JP7009920B2 - High resilience material - Google Patents

Description

The present invention relates to a high repulsion material made of a rubber crosslinked product obtained by using a cyclopentene ring-opening polymer, and more specifically, to be made of a rubber crosslinked product obtained by using a cyclopentene ring-opening polymer, and has an excellent rebound resilience. Regarding high resilience materials.

Conventionally, butadiene rubber has been widely used as a rubber material for forming various rubber parts. Butadiene, which is the raw material for butadiene rubber, is produced as a by-product in the production of ethylene by cracking naphtha. In recent years, the method of producing ethylene using natural gas such as ethane has expanded. Therefore, it is predicted that the production of butadiene will decrease. Therefore, various studies are underway to use synthetic rubber that does not use butadiene as a raw material as a substitute material for butadiene rubber.

As a kind of synthetic rubber being studied as an alternative material to butadiene rubber, there is a cyclopentene ring-opening polymer obtained by ring-opening polymerization of cyclopentene. For example, Patent Document 1 discloses a rubber composition for a tire containing a cyclopentene ring-opening polymer, a solution-polymerized styrene-butadiene rubber, and silica. According to the technique of Patent Document 1, although it is possible to provide a rubber crosslinked product having excellent low heat generation, the impact elastic modulus is not always sufficient, and therefore, it is suitable for tire applications requiring low heat generation. , It was not always suitable for applications that required a high elastic modulus.

International Publication No. 2016/060267

The present invention has been made in view of such an actual situation, and an object of the present invention is to provide a highly repulsive material having an excellent rebound resilience, which comprises a rubber crosslinked product obtained by using a cyclopentene ring-opening polymer. ..

As a result of diligent research to achieve the above object, the present inventors used a cyclopentene ring-opening polymer having a branched structure and contained a cyclopentene ring-opening polymer having such a branched structure. The present invention has been completed by finding that the above object can be achieved by using a rubber crosslinked product obtained by cross-linking a polymer composition obtained by blending a predetermined amount of carbon black with the rubber component.

That is, according to the present invention, a rubber obtained by cross-linking a polymer composition containing 20 to 200 parts by weight of carbon black with 100 parts by weight of a rubber component containing a cyclopentene ring-opening polymer having a branched structure. A high resilience material consisting of a crosslinked product is provided.

（上記式（I）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。）

（上記式（II）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。）

（上記式（III）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。）

（上記式（IV）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。） In the present invention, the cyclopentene ring-opening polymer having the branched structure starts from the branched structural unit represented by the following formula (I), the following formula (II), the following formula (III) or the following formula (IV). It is preferable to have a branched structure.

(In the above formula (I), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.)

(In the above formula (II), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.)

(In the above formula (III), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.)

(In the above formula (IV), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.)

Further, according to the present invention, the use of any of the above high-resilience materials as a high-resilience material used in an environment of 10 ° C. or lower is provided.

According to the present invention, it is possible to provide a high repulsion material which has an excellent rebound resilience and can be suitably used for applications requiring a high rebound resilience.

The high-resilience material of the present invention is a rubber obtained by cross-linking a polymer composition containing 20 to 200 parts by weight of carbon black with 100 parts by weight of a rubber component containing a cyclopentene ring-opening polymer having a branched structure. It consists of a crosslinked product.

The rubber component used in the present invention contains a cyclopentene ring-opening polymer having a branched structure. The cyclopentene ring-opening polymer having a branched structure used in the present invention contains a repeating unit obtained by ring-opening polymerization of cyclopentene as a repeating unit constituting the main chain, and has a branched structure in the main chain. It is a coalescence.

In the cyclopentene ring-opening polymer having a branched structure used in the present invention, the content ratio of the repeating unit obtained by ring-opening polymerization of cyclopentene is preferably 86 mol% or more, more preferably 92 mol% with respect to all the repeating units. The above is more preferably 95 mol% or more, and the upper limit thereof is preferably 99.99 mol% or less, more preferably 99.95 mol% or less, still more preferably 99.90 mol% or less.

Further, the cyclopentene ring-opening polymer having a branched structure used in the present invention preferably has a branched structural unit for introducing the branched structure into the polymer chain. The branched structural unit may be any structural unit derived from a monomer capable of ring-open copolymerization with cyclopentene and capable of forming a branched structure, and is not particularly limited, but is a ring having one double bond. A structural unit derived from a polycyclic diolefin compound having at least two structures, or a structural unit derived from a cyclic olefin compound having a ring structure having one double bond and a vinyl group is preferable.

By introducing a structural unit derived from a polycyclic diolefin compound having at least two ring structures having one double bond (hereinafter, appropriately referred to as “polycyclic diolefin compound”) as a branched structural unit. , A four-branched structure starting from such a structural unit can be introduced into the polymer chain. Further, as a branched structural unit, a structural unit derived from a cyclic olefin compound having a ring structure having one double bond and a vinyl group (hereinafter, appropriately referred to as “vinyl group-containing cyclic olefin compound”) is introduced. By doing so, a three-branched structure starting from such a structural unit can be introduced into the polymer chain. Among these, from the viewpoint that a tetracyclic diolefin structure can be introduced into the polymer chain, it is preferable to use a polycyclic diolefin compound and introduce a structural unit derived from the polycyclic diolefin compound. That is, as the cyclopentene ring-opening polymer having a branched structure used in the present invention, one having a four-branched structure is preferable, and by adopting one having a four-branched structure, the obtained rubber crosslinked product has a higher rebound resilience. Can be made.

上記式（１）中、Ｒ^１、Ｒ^２は、炭素数１～６のアルキレン基であり、ｎは０～２の整数であり、上記式（１）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。また、上記式（１）で表される化合物は、シクロペンテンと開環共重合した際に、上記式（１ａ）で表される分岐構造単位を与えることとなるものであり、上記式（１ａ）中、Ｒ^１、Ｒ^２、ｎは上記式（１）と同じであり、上記式（１ａ）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。

上記式（２）～（５）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。また、上記式（２）～（５）で表される化合物は、シクロペンテンと開環共重合した際に、それぞれ、上記式（２ａ）～（５ａ）で表される分岐構造単位を与えることとなり、上記式（２ａ）～（５ａ）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。 The polycyclic diolefin compound for forming a structural unit derived from the polycyclic diolefin compound is not particularly limited, but is represented by the following formula (1) or the following formulas (2) to (5). Examples include the represented compounds.

In the above formula (1), R ¹ and R ² are alkylene groups having 1 to 6 carbon atoms, n is an integer of 0 to 2, and in the above formula (1), the hydrogen atom has 1 to 6 carbon atoms. It may be substituted with an alkyl group of. Further, the compound represented by the above formula (1) gives a branched structural unit represented by the above formula (1a) when it is ring-opened copolymerized with cyclopentene, and the above formula (1a). Among them, R ¹ , R ² , and n are the same as those in the above formula (1), and in the above formula (1a), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.

In the above formulas (2) to (5), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms. Further, the compounds represented by the above formulas (2) to (5) give the branched structural units represented by the above formulas (2a) to (5a) when they are ring-opened copolymerized with cyclopentene, respectively. In the above formulas (2a) to (5a), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.

上記式（６）～（９）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。また、上記式（６）～（９）で表される化合物は、シクロペンテンと開環共重合した際に、それぞれ、上記式（６ａ）～（９ａ）で表される分岐構造単位を与えることとなるものであり、上記式（６ａ）～（９ａ）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。 Specific examples of the compound represented by the above formula (1) include compounds represented by the following formulas (6) to (9).

