JP6862774B2 - Polymer composition for anti-vibration rubber, cross-linked rubber, and anti-vibration rubber - Google Patents

Description

The present invention relates to a polymer composition for anti-vibration rubber, a crosslinked rubber product, and an anti-vibration rubber.

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

One of the synthetic rubbers being studied as an alternative material to butadiene rubber is a cyclopentene ring-opening polymer obtained by ring-opening polymerization of cyclopentene. For example, Japanese Patent Application Laid-Open No. 2016-37585 (Patent Document 1) discloses a polymer composition containing 30 parts by mass of silica with respect to 100 parts by mass of a rubber component containing a cyclopentene ring-opening polymer. The rubber crosslinked product obtained from this polymer composition is excellent in heat aging resistance and compression set resistance, and has a low dynamic ratio, so that it can be applied to applications as a vibration isolator.

Japanese Unexamined Patent Publication No. 2016-37585

However, although the anti-vibration rubber obtained by the technique of Patent Document 1 has high anti-vibration performance, it is not always suitable as an anti-vibration rubber that is required to have higher anti-vibration performance in a wide range of applications.

An object of the present invention is to provide a polymer composition for a vibration-proof rubber, which is excellent in vibration-proof performance and can obtain a highly versatile vibration-proof rubber.

In order to solve the above problems, one aspect of the present invention includes a rubber component containing a cyclopentene ring-opening polymer and ^{a carbon-based material having a nitrogen adsorption specific surface area of 200 m 2} / g or less, and contains the carbon-based material. A polymer composition for anti-vibration rubber having an amount of 30 to 100 parts by mass with respect to 100 parts by mass of the rubber component is provided.

According to one aspect of the present invention, it is possible to obtain a polymer composition for anti-vibration rubber, which has excellent anti-vibration properties and provides highly versatile anti-vibration rubber.

Hereinafter, embodiments of the present invention will be described in detail.

The polymer composition for anti-vibration rubber according to the embodiment of the present invention contains a rubber component containing a cyclopentene ring-opening polymer and ^{a carbon-based material having a nitrogen adsorption specific surface area of 200 m 2} / g or less, and is a carbon-based material. The content of the polymer composition is 1 to 200 parts by mass with respect to 100 parts by mass of the rubber component.

The rubber component contained in the polymer composition for anti-vibration rubber of the present embodiment contains a cyclopentene ring-opening polymer. The cyclopentene ring-opening polymer is a polymer containing a repeating unit obtained by ring-opening polymerization of cyclopentene as a repeating unit constituting its main chain.

The ratio of the repeating unit formed by ring-opening polymerization of cyclopentene constituting the main chain of the cyclopentene ring-opening polymer is preferably 80 mol% or more, more preferably 90 mol% or more, based on all the repeating units. More preferably, it is 95 mol% or more, and particularly preferably, it is composed of only repeating units obtained by ring-opening polymerization of cyclopentene.

The cyclopentene ring-opening polymer contained in the polymer composition for anti-vibration rubber of the present embodiment is a repeating unit derived from another monomer copolymerizable with cyclopentene as long as the characteristics of the cyclopentene ring-opening polymer are maintained. May be contained. The proportion of repeating units derived from other copolymerizable monomers is preferably 20 mol% or less, more preferably 10 mol% or less, and 5 mol% or less, based on all repeating units. It is more preferable to have.

Examples of other monomers copolymerizable with cyclopentene include monocyclic olefins other than cyclopentene, monocyclic dienes, monocyclic trienes, polycyclic olefins, polycyclic dienes, polycyclic cyclic trienes, and the like. .. Examples of the monocyclic olefin other than cyclopentene include cyclopentene having a substituent and cyclooctene which may have a substituent. Examples of the monocyclic diene include 1,5-cyclooctadiene which may have a substituent. Examples of the monocyclic triene include 1,5,9-cyclododecatriene which may have a substituent. 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 which may have a substituent such as dodeca-4-ene are exemplified.

The molecular weight of the cyclopentene ring-opening polymer is not particularly limited, but the value of the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography may be 100,000 to 1,000,000. It is preferably 150,000 to 900,000, more preferably 200,000 to 800,000. By having the cyclopentene ring-opening polymer having such a molecular weight, a rubber crosslinked product having excellent mechanical strength can be obtained.

