 23/08 LCD C08L 23/08 LCD 45/00 LKB 45/00 LKB 53/00 LMA 53/00 LMA C09D 153/00 PGY C09D 153/00 PGY C09J 153/00 JDJ C09J 153/00 JDJ C09K 3/10 C09K 3/10 Z (31) Priority claim number Japanese Patent Application No. 7-191854 (32) Priority Day 7 (1995) July 27 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-192720 (32) Priority Day Hei 7 (1995) July 28 (33) Priority Claiming country Japan (JP)

Claims (21)

[Claims] 1. A curable resin having a polymer chain of at least one polymer represented by the following formula (1). Embedded image [Formula (1) represents the composition formula of the polymer. A to F represent monomer units constituting the polymer main chain, and A to F may be arranged in any order. a to f represent the respective wt% of the monomer units AF with respect to the total weight of the monomer units AF. The standard polystyrene equivalent number average molecular weight of the polymer is in the range of 1,000 to 5,000,000. (A): One or more monomer units selected from a cyclic olefin monomer unit having no reactive group. (B): One or more monomer units selected from cyclic conjugated diene monomer units having no reactive group. (C): One or more monomer units selected from chain conjugated diene monomer units having no reactive group. (D): One or more monomer units selected from vinyl aromatic monomer units having no reactive group. (E): One or more monomers selected from polar monomer units having no reactive group. (F): One or more monomer units selected from ethylene and α-olefin monomer units having no reactive group. A to F satisfy the following relationships. a + b + c + d + e + f = 100, 0 ≦ a, b ≦ 10
0,0 ≦ c, d, e, f <100, a + b ≠ 0. Q _{1 to} Q ₆ are reactive groups directly bonded to A to F, and may be the same or different. The total number (J) of Q _{1 to} Q ₆ contained in the polymer molecule is 1 ≦ (J) ≦
4. ] 2. Each of the reaction-active groups Q _{1 to} Q ₆ in the formula (1) is independently a C _{4 to} C ₂₀ cyclodienyl group, a thiol group, a carboxyl group, an acid anhydride-containing group, or hydrazinocarbonyl. Group, amino group, hydroxyl group, epoxy group, imino group, isocyanato group, sulfonic acid group, ester group, silyl group, siloxy group, vinyl group, methylol group, oxazoline group, silanol group, silyl ether group, silyl ester group, ether Group, an epoxy group, a carbonyl group, a formyloxy group, an imide group, an acetoxy group, an alkoxysilane group, an oxazoline group, or a C _{1 to} C ₂₀ alkyl group to which any of these is bonded, and a C _{2 to} C ₂₀ unsaturated fat. family hydrocarbon group, a cycloalkyl group of _{C 3 ~C 20, C 5 ~C} 20
The curable resin according to claim 1, wherein the aryl group, the C _{4 to} C ₂₀ cyclodienyl group, or an organic compound residue containing any of these. 3. The reaction-active groups Q _{1 to} Q ₆ in the formula (1).
Are each independently a functional group selected from a silyl group, a silyl ether group, a siloxy group, a silanol group or a silyl ester group or an organic compound residue containing the same, a vinyl group or an organic compound residue containing the same. The curable resin according to claim 2, which is a group, an epoxy group, or an organic compound residue containing the group. 4. The at least one polymer represented by formula (1) has a = 100.
The curable resin according to any one of 1 to 3. 5. The curable resin according to claim 1, wherein at least one polymer represented by the formula (1) has a + b = 100 and 0 <b. 6. The curable resin according to claim 1, wherein at least one polymer represented by the formula (1) has a + c = 100 and 0 <c. 7. At least one polymer of the formula (1) has 0.001 ≦ a + b <100 and 0.01 ≦
The curable resin according to claim 1, wherein a <100. 8. At least one polymer represented by the formula (1) is a + b + c = 100 and satisfies at least one condition of 0 <b and 0 <c. The curable resin according to any one of 3 above. 9. At least one polymer represented by the formula (1) is 0.01 ≦ a + b + c <100, and at least one condition of 0.1 ≦ a <100, 0 ≦ b and 0 <c is satisfied. The curable resin according to any one of claims 1 to 3, wherein 10. The curable resin according to claim 1, wherein at least one polymer represented by the formula (1) has b = 0 and c = 0. 11. The block copolymer according to claim 1, wherein the at least one polymer represented by the formula (1) is a block copolymer having a block unit containing at least one monomer unit A. The curable resin according to. 12. A sealing agent comprising the curable resin according to claim 1. 13. An adhesive comprising the curable resin according to claim 1. 14. A coating material comprising the curable resin according to claim 1. 15. A cement admixture comprising the curable resin according to any one of claims 1 to 11. 16. A resin composition comprising the resin (X) according to any one of claims 1 to 11 and a resin (Y) other than (X), the sum of (X) and (Y). For weight
A curable resin composition in which 0.01 wt% ≦ Y ≦ 99.9 wt%. 17. A resin composition comprising the resin (X) according to any one of claims 1 to 11, a resin (Y) other than (X), and one or more cross-linking agents (Z). There
0 wt with respect to the total weight of (X), (Y) and (Z)
A curable resin composition in which% ≦ Y <100 wt% and 0 wt% <Z <100 wt%. 18. A sealing agent comprising the resin composition according to claim 16 or 17. 19. An adhesive comprising the resin composition according to claim 16 or 17. 20. A coating material comprising the resin composition according to claim 16 or 17. 21. An admixture for cement, which comprises the resin composition according to claim 16 or 17.