In the above formulas (6) to (9), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms. Further, the compounds represented by the above formulas (6) to (9) are given the branched structural units represented by the above formulas (6a) to (9a) when they are ring-opened copolymerized with cyclopentene, respectively. In the above formulas (6a) to (9a), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.

Among the above-mentioned compounds, it is preferable to use the compound represented by the above formula (3), the above formula (6) or the above formula (7) from the viewpoint that the branched structure can be formed more appropriately. That is, the cyclopentene ring-opening polymer having a branched structure used in the present invention has a branched structural unit represented by the above formula (3a), the above formula (6a) or the above formula (7a) as the branched structure unit. Is preferable.

上記式（１０）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。また、上記式（１０）で表される化合物は、シクロペンテンと開環共重合した際に、上記式（１０ａ）で表される分岐構造単位を与えることとなるものであり、上記式（１０ａ）中、水素原子は炭素数１～６のアルキル基で置換されていてもよい。 The vinyl group-containing cyclic olefin compound for forming a structural unit derived from the vinyl group-containing cyclic olefin compound is not particularly limited, but is monocyclic having a vinyl group such as 4-vinylcyclopentene and 5-vinylcyclooctene. Olefins; norbornenes having a vinyl group such as 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-styryl-2-norbornene; and the like. In addition, these compounds may be those in which a hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms. Among these, 5-vinyl-2-norbornene (hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms) represented by the following formula (10) is also used because the branched structure can be formed more appropriately. Including) is preferable.

In the above formula (10), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms. Further, the compound represented by the above formula (10) gives a branched structural unit represented by the above formula (10a) when it is ring-opened copolymerized with cyclopentene, and the above formula (10a). Among them, the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.

In addition to the above-mentioned compounds, the compounds for forming the branched structural unit include 1,2,4-trivinylcyclohexane and 1,3,5-tri as compounds into which a tribranched structure can be introduced. A compound having three vinyl groups such as vinylcyclohexane can also be used. Alternatively, a branched structure having four or more branches may be introduced by using a compound having four or more vinyl groups such as a divinylbenzene oligomer and a 1,2-polybutadiene oligomer.

The content ratio of the branched structural unit in the cyclopentene ring-opening polymer having a branched structure used in the present invention is preferably 0.01 mol% or more, more preferably 0.05 mol% or more, based on all the repeating units. It is more preferably 0.1 mol% or more, and the upper limit thereof is preferably 4 mol% or less, more preferably 3 mol% or less, still more preferably 2.6 mol% or less. By setting the content ratio of the branched structural unit in the above range, it is possible to appropriately prevent gelation of the obtained cyclopentene ring-opening polymer having a branched structure and further increase the rebound resilience when the rubber crosslinked product is formed. ..

Further, the cyclopentene ring-opening polymer having a branched structure used in the present invention is a single amount copolymerizable with cyclopentene and a monomer capable of forming a branched structure as long as the characteristics as a cyclopentene ring-opening polymer are maintained. It may contain repeating units derived from the body. The content ratio of the repeating unit derived from the other copolymerizable monomer is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 5 mol% or less, based on all the repeating units. It is 1 mol% or less.

Examples of other monomers copolymerizable with cyclopentene include monocyclic olefins other than cyclopentene, monocyclic dienes, monocyclic trienes, polycyclic cyclic olefins, polycyclic dienes, polycyclic cyclic trienes and the like. .. Examples of monocyclic olefins other than cyclopentene include cyclooctene. Examples of the monocyclic diene include 1,5-cyclooctadiene. Examples of the monocyclic triene include 1,5,9-cyclododecatriene. The polycyclic olefins, polycyclic dienes, and polycyclic cyclic trienes include 2-norbornene, dicyclopentadiene, 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene. , Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Norbornene compounds such as dodeca-4-ene are exemplified. The cyclopentene and other monomers copolymerizable with the cyclopentene may have a substituent or may be unsubstituted. Further, the other monomer copolymerizable with the cyclopentene may be used alone or in combination of two or more.

The molecular weight of the cyclopentene ring-opening polymer having a branched structure is not particularly limited, but is 100,000 to 1,000,000 as the value of the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography. It is preferably 150,000 to 900,000, more preferably 200,000 to 800,000. When the cyclopentene ring-opening polymer having a branched structure has such a molecular weight, the mechanical properties of the rubber crosslinked product can be further improved.

The ratio (Mw / Mn) of the polystyrene-equivalent number average molecular weight (Mn) to the weight average molecular weight (Mw) measured by gel permeation chromatography of the cyclopentene ring-opening polymer having a branched structure is not particularly limited. However, it is usually 4.0 or less, preferably 3.5 or less, and more preferably 3.0 or less. By having such Mw / Mn, the mechanical properties of the rubber crosslinked product can be made more excellent.

The cis / trans ratio of the double bond present in the repeating unit constituting the cyclopentene ring-opening polymer having a branched structure is not particularly limited, but is usually set in the range of 10/90 to 90/10. From the viewpoint of making the rubber crosslinked product more excellent in low temperature characteristics, it is preferably in the range of 90/10 to 51/49, and more preferably in the range of 90/10 to 55/45. Alternatively, from the viewpoint of making the rubber crosslinked product more excellent in fracture strength characteristics, the range is preferably in the range of 10/90 to 49/51, and more preferably in the range of 10/90 to 45/55. ..

The method for adjusting the cis / trans ratio of the cyclopentene ring-opening polymer having a branched structure is not particularly limited, but for example, a monomer mixture containing cyclopentene and a monomer capable of forming a branched structure is polymerized. Further, a method of controlling the polymerization conditions in obtaining a cyclopentene ring-opening polymer having a branched structure and the like can be mentioned. As an example, the higher the polymerization temperature when polymerizing a monomer mixture containing cyclopentene and a monomer capable of forming a branched structure, the higher the trans ratio can be, and the monomer concentration in the polymerization solution can be increased. The lower the value, the higher the transformer ratio.

The glass transition temperature of the cyclopentene ring-opening polymer having a branched structure is not particularly limited, but is preferably −90 ° C. or lower, more preferably −95 ° C., from the viewpoint of exhibiting excellent properties at low temperatures. Below, it is more preferably −98 ° C. or lower. The glass transition temperature of the cyclopentene ring-opening polymer having a branched structure can be adjusted, for example, by adjusting the cis / trans ratio in the double bond present in the repeating unit.

The cyclopentene ring-opening polymer having a branched structure may have a molecular structure consisting of only carbon atoms and hydrogen atoms, but may contain atoms other than carbon atoms and hydrogen atoms in the molecular structure. More specifically, it may contain a modifying group containing an atom selected from the group consisting of an atom of Group 15 of the Periodic Table, an atom of Group 16 of the Periodic Table, and an atom of silicon.

As such a modifying group, a modifying group containing an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, and a silicon atom is preferable, and among these, a nitrogen atom and an oxygen atom are preferable. , And a modifying group containing an atom selected from the group consisting of silicon atoms is more preferred, and a modifying group containing a silicon atom is even more preferred.

Examples of the modifying group containing a nitrogen atom include an amino group, a pyridyl group, an imino group, an amide group, a nitro group, a urethane bonding group, or a hydrocarbon group containing these groups. Examples of the modifying group containing an oxygen atom include a hydroxyl group, a carboxylic acid group, an ether group, an ester group, a carbonyl group, an aldehyde group, an epoxy group, or a hydrocarbon group containing these groups. Examples of the modifying group containing a silicon atom include an alkylsilyl group, an oxysilyl group, and a hydrocarbon group containing these groups. Examples of the modifying group containing a phosphorus atom include a phosphoric acid group, a phosphino group, and a hydrocarbon group containing these groups. Examples of the modifying group containing a sulfur atom include a sulfonyl group, a thiol group, a thioether group, and a hydrocarbon group containing these groups. Further, the modifying group may be a modifying group containing a plurality of the above-mentioned groups. Among these, as a specific example of a particularly suitable modifying group, an amino group, a pyridyl group, an imino group, an amide group, a hydroxyl group, a carboxylic acid group, an aldehyde group, an epoxy group, an oxysilyl group, or a carbide containing these groups Examples include hydrogen groups, with oxysilyl groups being particularly preferred. The oxysilyl group means a group having a silicon-oxygen bond.