The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) of the cyclopentene ring-opening polymer measured by gel permeation chromatography is not particularly limited, but 4 It is 0.0 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 is not particularly limited, but can be set in the range of 10/90 to 90/10. From the viewpoint of obtaining a rubber crosslinked product having excellent low temperature characteristics, the range is preferably 90/10 to 51/49, and more preferably 90/10 to 55/45. Further, from the viewpoint of obtaining a rubber crosslinked product having excellent 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 is not particularly limited, and for example, a method for controlling the polymerization conditions when polymerizing cyclopentene to obtain a cyclopentene ring-opening polymer is used. Can be mentioned. As an example, the higher the polymerization temperature at the time of polymerizing cyclopentene, the higher the trans ratio can be, and the lower the monomer concentration in the polymerization solution, the higher the trans ratio can be.

The glass transition temperature (Tg) of the cyclopentene ring-opening polymer is not particularly limited, but is preferably −90 ° C. or lower, more preferably −95 ° C. or lower, from the viewpoint of exhibiting excellent properties at low temperatures. , More preferably −98 ° C. or lower. The glass transition temperature of the cyclopentene ring-opening polymer 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 may have a molecular structure consisting of only carbon atoms and hydrogen atoms, or 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. By containing such a modifying group, the affinity between the cyclopentene ring-opening polymer and the carbon-based material can be improved.

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, an oxygen atom, and the like. A modifying group containing an atom selected from the group consisting of a silicon atom and a silicon atom is more preferable, and a modifying group containing a silicon atom is further preferable.

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, and 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, and 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. Of these, from the viewpoint of improving the affinity between the cyclopentene ring-opening polymer and the carbon-based material, 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 and an oxysilyl group. , Or a hydrocarbon group containing these groups is preferable, and among them, an oxysilyl group is particularly preferable from the viewpoint of improving anti-vibration properties in the case of a rubber crosslinked product. The oxysilyl group refers to a group having a silicon-oxygen bond.

Specific examples of the oxysilyl group include an alkoxysilyl group, an aryloxysilyl group, an asyloxysilyl 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 into cyclopentene ring-opening polymer.

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 thereof include a silyl group.

The allyloxysilyl group is a group formed by bonding one or more allyloxy groups 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.

An 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 (acyloxy) (dimethyl). Examples thereof include a silyl group.

The alkylsiloxysilyl group is a group formed by bonding one or more alkylsiloxy groups 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.

Arylsiloxysilyl groups are groups formed by bonding one or more arylsiloxy groups to a silicon atom, and specific examples thereof include tris (triphenylsiloxy) silyl group, triphenylsiloxy (dimethyl) silyl group, and tris. (Diphenylsiloxy) silyl group and the like can be mentioned.

A hydroxysilyl group is a group formed by bonding one or more hydroxy groups 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 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, the cyclopentene ring-opening polymer has a modifying group at the end of the polymer chain. Is preferable.

When the cyclopentene ring-opening polymer has a modifying group at the end of the polymer chain, both polymer chain ends (both) even if the modifying group is introduced only at one of the polymer chain ends (one end). A modifying group may be introduced into the terminal), or a mixture of these may be used. Further, these may be mixed with an unmodified cyclopentene ring-opening polymer in which a specific modifying group is not introduced at the end of the polymer chain.

When the cyclopentene ring-opening polymer 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 is not particularly limited, but the modifying group is introduced. The value of the percentage of the number of terminal ends of the cyclopentene ring-opening polymer chain / the number of cyclopentene ring-opening polymer chains is preferably 60% or more, more preferably 80% or more, still more preferably 100% 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 ^{1 H-NMR spectrum measurement and the gel permeation chromatograph.} It can be obtained from the number average molecular weight obtained from the chromatography.

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

That is, the cyclopentene ring-opening polymer contains cyclopentene in the presence of a polymerization catalyst containing, for example, a transition metal compound (A) of Group 6 of the periodic table and an organoaluminum compound (B) represented by the following general formula (1). It can be obtained by ring-opening polymerization of the containing monomer.
(R ¹ ) _3-x Al (OR ² ) _x (1)
(In the above general formula (1), R ¹ and R ² represent hydrocarbon groups having 1 to 20 carbon atoms, and x is 0 <x <3.)