Specific examples of the oxysilyl group include an alkoxysilyl group, an aryloxysilyl group, an acyloxy group, an alkylsiloxysilyl group, an arylsiloxysilyl group, a hydroxysilyl group and the like. Among these, an alkoxysilyl group is preferable from the viewpoint of high introduction effect.

An alkoxysilyl group is a group in which one or more alkoxy groups are bonded to a silicon atom, and specific examples thereof include a trimethoxysilyl group, a (dimethoxy) (methyl) silyl group, and a (methoxy) (dimethyl) silyl group. Group, triethoxysilyl group, (diethoxy) (methyl) silyl group, (ethoxy) (dimethyl) silyl group, (dimethoxy) (ethoxy) silyl group, (methoxy) (diethoxy) silyl group, tripropoxysilyl group, tributoxy Examples include a silyl group.

The allyloxysilyl group is a group in which one or more allyloxy groups are bonded to a silicon atom, and specific examples thereof include a triphenoxysilyl group, a (diphenoxy) (methyl) silyl group, and (phenoxy) (dimethyl). Examples thereof include a silyl group, a (diphenoxy) (ethoxy) silyl group, and a (phenoxy) (diethoxy) silyl group. Of these, the (diphenoxy) (ethoxy) silyl group and the (phenoxy) (diethoxy) silyl group also have an alkoxy group in addition to the aryloxy group, and thus are also classified as an alkoxysilyl group.

The asyloxysilyl group is a group in which one or more asyloxy groups are bonded to a silicon atom, and specific examples thereof include a triacyloxysilyl group, a (diasiloxy) (methyl) silyl group, and (acidoxy) (dimethyl). Examples include a silyl group.

The alkylsiloxysilyl group is a group in which one or more alkylsiloxy groups are bonded to a silicon atom, and specific examples thereof include a tris (trimethylsiloxy) silyl group, a trimethylsiloxy (dimethyl) silyl group, and a triethylsiloxy (triethylsiloxy). Examples thereof include a diethyl) silyl group and a tris (dimethylsiloxy) silyl group.

The arylsiloxysilyl group is a group in which one or more arylsiloxy groups are bonded to a silicon atom, and specific examples thereof include a tris (triphenylsiloxy) silyl group, a triphenylsiloxy (dimethyl) silyl group, and a tris. (Diphenylsiloxy) Cyril group and the like can be mentioned.

A hydroxysilyl group is a group in which one or more hydroxy groups are bonded to a silicon atom, and specific examples thereof include a trihydroxysilyl group, a (dihydroxy) (methyl) silyl group, and a (hydroxy) (dimethyl) silyl group. , (Dihydroxy) (ethoxy) silyl group, (hydroxy) (diethoxy) silyl group and the like. Of these, the (dihydroxy) (ethoxy) silyl group and the (hydroxy) (diethoxy) silyl group also have an alkoxy group in addition to the hydroxy group, and thus are also classified as an alkoxysilyl group.

When the cyclopentene ring-opening polymer having a branched structure has such a modifying group, the introduction position of the modifying group is not particularly limited, but from the viewpoint of further enhancing the introduction effect, it is at the end of the polymer chain. It preferably has a modifying group. When the polymer chain has a modifying group at the end, a terminal-modified cyclopentene ring-opening polymer having a branched structure having a modifying group at the end of the polymer chain and a modifying group at the end of the polymer chain are introduced. An unmodified cyclopentene ring-opening polymer having a branched structure may be mixed.

When the cyclopentene ring-opening polymer having a branched structure has a modifying group at the end of the polymer chain, the introduction ratio of the modifying group at the end of the polymer chain of the cyclopentene ring-opening polymer having a branched structure is not particularly limited. However, the value of the percentage of the number of terminal chains of the cyclopentene ring-opening polymer chain having a branched structure into which a modifying group has been introduced / the number of cyclopentene ring-opened polymer chains having a branched structure is preferably 60% or more, more preferably. It is 80% or more, more preferably 90% or more. The method for measuring the introduction ratio of the modifying group to the terminal of the polymer chain is not particularly limited, but for example, the peak area ratio corresponding to the modifying group obtained by 1H ^- NMR spectrum measurement and gel permeation chromatography. It can be obtained from the number average molecular weight obtained from.

The method for synthesizing the cyclopentene ring-opening polymer having a branched structure is not particularly limited as long as the target polymer can be obtained, and it may be synthesized according to a conventional method. For example, it may be synthesized by the method described below. Can be done.

That is, the cyclopentene ring-opening polymer having a branched structure is, for example, in the presence of a polymerization catalyst containing the Group 6 transition metal compound (A) in the periodic table and the organic aluminum compound (B) represented by the following formula (11). , Cyclopentene and a monomer mixture containing a monomer capable of forming a branched structure can be obtained by ring-opening polymerization.
(R ³ ) _3-x Al (OR ⁴ ) _x (11)
(In the above formula (11), R ³ and R ⁴ represent a hydrocarbon group having 1 to 20 carbon atoms, and x is 0 <x <3.)

The amount of each monomer used in the monomer mixture containing cyclopentene and the monomer capable of forming a branched structure used for the polymerization may be an amount corresponding to the above-mentioned content ratio.

The periodic table Group 6 transition metal compound (A) is a compound having a Group 6 transition metal atom in the periodic table (long periodic table, the same applies hereinafter), specifically, a chromium atom, a molybdenum atom, or a tungsten atom. A compound having a molybdenum atom or a compound having a tungsten atom is preferable, and a compound having a tungsten atom is more preferable from the viewpoint of high solubility in cyclopentene or a monomer capable of forming a branched structure. .. The group 6 transition metal compound (A) in the periodic table may be any compound having a transition metal atom in group 6 of the periodic table, and is not particularly limited, but is a halide or alcoholate of the transition metal atom in group 6 of the periodic table. , Arilate, oxidized compounds and the like, and among these, halides are preferable from the viewpoint of high polymerization activity.

Specific examples of such a transition metal compound (A) of Group 6 of the periodic table include molybdenum compounds such as molybdenum pentachloride, molybdenum oxotetrachloride, and molybdenum (phenylimide) tetrachloride; tungsten hexachloride, tungsten oxotetrachloride, and the like. Tungsten compounds such as tungsten (phenylimide) tetrachloride, monocatecholate tungsten tetrachloride, bis (3,5-ditershaributyl) catecholate tungsten dichloride, bis (2-chloroeterate) tetrachloride, tungsten oxotetraphenorate ; And so on.

The amount of the Group 6 transition metal compound (A) used in the periodic table is the molar ratio of "Group 6 transition metal atom in the polymerization catalyst: the monomer mixture used for the polymerization", and is usually 1: 100 to 1: 200. It is in the range of 000, preferably 1: 200 to 1: 150,000, and more preferably 1: 500 to 1: 100,000. If the amount of the Group 6 transition metal compound (A) used in the periodic table is too small, the polymerization reaction may not proceed sufficiently. On the other hand, if the amount is too large, it becomes difficult to remove the catalyst residue from the cyclopentene ring-opening polymer having a branched structure, and various properties of the obtained rubber crosslinked product may be deteriorated.

The organoaluminum compound (B) is a compound represented by the above formula (11). Specific examples of the hydrocarbon groups having 1 to 20 carbon atoms represented by R ³ and R ⁴ in the formula (11) include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an isobutyl group, and an n-butyl group. , T-butyl group, n-hexyl group, alkyl group such as cyclohexyl group; phenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diisopropylphenyl group, aryl group such as naphthyl group; And so on. In the compound represented by the formula (11), the groups represented by R ³ and R ⁴ may be the same or different, but the resulting branched cyclopentene ring-opening polymer having a branched structure may be used. Of R ³ and R ⁴ , at least R ⁴ is preferably an alkyl group in which four or more carbon atoms are continuously bonded, particularly preferably, from the viewpoint that the cis ratio can be controlled within the above-mentioned preferable range. , N-butyl group, 2-methyl-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, or n-decyl group is more preferable.

Further, in the above equation (11), x is 0 <x <3. That is, in the formula (11), the composition ratio of R ³ and OR ⁴ can take any value in each range of 0 <3-x <3 and 0 <x <3, respectively. X is 0.5 <x <1.5 from the viewpoint that the polymerization activity can be increased and the cis ratio of the obtained cyclopentene ring-opening polymer having a branched structure can be controlled within the above-mentioned suitable range. Is preferable.

The organoaluminum compound (B) represented by the above formula (11) can be synthesized, for example, by reacting trialkylaluminum with an alcohol as shown in the following formula (12).
(R ³ ) ₃ Al + xR ⁴ OH → (R ³ ) _3-x Al (OR ⁴ ) _x + (R ³ ) _x H (12)

As shown in the above formula (12), x in the above formula (11) can be arbitrarily controlled by defining the reaction ratio of the corresponding trialkylaluminum and the alcohol.

The amount of the organic aluminum compound (B) used varies depending on the type of the organic aluminum compound (B) used, but with respect to the Group 6 transition metal atom of the Periodic Table constituting the Group 6 Transition Metal Compound (A) of the Periodic Table. The ratio is preferably 0.1 to 100 times, more preferably 0.2 to 50 times, and even more preferably 0.5 to 20 times. If the amount of the organoaluminum compound (B) used is too small, the polymerization activity may be insufficient, and if it is too large, side reactions tend to easily occur during ring-opening polymerization.

The ring-opening polymerization reaction may be carried out without a solvent or in a solution. As the solvent used when the ring-opening polymerization reaction is carried out in the solution, cyclopentene used for the ring-opening polymerization, a monomer capable of forming a branched structure, and the above-mentioned polymerization catalyst, which are inactive in the polymerization reaction, can be dissolved. Any solvent may be used, and the solvent is not particularly limited, and examples thereof include a hydrocarbon solvent and a halogen solvent. Specific examples of hydrocarbon-based solvents include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane; cyclohexane, cyclopentane and methyl. Aromatic hydrocarbons such as cyclohexane; and the like. Specific examples of the halogen-based solvent include alkyl halogens such as dichloromethane and chloroform; aromatic halogens such as chlorobenzene and dichlorobenzene; and the like.

Further, the modified group-containing olefinically unsaturated compound having the above-mentioned modifying group and having one olefinic carbon-carbon double bond having metathesis reactivity in the polymerization reaction system of the ring-opening polymerization reaction. In the presence of the hydrocarbon (C), a modifying group can be introduced at the end of the polymer chain of the cyclopentene ring-opening polymer having a branched structure. For example, when an oxysilyl group is introduced at the end of the polymer chain of a cyclopentene ring-opening polymer having a branched structure, an oxysilyl group-containing olefinically unsaturated hydrocarbon may be present in the polymerization reaction system.

Examples of such an oxysilyl group-containing olefinically unsaturated hydrocarbon include vinyl (trimethoxy) silane and vinyl (trimethoxy) silane, vinyl (trimethoxy) silane, as an example of introducing one oxysilyl group into the polymer chain of a cyclopentene ring-opening polymer having a branched structure. Triethoxy) silane, allyl (trimethoxy) silane, allyl (methoxy) (dimethyl) silane, allyl (triethoxy) silane, allyl (ethoxy) (dimethyl) silane, styryl (trimethoxy) silane, styryl (triethoxy) silane, 2-styrylethyl Alkoxysilane compounds such as (triethoxy) silane, allyl (triethoxysilylmethyl) ether, allyl (triethoxysilylmethyl) (ethyl) amine; vinyl (triphenoxy) silane, allyl (triphenoxy) silane, allyl (phenoxy) ( Allyloxysilane compounds such as dimethyl) silane; acyloxysilane compounds such as vinyl (triacetoxy) silane, allyl (triacetoxy) silane, allyl (diacetoxy) methylsilane, allyl (acetoxy) (dimethyl) silane; allyltris (trimethylsiloxy) Alkylsiloxysilane compounds such as silanes; arylsiloxysilane compounds such as allyltris (triphenylsiloxy) silanes; 1-allylheptamethyltrisiloxane, 1-allylnonamethyltetrasiloxane, 1-allylnonamethylcyclopentasiloxane, 1-allyl Polysiloxane compounds such as undecamethylcyclohexasiloxane; and the like. Further, 1,4-bis (trimethoxysilyl) -2-butene and 1,4-bis (triethoxy) are used to introduce two oxysilyl groups into the polymer chain of the cyclopentene ring-opening polymer having a branched structure. Alkoxysilane compounds such as silyl) -2-butene and 1,4-bis (trimethoxysilylmethoxy) -2-butene; allyloxysilane compounds such as 1,4-bis (triphenoxysilyl) -2-butene; 1 , 4-bis (triacetoxysilyl) -2-butene and other acyloxysilane compounds; 1,4-bis [tris (trimethylsiloxy) silyl] -2-butene and other alkylsiloxysilane compounds; 1,4-bis [ Tris (triphenylsiloxy) silyl] -2-butene and other arylsiloxysilane compounds; 1,4-bis (heptamethyltrisiloxy) -2-butene, 1,4-bis (undecamethylcyclohexasiloxy) -2 -Polysiloxane compounds such as butene; and the like.

The amount of the modified group-containing olefinically unsaturated hydrocarbon (C) such as the oxysilyl group-containing olefinically unsaturated hydrocarbon may be appropriately selected depending on the molecular weight of the cyclopentene ring-opening polymer having a branched structure to be produced. , Usually 1/100 to 1 / 100,000, preferably 1/200 to 1/50, in terms of molar ratio to a monomer mixture containing cyclopentene used for polymerization and a monomer capable of forming a branched structure. 000, more preferably in the range of 1/500 to 1 / 10,000. The modified group-containing olefinically unsaturated hydrocarbon (C) also acts as a molecular weight adjusting agent in addition to the action of introducing a modifying group into the polymer chain end of the cyclopentene ring-opening polymer having a branched structure.

Alternatively, when the above-mentioned modifying group is not introduced into the cyclopentene ring-opening polymer having a branched structure, 1-as a molecular weight adjusting agent in order to adjust the molecular weight of the obtained cyclopentene ring-opening polymer having a branched structure. Olefin compounds such as butene, 1-pentene, 1-hexene, 1-octene and 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4- Diolefin compounds such as pentadiene and 2,5-dimethyl-1,5-hexadiene may be used and added to the polymerization reaction system. The amount of the molecular weight adjusting agent used may be appropriately selected from the same range as that of the above-mentioned modified group-containing olefinically unsaturated hydrocarbon (C).