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), and specifically, a chromium atom, a molybdenum atom, or tungsten. It is a compound having an atom. Of these, 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. The compound having a transition metal atom of Group 6 of the periodic table is not particularly limited, and examples thereof include halides, alcoholates, allylates, and oxidates of the transition metal atom of Group 6 of the periodic table, and among these, the polymerization activity is high. Halides are preferred from the standpoint of high cost.

Specific examples of such a Group 6 transition metal compound (A) in 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 oxotetraphenylate. ; Etc. can be mentioned.

The amount of the Group 6 transition metal compound (A) used in the periodic table may be in the range of 1: 100 to 1: 200,000 in terms of the molar ratio of "Group 6 transition metal atom in the polymerization catalyst: cyclopentene". It is possible, preferably in the range of 1: 200 to 1: 150,000, more preferably in the range of 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, and various properties of the obtained rubber crosslinked product may be deteriorated.

The organoaluminum compound (B) is a compound represented by the above general formula (1). ^{Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 1} and R ² in the general formula (1) are methyl group, ethyl group, isopropyl group, n-propyl group, isobutyl group and n-butyl. Alkyl groups such as groups, t-butyl groups, n-hexyl groups and cyclohexyl groups; aryl groups such as phenyl groups, 4-methylphenyl groups, 2,6-dimethylphenyl groups, 2,6-diisopropylphenyl groups and naphthyl groups. ; Etc. can be mentioned. In the compound represented by the general formula (1), the ^{groups represented by R 1} and R ² may be the same or different, but the cis ratio of the obtained cyclopentene ring-opening polymer is described above. ^{Of R 1} and R ² , at least R ² is preferably an alkyl group in which four or more carbon atoms are continuously bonded, and in particular, n-butyl, from the viewpoint that it can be controlled within a suitable range. More preferably, it is a group, a 2-methyl-pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, or an n-decyl group.

Further, in the above general formula (1), x is 0 <x <3. That is, in the general formula (1), ^{the composition ratio of R 1} and OR ² can take arbitrary values in the respective ranges of 0 <3-x <3 and 0 <x <3, respectively. It is preferable that 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 can be controlled within the above-mentioned preferable range.

The organoaluminum compound (B) represented by the general formula (1) can be synthesized, for example, by reacting trialkylaluminum with an alcohol, as shown in the following general formula (2).
(R ¹ ) ₃ Al + xR ² OH → (R ¹ ) _3-x Al (OR ² ) _x + (R ¹ ) _x H (2)

As shown in the general formula (2), x in the general formula (1) can be arbitrarily controlled by defining the reaction ratio of the corresponding trialkylaluminum to the alcohol.

The amount of the organoaluminum compound (B) used varies depending on the type of the organoaluminum compound (B) used, but with respect to the group 6 transition metal atom of the periodic table that constitutes 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 occur easily during ring-opening polymerization.

The ring-opening polymerization reaction may be carried out without a solvent or in a solution. The solvent used when the ring-opening polymerization reaction is carried out in the solution is not particularly limited as long as it is inactive in the polymerization reaction and can dissolve cyclopentene used for the ring-opening polymerization or the above-mentioned polymerization catalyst. For example, a hydrocarbon solvent or a halogen solvent can be mentioned. 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. Alicyclic 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, as a compound having one olefinic carbon-carbon double bond having the above-mentioned modifying group and metathesis reactivity in the polymerization reaction system of the ring-opening polymerization reaction, the modified group-containing olefinically unsaturated carbonic acid is used. Hydrogen (C) may be present. Due to the presence of such a modifying group-containing olefinically unsaturated hydrocarbon (C), a modifying group can be introduced at the end of the polymer chain of the cyclopentene ring-opening polymer. For example, when an oxysilyl group is introduced at the end of the polymer chain of a cyclopentene ring-opening polymer, 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, which introduces a modifying group only at one end (one end) of the polymer chain of the cyclopentene ring-opening polymer. Vinyl (triethoxy) silane, allyl (trimethoxy) silane, allyl (methoxy) (dimethyl) silane, allyl (triethoxy) silane, allyl (ethoxy) (dimethyl) silane, styryl (trimethoxy) silane, styryl (triethoxy) silane, 2- Alkoxysilane compounds such as styrylethyl (triethoxy) silane, allyl (triethoxysilylmethyl) ether, allyl (triethoxysilylmethyl) (ethyl) amine; vinyl (triphenoxy) silane, allyl (triphenyloxy) silane, allyl (phenoxy) ) Allyloxysilane compounds such as (dimethyl) silane; asyloxysilane compounds such as vinyl (triacetoxy) silane, allyl (triacetoxy) silane, allyl (diacetoxy) methylsilane, allyl (acetoxy) (dimethyl) silane; allyltris (trimethyl) Alkylsiloxysilane compounds such as siloxy) silane; arylsiloxysilane compounds such as allyltris (triphenylsiloxy) silane; 1-allylheptamethyltrisiloxane, 1-allylnonamethyltetrasiloxane, 1-allylnonamethylcyclopentasiloxane, 1 -Polysiloxane compounds such as allylundecamethylcyclohexasiloxane; and the like. Further, 1,4-bis (trimethoxysilyl) -2-butene and 1,4-bis (tri) are used to introduce modifying groups into both ends (both ends) of the polymer chain of the cyclopentene ring-opening polymer. Alkoxysilane compounds such as ethoxysilyl) -2-butene and 1,4-bis (trimethoxysilylmethoxy) -2-butene; allyloxysilane compounds such as 1,4-bis (triphenoxysilyl) -2-butene; Asyloxysilane compounds such as 1,4-bis (triacetoxysilyl) -2-butene; alkylsiloxysilane compounds such as 1,4-bis [tris (trimethylsiloxy) silyl] -2-butene; 1,4-bis [Tris (triphenylsiloxy) silyl] -2-butene and other arylsiloxysilane compounds; 1,4-bis (heptamethyltrisiloxy) -2-butene, 1,4-bis (undecamethylcyclohexasiloxy)- Polysiloxane compounds such as 2-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 according to the molecular weight of the cyclopentene ring-opening polymer to be produced, but is used for the polymerization. The molar ratio to cyclopentene can be in the range of 1/100 to 1 / 100,000, preferably 1/200 to 1 / 50,000, more preferably 1/500 to 1 / 10,000. Is the range of. The modifying group-containing olefinically unsaturated hydrocarbon (C) also acts as a molecular weight modifier in addition to the action of introducing a modifying group into the polymer chain terminal of the cyclopentene ring-opening polymer.

When the above-mentioned modifying group is not introduced into the cyclopentene ring-opening polymer, 1-butene, 1-pentene, 1-butene, 1-pentene, 1- are used as molecular weight adjusting agents in order to adjust the molecular weight of the obtained cyclopentene ring-opening polymer. Olefin compounds such as hexene and 1-octene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl- A diolefin compound such as 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 not particularly limited, but is preferably 1 minute to 72 hours, more preferably 10 minutes to 20 hours.

Further, instead of the method using a polymerization catalyst containing the above-mentioned Group 6 transition metal compound (A) in the periodic table and the organoaluminum compound (B) represented by the general formula (1), a ruthenium carbene complex is used as the polymerization catalyst. It is also possible to produce a cyclopentene ring-opening polymer by a method of ring-opening polymerization of a monomer containing cyclopentene 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) benzylidene ruthenium dichloride, bis (triphenylphosphine) -3,3-diphenylpropenilidene ruthenium dichloride, (3-phenyl-1H-inden-1). -Ilidene) bis (tricyclohexylphosphine) ruthenium dichloride, bis (tricyclohexylphosphine) t-butylbinylidene ruthenium dichloride, bis (1,3-diisopropylimidazolin-2-iriden) benziliden ruthenium dichloride, bis (1,3-dicyclohexylmidazoline) -2-Ilidene) benziliden ruthenium dichloride, (1,3-dimeshtyl imidazoline -2-iriden) (tricyclohexylphosphine) benziliden ruthenium dichloride, (1,3-dimeshtyl imidazoline -2-iriden) (tricyclohexylphosylphos) Examples thereof include (phosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride, (1,3-dimesityl imidazolidine-2-ylidene) (tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride.

The amount of the ruthenium carbene complex used can be in the range of 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to the molar ratio of metallic ruthenium to cyclopentene in the catalyst. 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, 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 general formula (1) is used. The same solvent (hydrocarbon-based solvent, halogen-based solvent, etc.) as in the case of use can be used.

Further, the polymerization reaction temperature and the polymerization reaction time when the ruthenium carbene complex is used as the polymerization catalyst are also the same as those of the above-mentioned Group 6 transition metal compound (A) in the periodic table and the organoaluminum compound (B) represented by the general formula (1). This is the same as the polymerization reaction temperature and the polymerization reaction time when a polymerization catalyst containing the above is used.