The polymerization reaction temperature is not particularly limited, but is preferably −100 ° C. or higher, more preferably −50 ° C. or higher, still more preferably −20 ° C. or higher, and particularly preferably 0 ° C. or higher. The upper limit of the polymerization reaction temperature is not particularly limited, but is preferably less than 100 ° C, more preferably less than 90 ° C, still more preferably less than 80 ° C, and particularly preferably less than 70 ° C. The polymerization reaction time is also not particularly limited, but is preferably 1 minute to 72 hours, more preferably 10 minutes to 20 hours.

Alternatively, instead of the method using a polymerization catalyst containing the above-mentioned Group 6 transition metal compound (A) in the periodic table and the organic aluminum compound (B) represented by the formula (11), a ruthenium carben complex is used as the polymerization catalyst. Further, a cyclopentene ring-opening polymer having a branched structure can also be produced by a method of ring-opening polymerization of a monomer mixture containing cyclopentene and a monomer capable of forming a branched structure in the presence of a ruthenium carben complex. ..

The ruthenium carbene complex is not particularly limited as long as it serves as a ring-opening polymerization catalyst for cyclopentene. Specific examples of the preferably used ruthenium carben complex include bis (tricyclohexylphosphine) benziliden ruthenium dichloride, bis (triphenylphosphine) -3,3-diphenylpropeniliden ruthenium dichloride, (3-phenyl-1H-inden-1). -Iliden) bis (tricyclohexylphosphine) ruthenium dichloride, bis (tricyclohexylphosphin) t-butylvinylidene ruthenium dichloride, bis (1,3-diisopropylimidazolin-2-iriden) benziliden ruthenium dichloride, bis (1,3-dicyclohexylimidazolin) -2-Ilidene) Benzilidene Ruthenium Dichloride, (1,3-Dimethylimidazolin-2-Ilidene) (Tricyclohexylphosphine) Benzylidene Ruthenium Dichloride, (1,3-Dimethylimidazolidine-2-Ilidene) (Tricyclohexyl) Examples thereof include benzylidene ruthenium dichloride, bis (tricyclohexyl phosphine) ethoxymethyridene ruthenium dichloride, (1,3-dimeshtyl imidazoline-2-iriden) (tricyclohexylphosphine) ethoxymethyridene ruthenium dichloride.

The amount of the ruthenium carbene complex used is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to the molar ratio of (metal ruthenium in the catalyst: monomer used for polymerization). It is in the range of 1: 1,500,000, more preferably 1: 10,000 to 1: 1,000,000. If the amount of the ruthenium carbene complex used is too small, the polymerization reaction may not proceed sufficiently. On the other hand, if the amount is too large, it becomes difficult to remove the catalyst residue from the obtained cyclopentene ring-opening polymer having a branched structure, and various properties may be deteriorated when the rubber crosslinked product is obtained.

When a ruthenium carbene complex is used as the polymerization catalyst, the ring-opening polymerization reaction may be carried out without a solvent or in a solution. As the solvent used when the ring-opening polymerization reaction is carried out in the solution, a polymerization catalyst containing the above-mentioned Group 6 transition metal compound (A) of the periodic table and the organoaluminum compound (B) represented by the formula (11) is used. You can use the same as in the case.

The polymerization reaction temperature and the polymerization reaction time are also the same as in the case of using the polymerization catalyst containing the above-mentioned Group 6 transition metal compound (A) in the periodic table and the organoaluminum compound (B) represented by the formula (11).

Then, a method using a polymerization catalyst containing the above-mentioned Group 6 transition metal compound (A) of the periodic table and the organic aluminum compound (B) represented by the formula (11), or a method using a ruthenium carben complex as the polymerization catalyst. If desired, an antiaging agent such as a phenol-based stabilizer, a phosphorus-based stabilizer, or a sulfur-based stabilizer may be added to the cyclopentene ring-opening polymer having a branched structure. The amount of the antiaging agent added may be appropriately determined according to the type and the like. Further, if desired, a spreading oil may be blended. When a cyclopentene ring-opening polymer having a branched structure is obtained as the polymer solution, a known recovery method may be adopted in order to recover the polymer from the polymer solution. For example, a solvent may be used by steam stripping or the like. After separation, a method of filtering the solid and then drying it to obtain a solid rubber can be adopted.

The rubber component used in the present invention may contain other rubbers in addition to the cyclopentene ring-opening polymer having a branched structure. Examples of rubbers other than the cyclopentene ring-opening polymer having a branched structure include natural rubber (NR), polyisoprene rubber (IR), solution-polymerized SBR (solution-polymerized styrene-butadiene rubber), and emulsified-polymerized SBR (emulsified-polymerized styrene-butadiene rubber). ), Low cis BR (polybutadiene rubber), high cis BR, high trans BR (trans bond content of butadiene part 70-95%), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, ethylenepropylene diene rubber ( EPDM), emulsified polymerized styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polyisoprene-SBR block copolymer rubber, polystyrene-polybutadiene-polystyrene block copolymer, acrylic rubber, epichlorohydrin rubber, fluororubber , Silicon rubber, ethylene-propylene rubber, urethane rubber and the like. Of these, NR, BR, IR, solution polymerization SBR, emulsion polymerization SBR, and EPDM are preferably used. These rubbers can be used alone or in combination of two or more.

In the rubber component used in the present invention, the content of the cyclopentene ring-opening polymer having a branched structure is preferably 10% by weight or more with respect to the total rubber component from the viewpoint of making the effect of the present invention more remarkable. Yes, more preferably 50% by weight or more, still more preferably 70% by weight or more. On the other hand, the content of rubber other than the cyclopentene ring-opening polymer having a branched structure is preferably 90% by weight or less, more preferably 50% by weight or less, still more preferably 30% by weight, based on the total rubber component. % Or less.

The polymer composition used in the present invention is obtained by blending carbon black with a rubber component containing a cyclopentene ring-opening polymer having the above-mentioned branched structure.

Examples of carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Among these, it is preferable to use furnace black, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, MAF, and FEF. Can be mentioned. These can be used alone or in combination of two or more.

Carbon black has a nitrogen adsorption specific surface area (N ₂ SA) of preferably 5 to 200 m ² / g, more preferably 20 to 150 m ² / g, and a dibutyl phthalate (DBP) adsorption amount of preferably 5 to 200 ml. / 100 g, more preferably 50-160 ml / 100 g. The nitrogen adsorption specific surface area can be measured by the BET method in accordance with ASTM D-4820.

The content of carbon black in the polymer composition used in the present invention is 20 to 200 parts by weight, preferably 25 to 200 parts by weight, based on 100 parts by weight of the rubber component containing the cyclopentene ring-opening polymer having a branched structure. It is 150 parts by weight, more preferably 35 to 100 parts by weight. According to the present invention, as the cyclopentene ring-opening polymer, a polymer having a branched structure is used, and the content of carbon black is within the above range to increase the elastic modulus when the rubber is crosslinked. This makes it possible to suitably apply the obtained rubber crosslinked product as a high repulsion material that requires a high rebound resilience. If the content of carbon black is too small, the obtained rubber crosslinked product will be inferior in mechanical properties. On the other hand, if the content of carbon black is too large, the processability as a polymer composition will be inferior.

In addition to the above components, the polymer composition used in the present invention contains a cross-linking agent, a cross-linking accelerator, a cross-linking activator, an antioxidant, an activator, a process oil, a plasticizer, a wax, and carbon according to a conventional method. A required amount of a compounding agent such as a filler other than black can be blended.