Then, a method using 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 general formula (1), or a method using a ruthenium carbene 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 obtained in the above. The amount of the anti-aging 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 is obtained as the polymer solution, a known recovery method may be used to recover the polymer from the polymer solution. For example, after separating the solvent by steam stripping or the like, the polymer may be recovered. A method of filtering the solid and further drying it to obtain a solid rubber can be adopted.

The rubber component contained in the polymer composition for anti-vibration rubber of the present embodiment may contain other rubbers in addition to the cyclopentene ring-opening polymer. Examples of rubbers other than the cyclopentene ring-opening polymer include natural rubber (NR), isoprene rubber (IR), solution-polymerized SBR (solution-polymerized styrene-butadiene rubber), emulsified-polymerized SBR (emulsified-polymerized styrene-butadiene rubber), and low cis BR. (Butadiene 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 polymerization Styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polyisoprene-SBR block copolymer rubber, polystyrene-polybutadiene-polystyrene block copolymer, acrylic rubber, epichlorohydrin rubber, fluorine rubber, silicon rubber, ethylene -Examples include propylene rubber and urethane rubber. Of these, natural rubber, isoprene rubber, butadiene rubber, solution-polymerized styrene-butadiene rubber, emulsion-polymerized styrene-butadiene rubber, and ethylenepropylene diene rubber are preferable, and natural rubber is more preferable from the viewpoint of improving anti-vibration properties when used as a rubber cross-linking agent. It is preferably used. These rubbers can be used alone or in combination of two or more.

In the rubber component contained in the polymer composition for anti-vibration rubber of the present embodiment, the content of the cyclopentene ring-opening polymer is based on the total rubber component from the viewpoint of making the effect of the present invention more remarkable. It is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and preferably 90% by mass or less. On the other hand, the content of rubber other than the cyclopentene ring-opening polymer is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, based on the total rubber components. , Preferably 10% by mass or more.

The polymer composition for anti-vibration rubber according to the embodiment of the present invention contains a carbon-based material in the rubber component containing the cyclopentene ring-opening polymer described above.

The carbon-based material is not particularly limited, and a carbon-based material such as carbon black or graphite can be used. Of these, it is preferable to use carbon black.

Specific examples of carbon black include furnace black, acetylene black, thermal black, channel black and the like. 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, FEF and the like. Be done. Specific examples of graphite include natural graphite such as scaly graphite and scaly graphite, and artificial graphite. The carbon-based materials described above can be used alone or in combination of two or more.

Carbon-based material, the nitrogen adsorption specific surface area _(N 2 SA) of not more than 200 meters ² / g, preferably from 5 to 200 m ² / g, more preferably 20~150m ² / g. The amount of dibutyl phthalate (DBP) adsorbed is preferably 5 to 200 ml / 100 g, more preferably 50 to 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 the carbon-based material in the polymer composition for anti-vibration rubber of the present embodiment is 1 to 200 parts by mass, preferably 20 parts by mass with respect to 100 parts by mass of the rubber component containing the cyclopentene ring-opening polymer. It is ~ 150 parts by mass, more preferably 30 to 100 parts by mass. By setting the content of the carbon-based material in the above range, it is possible to enhance the anti-vibration characteristics when the rubber is crosslinked, and it is possible to provide a highly versatile anti-vibration rubber. If the content of the carbon-based material is too small, the obtained rubber crosslinked product will be inferior in mechanical properties. On the other hand, if the content of the carbon-based material is too large, the processability of the polymer composition may decrease.

In addition to the above components, the polymer composition for anti-vibration rubber of the present embodiment contains a cross-linking agent, a cross-linking accelerator, a cross-linking activator, 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 the system material can be blended.

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

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 diolto-trilguanidine and 1-orthotrilbiguanidine; thiourea-based cross-linking accelerators; thiazole-based cross-linking accelerators; thiuram-based cross-linking accelerators; ; Etc. can be mentioned. 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 cross-linking accelerator is preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the rubber component in the polymer composition for anti-vibration rubber.

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 when a higher fatty acid is used as the cross-linking activator, the blending amount is preferably with respect to 100 parts by mass of the rubber component in the polymer composition for anti-vibration rubber. It is 0.05 to 15 parts by mass, more preferably 0.5 to 5 parts by mass, and when zinc oxide is used as the cross-linking activator, the blending amount is 100 parts by mass of the rubber component in the polymer composition for anti-vibration rubber. It is preferably 0.05 to 15 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to parts. These cross-linking activators may be used alone or in combination of two or more.