Examples of the cross-linking agent include sulfur, sulfur halides, organic peroxides, quinonedioximes, organic polyvalent amine compounds, zinc acrylates, and alkylphenol resins having a methylol group. Of these, sulfur and organic peroxides are preferably used. The amount of the cross-linking agent to be blended is preferably 0.5 to 5 parts by weight, more preferably 0.7 to 4 parts by weight, still more preferably 1 to 3 parts by weight, based on 100 parts by weight of the rubber component in the polymer composition. It is a department.

Examples of the cross-linking accelerator include N-cyclohexyl-2-benzothiazolyl sulfenamide, Nt-butyl-2-benzothiazolyl sulfenamide, N-oxyethylene-2-benzothiazolyl sulfenamide, and the like. Sulfenamide-based cross-linking accelerators such as N-oxyethylene-2-benzothiazolyl sulfenamide, N, N'-diisopropyl-2-benzothiazolyl sulfenamide; 1,3-diphenylguanidine, 1,3- Guanidin-based cross-linking accelerators such as dioltotrilguanidine and 1-orthotrilbiguanidine; thiourea-based cross-linking promoters; thiazole-based cross-linking promoters; thiuram-based cross-linking promoters; dithiocarbamic acid-based cross-linking promoters; xanthogenic acid-based cross-linking promoters ; And so on. Among these, those containing a sulfenamide-based cross-linking accelerator are particularly preferable. These cross-linking accelerators may be used alone or in combination of two or more. The blending amount of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component in the polymer composition.

Examples of the cross-linking activator include higher fatty acids such as stearic acid and zinc oxide. The blending amount of the cross-linking activator is not particularly limited, but the blending amount when the higher fatty acid is used as the cross-linking activator is preferably 0.05 to 0.05 with respect to 100 parts by weight of the rubber component in the polymer composition. It is 15 parts by weight, more preferably 0.5 to 5 parts by weight, and the blending amount when zinc oxide is used as the crosslinking activator is preferably 0 with respect to 100 parts by weight of the rubber component in the polymer composition. It is 0.05 to 15 parts by weight, more preferably 0.5 to 5 parts by weight.

As the process oil, mineral oil or synthetic oil may be used. As the mineral oil, aroma oil, naphthenic oil, paraffin oil and the like are usually used.

Examples of fillers other than carbon black include metal powders such as aluminum powder; inorganic powders such as hard clay, talc, calcium carbonate, titanium oxide, calcium sulfate, calcium carbonate and aluminum hydroxide; and organic powders such as starch and polystyrene powder. Powders such as powders; short fibers such as glass fibers (milled fibers), carbon fibers, aramid fibers, potassium titanate whiskers; silica, mica; and the like. These fillers may be used alone or in combination of two or more.

The method for obtaining the polymer composition used in the present invention is not particularly limited, and each component may be kneaded according to a conventional method. For example, a compounding agent such as carbon black excluding a crosslinking agent and a crosslinking accelerator. And a rubber component such as a cycloolefin ring-opening polymer having a branched structure are kneaded, and then a cross-linking agent and a cross-linking accelerator are mixed with the kneaded product to obtain a desired composition. The kneading temperature of the compounding agent excluding the crosslinking agent and the crosslinking accelerator and the rubber component is preferably 70 to 200 ° C, more preferably 100 to 180 ° C. The kneading time is preferably 30 seconds to 30 minutes. Mixing of the kneaded product with the cross-linking agent and the cross-linking accelerator is usually carried out after cooling to 100 ° C. or lower, preferably 80 ° C. or lower.

The rubber crosslinked product according to the present invention can be obtained by cross-linking the above-mentioned polymer composition. The cross-linking method is not particularly limited and may be selected according to the shape, size and the like of the rubber cross-linked product. The polymer composition may be filled in a mold and crosslinked at the same time as molding by heating, or the polymer composition previously molded may be heated and crosslinked. The crosslinking temperature is preferably 120 to 200 ° C., more preferably 140 to 180 ° C., and the crosslinking time is usually about 1 to 120 minutes.

Further, depending on the shape and size of the rubber crosslinked product, even if the surface is crosslinked, it may not be sufficiently crosslinked to the inside, so that it may be further heated for secondary crosslinking.

As the heating method, a general method used for cross-linking rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.

The rubber crosslinked product according to the present invention thus obtained has an excellent impact modulus. Specifically, the rubber crosslinked product according to the present invention has a rebound resilience rate of 63% or more at a temperature of 23 ° C., which is measured using a Rupke-type rebound resilience tester in accordance with JIS K6255: 1996. Is preferable, and 65% or more is more preferable. The upper limit of the elastic modulus at a temperature of 23 ° C. is not particularly limited, but is preferably 90% or less.

Further, the rubber crosslinked product according to the present invention has an excellent elastic modulus at room temperature (temperature 23 ° C.) and also has an excellent elastic modulus even in a low temperature (for example, 10 ° C. or lower) environment. Is. Specifically, the rubber crosslinked product according to the present invention has a rebound resilience at a temperature of 0 ° C., preferably 55% or more, more preferably 60% or more, and has a rebound resilience at a temperature of −40 ° C. It is preferably 40% or more, more preferably 45% or more, and has an excellent rebound resilience even in a low temperature environment.

The present invention uses such a rubber crosslinked product as a high repulsion material, and since the high repulsion material of the present invention is made of such a rubber crosslinked product, it has a high rebound resilience. It is a thing. The high-resilience material of the present invention makes use of such characteristics and is suitable for various sports applications such as golf balls, rubber members of table tennis rackets, and athletic shoes, which require a high elastic modulus. Can be used. In particular, since the rubber crosslinked product of the present invention has an excellent rebound resilience even in a low temperature environment, it can be preferably used as a high repulsion material used in an environment of 10 ° C. or lower, and is 0 ° C. It can be more preferably used as a high-resilience material used in the following environment, and particularly preferably as a high-resilience material used in an environment of −10 ° C. or lower.

Hereinafter, the present invention will be described based on more detailed examples, but the present invention is not limited to these examples. In the following, "part" is based on weight unless otherwise specified. In addition, various tests and evaluations were carried out according to the following methods.

[Molecular weight of cyclopentene ring-opening (co) polymer, butadiene rubber]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the cyclopentene ring-opening (co) polymer and butadiene rubber were obtained by gel permeation chromatography (GPC) to obtain a chart based on the polystyrene-equivalent molecular weight. Obtained based on the chart. The specific measurement conditions for gel permeation chromatography are as follows.
Measuring instrument: HLC-8320 EcoSCE (manufactured by Tosoh Corporation)
Column: Two GMH-HR-H (manufactured by Tosoh Corporation) were connected in series.
Detector: Differential refractometer RI-8020 (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Column temperature: 40 ° C

[Ratio of structural units derived from monomers capable of forming a branched structure in the cyclopentene ring-opening copolymer]
¹ Obtained by measuring the monomer composition ratio in the cyclopentene ring-opening copolymer by 1 H-NMR spectrum measurement.

[Sis / trans ratio of cyclopentene ring-opening (co) polymer, vinyl / cis / trans ratio of butadiene rubber]
¹³ Obtained from C-NMR spectrum measurement.

[Introduction rate of oxysilyl group of cyclopentene ring-opening (co) polymer]
¹ By H-NMR spectrum measurement, the ratio of the peak integrated value derived from the oxysilyl group to the peak integrated value derived from the carbon-carbon double bond in the terminal-modified cyclopentene ring-opening (co) polymer main chain was obtained. Based on the ratio of peak integral values and the measured value of number average molecular weight (Mn) by GPC, the introduction rate of oxysilyl group [(cyclopentene ring-opening (co) polymer chain terminal number with oxysilyl group introduced / terminal-modified cyclopentene opening) Percentage of ring (co) polymer chain)] was calculated.

[Glass transition temperature (Tg)]
The glass transition temperature (Tg) was measured at a temperature rise of 10 ° C./min using a differential scanning calorimeter (DSC, X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.).

[Repulsive elasticity test]
The polymer composition as a sample was press-molded at 150 ° C. for 30 minutes while pressurizing using a mold to obtain a cylindrical rubber crosslinked product having a diameter of 29 mm and a thickness of 12.5 mm. Then, with respect to the obtained columnar rubber crosslinked product, a Rupke type rebound resilience tester (manufactured by Polymer Meter Co., Ltd.) was used as a testing machine, and the temperature was -40 ° C, 0 ° C, in accordance with JIS K6255: 1996. The rebound resilience was measured under the conditions of holding force: 29 to 39 N under each temperature condition of 23 ° C. and 23 ° C.

[Reference Example 1]
Preparation of diisobutylaluminum monomethoxyd / toluene solution (2.5% by weight) In a nitrogen atmosphere, in a glass container containing a stirrer, 61 parts of toluene and 25.4% by weight of triisobutylaluminum / n-hexane solution ( Tosoh Finechem Co., Ltd.) 7.8 copies were added. Then, the container was cooled to −45 ° C., and 0.32 part of methanol (equivalent amount to triisobutylaluminum) was slowly added dropwise with vigorous stirring. Then, the mixture was allowed to stand until it reached room temperature with stirring to prepare a diisobutylaluminum monomethoxyd / toluene solution (2.5% by weight).

[Reference Example 2]
Preparation of diisobutylaluminum mono (n-hexoxide) / toluene solution (2.5% by weight) 88 parts of toluene and 25.4% by weight of triisobutylaluminum / n in a glass container containing a stir bar under a nitrogen atmosphere. -7.8 parts of a hexane solution (manufactured by Tosoh Finechem) was added. Then, the container was cooled to −45 ° C., and 1.02 parts of n-hexanol (equivalent amount to triisobutylaluminum) was slowly added dropwise with vigorous stirring. Then, the mixture was allowed to stand until it reached room temperature with stirring to prepare a diisobutylaluminum mono (n-hexoxide) / toluene solution (2.5% by weight).

[Synthesis Example 1]
Under a nitrogen atmosphere, 3000 parts of cyclopentene, 16.2 parts of norbornadiene (NBD), 9.32 parts of 1,2-bis (triethoxysilyl) ethylene, and 2.5 prepared in Reference Example 1 in a pressure-resistant glass reaction vessel equipped with a stirrer. 5 parts by weight of diisobutylaluminum monomethoxyde / toluene solution was added and heated to 50 ° C. To this, 14.5 parts of a 1.0% by weight WCl ₆ / toluene solution was added, and a polymerization reaction was carried out at 50 ° C. for 4 hours. After the polymerization reaction for 4 hours, excess ethyl alcohol was added to the pressure-resistant glass reaction vessel to stop the polymerization, and then the solution in the pressure-resistant glass reaction vessel was mixed with 2,6-di-t-butyl-p-cresol (BHT). ) Pour into a large excess of ethyl alcohol. Then, the precipitated polymer was recovered, washed with ethyl alcohol, and vacuum dried at 40 ° C. for 3 days to introduce a triethoxysilyl group at the end of the polymer chain. 466 copies were obtained. This terminal-modified cyclopentene / norbornadiene ring-opening copolymer is derived from the allylic proton in the norbornadiene structural unit in which only the olefin moiety of ^one ring is opened by 1H-NMR spectrum measurement and various two-dimensional NMR spectrum measurements. A peak was observed around 3.50 to 3.62 ppm. In addition, a peak derived from the allylic proton in the norbornadiene structural unit in which all the olefin sites of the two rings were opened to form a branched structure was observed around 3.19 to 3.30 ppm. From these observation results, it was confirmed that it is a branched polymer having a branched structure derived from norbornadiene in the main chain of the cyclopentene ring-opening polymer. Further, in the structure derived from all norbornadiene, the content ratio of the structural unit (4-branched structural unit) in which all the olefin moieties of the two rings are opened is 54%, and only the olefin moiety of one ring is opened. It was also confirmed that the content ratio of (non-branched structural unit) was 46%. Then, each measurement was carried out for the obtained terminal-modified cyclopentene / norbornadiene ring-opening copolymer according to the above method. The results are shown in Table 1.

[Synthesis Example 2]
A terminal-modified cyclopentene / norbornadiene ring-opening copolymer in which a polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that the amount of norbornadiene used was changed to 30.4 parts, and a triethoxysilyl group was introduced at the end of the polymer chain. Obtained 550 copies. Then, each measurement of the obtained terminal-modified cyclopentene / norbornadiene ring-opening copolymer was carried out in the same manner as in Synthesis Example 1. The results are shown in Table 1.

[Synthesis Example 3]
Under a nitrogen atmosphere, 3000 parts of cyclopentene, 16.2 parts of norbornadiene (NBD), 2.8 parts of 1-hexene, and 2.5% by weight of diisobutylaluminum monomethoxyde prepared in Reference Example 1 in a pressure-resistant glass reaction vessel equipped with a stirrer. / 1 part of toluene solution was added and heated to 50 ° C. To this, 2.9 parts of a 1.0% by weight WCl ₆ / toluene solution was added, and a polymerization reaction was carried out at 50 ° C. for 4 hours. After the polymerization reaction for 4 hours, excess ethyl alcohol was added to the pressure-resistant glass reaction vessel to stop the polymerization, and then the solution in the pressure-resistant glass reaction vessel was mixed with 2,6-di-t-butyl-p-cresol (BHT). ) Pour into a large excess of ethyl alcohol. Then, the precipitated polymer was recovered, washed with ethyl alcohol, and vacuum dried at 40 ° C. for 3 days to obtain 723 parts of an unmodified cyclopentene / norbornadiene ring-opening copolymer. The obtained unmodified cyclopentene / norbornadiene ring-opening copolymer was measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

The cyclopentene / norbornadiene ring-opening copolymer obtained in Synthesis Examples 2 and 3 was also measured by 1H-NMR spectrum measurement and various two-dimensional NMR spectrum measurements in the same manner as in Synthesis Example ¹ . It was confirmed that the cyclopentene ring-opening polymer was a branched polymer having a branched structure derived from norbornadiene in the main chain. Further, also in the cyclopentene / norbornadiene ring-opening copolymer obtained in Synthesis Examples 2 and 3, the ratio of the structural units (4-branched structural units) in which all the olefin moieties of the two rings are opened in the structure derived from all norbornadiene. Was in the range of 50 to 60%, and the proportion of structural units (non-branched structural units) in which only the olefin moiety of one ring was opened was in the range of 40 to 50%.

[Synthesis Example 4]
The polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that 2.94 parts of 5-vinyl-2-norbornene was used instead of norbornadiene, and a triethoxysilyl group was introduced at the end of the polymer chain. 792 parts of 5-vinyl-2-norbornene ring-opening copolymer was obtained. The obtained terminal-modified cyclopentene / 5-vinyl-2-norbornene ring-opening copolymer was measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

The terminal-modified cyclopentene / norbornadiene ring-opening copolymer obtained in Synthesis Example 4 was measured by 1H ^- NMR spectral measurement. As a result, 5-vinyl-2-norbornene was contained in the main chain of the cyclopentene ring-opening polymer. It was confirmed that the polymer had a branched structure of origin.

[Synthesis Example 5]
Under a nitrogen atmosphere, in a glass container containing a stirrer, 87 parts of 1.0 wt% WCl ₆ / toluene solution and 2.5 wt% diisobutylaluminum mono (n-hexoxide) / toluene prepared in Reference Example 2 43 parts of the solution was added and stirred for 15 minutes to obtain a catalytic solution. Then, under a nitrogen atmosphere, 300 parts of cyclopentene and 1.24 parts of 1,4-bis (triethoxysilyl) -2-butene were added to a pressure-resistant glass reaction vessel equipped with a stirrer, and the catalyst solution 130 prepared above was added thereto. The parts were added and a polymerization reaction was carried out at 25 ° C. for 4 hours. After the polymerization reaction for 4 hours, excess ethyl alcohol was added to the pressure-resistant glass reaction vessel to stop the polymerization, and then Irganox 1520L (manufactured by Ciba Specialty Chemicals) was added as an antiaging agent to the weight obtained by the polymerization. 0.2 part was added to 100 parts of the coalescence. Next, the polymer was coagulated with a large amount of ethanol to recover the polymer, and vacuum dried at 40 ° C. for 3 days to introduce 78 parts of a terminal-modified cyclopentene ring-opening polymer into which a triethoxysilyl group was introduced at the terminal of the polymer chain. Got The obtained terminal-modified cyclopentene ring-opening polymer was measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

[Synthesis Example 6]
After charging 5670 g of cyclohexane and 700 g of 1,3-butadiene in an autoclave with a stirrer, n-butyllithium is required to neutralize the polymerization-inhibiting impurities contained in cyclohexane and 1,3-butadiene. A large amount was added, and 8.33 mmol was added as the amount of n-butyllithium used in the polymerization reaction, and the polymerization was started at 50 ° C. After 20 minutes from the start of the polymerization, 300 g of 1,3-butadiene was continuously added over 30 minutes. The maximum temperature during the polymerization reaction was 80 ° C.
After the completion of continuous addition, the polymerization reaction was continued for another 15 minutes, and after confirming that the polymerization conversion was in the range of 95% to 100%, 1,6-bis (trichlorosilyl) hexane 0 was added to the polymerization solution. .333 mmol (corresponding to 0.04 times mol of n-butyllithium used for polymerization) was added in the form of a 40 wt% cyclohexane solution and reacted for 30 minutes. Further, after that, 2.92 mmol of polyorganosiloxane represented by the following formula (13) (corresponding to 0.35 times mol of n-butyllithium used for polymerization) was added in the form of a 20 wt% xylene solution, and 30 was added. After reacting for 1 minute, 8.33 mmol of tetramethoxysilane (corresponding to 1 times mol of n-butyllithium used for polymerization) was added in a 25 wt% cyclohexane solution, and the reaction was carried out for 30 minutes. Then, as a polymerization inhibitor, methanol corresponding to twice the mole of n-butyllithium used was added to obtain a solution containing terminal-modified polybutadiene. Then, 0.2 part of Irganox 1520L (manufactured by Ciba Specialty Chemicals) was added to the obtained solution as an antiaging agent per 100 parts of the rubber component, the solvent was removed by steam stripping, and then the temperature was 60 ° C. The terminal-modified butadiene rubber was obtained by vacuum drying for 24 hours. The weight average molecular weight (Mw) of the obtained terminal-modified butadiene rubber was 553,000, and the vinyl / cis / trans ratio was vinyl / cis / trans = 10/45/45.

[Example 1]
In a Banbury-type mixer, 100 parts of the terminal-modified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 1 was kneaded for 30 seconds, then 2 parts of stearic acid, 3 parts of zinc oxide, and carbon black (trade name "IRB"). # 8 ”, manufactured by CONTINENTAL CARBON, nitrogen adsorption specific surface area (BET method): 76.3 m ² / g) 60 parts, and process oil (manufactured by JX Nikko Nisseki Energy Co., Ltd., trade name“ Aromax T-DAE ” ) 15 parts were added and kneaded at 110 ° C. for 180 seconds, the compounding agent remaining on the upper part of the ram was cleaned, and then kneaded for another 150 seconds to discharge the kneaded product from the mixer. Next, the kneaded product was cooled to room temperature, and then, on an open roll at 23 ° C., the obtained kneaded product, 1,5 parts of sulfur, and N- (tert-butyl) -2-benzo as a cross-linking accelerator were used. After kneading with 0.9 part of thiazolyl sulfenamide (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name "Noxeller NS-P"), a sheet-shaped polymer composition was obtained.

Then, using the obtained polymer composition, a rubber crosslinked product was obtained according to the above method, and a rebound resilience test (each temperature condition of −40 ° C., 0 ° C. and 23 ° C.) was performed. The results are shown in Table 1.

[Example 2]
Example 1 and Example 1 except that 100 parts of the terminal-modified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 2 was used instead of 100 parts of the terminal-modified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 1. In the same manner, a polymer composition was obtained and evaluated in the same manner. The results are shown in Table 1.

[Example 3]
Example 1 and Example 1 except that 100 parts of the unmodified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 3 was used instead of 100 parts of the terminal-modified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 1. In the same manner, a polymer composition was obtained and evaluated in the same manner. The results are shown in Table 1.

[Example 4]
Instead of 100 parts of the terminal-modified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 1, 100 parts of the terminal-modified cyclopentene / 5-vinyl-2-norbornene ring-opening copolymer obtained in Synthesis Example 4 was used. Except for the above, a polymer composition was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

[Comparative Example 1]
Same as Example 1 except that 100 parts of the terminal-modified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 5 was used instead of 100 parts of the terminal-modified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 5. The polymer composition was obtained and evaluated in the same manner. The results are shown in Table 1.

[Comparative Example 2]
The weight was the same as in Example 1 except that 100 parts of the terminal-modified butadiene rubber obtained in Synthesis Example 6 was used instead of 100 parts of the terminal-modified cyclopentene / norbornadiene ring-opening polymer obtained in Synthesis Example 1. A combined composition was obtained and evaluated in the same manner. The results are shown in Table 1.

As shown in Table 1, from the results of Examples 1 to 4, the predetermined rubber crosslinked product of the present invention obtained by cross-linking a cyclopentene ring-opening polymer having a branched structure and a polymer composition containing a predetermined amount of carbon black. Is at room temperature (23 ° C.) as compared with the case where a cyclopentene ring-opening polymer having no branched structure or a butadiene rubber is used instead of the cyclopentene ring-opening polymer having a branched structure (Comparative Examples 1 and 2). It has a high rebound resilience and is suitable as a high repulsion material. Furthermore, it has a high rebound resilience at -40 ° C and 0 ° C and is used as a high repulsion material in a low temperature (for example, 10 ° C or lower) environment. , It can be said that it is particularly suitable.

Claims (3)

A high-resilience material made of a rubber crosslinked product obtained by cross-linking a polymer composition containing 20 to 200 parts by weight of carbon black with respect to 100 parts by weight of a rubber component containing a cyclopentene ring-opening polymer having a branched structure. There,
The cyclopentene ring-opening polymer is a structural unit derived from a polycyclic diolefin compound having at least two ring structures having one double bond as a branched structural unit, and is represented by the following formula (I). Branch structure With a branch structure starting from the unit ,
The content ratio of the branched structural unit in the cyclopentene ring-opening polymer is 0.01 mol% or more and 4 mol% or less.
A high-resilience material having a rebound resilience of 65% or more at a temperature of 23 ° C. measured using a Rupke-type rebound resilience tester in accordance with JIS K6255: 1996.

(In the above formula (I), the hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms.) The high-resilience material according to claim 1, wherein the cyclopentene ring-opening polymer having a branched structure has a structural unit derived from norbornadiene as the branched structural unit. Use of the high-resilience material according to claim 1 or 2 as a high-resilience material used in an environment of 10 ° C. or lower.