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 can be used.

Examples of fillers other than carbon-based materials 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 starch and polystyrene powder. Examples include powders such as organic powders; short fibers such as glass fibers (milled fibers), carbon fibers, aramid fibers, and 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 for anti-vibration rubber of the present embodiment is not particularly limited, and each component may be kneaded according to a conventional method. For example, a carbon-based material excluding a cross-linking agent and a cross-linking accelerator may be used. After kneading a compounding agent such as a material and a rubber component such as a cycloolefin ring-opening polymer, a cross-linking agent and a cross-linking accelerator can be mixed with the kneaded product to obtain a desired composition. The kneading temperature of the compounding agent excluding the cross-linking agent and the cross-linking 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. The kneaded product and the cross-linking agent and the cross-linking accelerator can be mixed at 100 ° C. or lower, preferably after cooling to 80 ° C. or lower.

The rubber crosslinked product according to the embodiment of the present invention can be obtained by crosslinking the above-mentioned polymer composition for anti-vibration rubber.

The cross-linking method for cross-linking the anti-vibration rubber polymer composition of the present embodiment is not particularly limited and may be selected according to the shape, size and the like of the cross-linked rubber product. In this case, the polymer composition for anti-vibration rubber may be filled and heated in a mold to be crosslinked at the same time as molding, and the pre-molded polymer composition for anti-vibration rubber may be heated. May be crosslinked. The cross-linking temperature is preferably 120 to 200 ° C., more preferably 140 to 180 ° C., and the cross-linking time is about 1 to 120 minutes.

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

Molding of the polymer composition for anti-vibration rubber can be performed, for example, by using a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll or the like. Further, as the heating method, a general method used for cross-linking rubber such as press heating, steam heating, oven heating, hot air heating and the like may be appropriately selected.

Since the crosslinked rubber of the present embodiment thus obtained has a low dynamic ratio and a high loss tangent, it is suitably used as a vibration-proof rubber having excellent vibration-proof performance. Further, since the crosslinked rubber of the present embodiment can reduce both high-frequency and low-frequency vibrations, it is suitably used as a highly versatile anti-vibration rubber.

Since the anti-vibration rubber according to the embodiment of the present invention is obtained by using the above-mentioned crosslinked rubber, the anti-vibration rubber of the present embodiment has excellent anti-vibration characteristics and high versatility. Therefore, the anti-vibration rubber of the present embodiment can be used as various anti-vibration members for, for example, railroad vehicles, generators, automobiles, trucks / buses, ships, houses, and the like. Further, since the anti-vibration rubber of the present embodiment uses a rubber crosslinked product that can reduce both low-frequency and high-frequency vibrations, an engine mount member that generates low-frequency and high-frequency vibrations and high-frequency vibrations are generated. It can be widely used for applications such as suspension members. Therefore, the anti-vibration rubber of the present embodiment is particularly preferably used for various mounts such as engine mounts for automobiles and liquid-filled mounts, and anti-vibration rubbers for automobiles such as various bushes, dampers, support rubbers, and bearings. Be done.

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

[Molecular weight of cyclopentene ring-opening polymer, butadiene rubber]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the cyclopentene ring-opening polymer and the butadiene rubber were measured by gel permeation chromatography (GPC). For measurement by GPC, two H-type columns (Tosoh, HZ-M) are connected in series by a GPC system (Tosoh, HLC-8220), and tetrahydrofuran is used as a solvent at a column temperature of 40 ° C. went. A differential refractometer (manufactured by Tosoh Corporation, RI-8320) was used as the detector. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured as polystyrene-equivalent values.

[Glass transition temperature (Tg) of cyclopentene ring-opening polymer]
Using a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Corporation, X-DSC7000), measurements were taken from −150 ° C. to 40 ° C. at a temperature rise of 10 ° C./min.

[Sis / trans ratio of cyclopentene ring-opening polymer, vinyl / cis / trans ratio of butadiene rubber]
¹³ Determined by C-NMR spectrum measurement.

[Introduction rate of oxysilyl group in terminally modified cyclopentene ring-opening 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 polymer main chain was obtained, and this peak integrated value was obtained. Based on the ratio of Percentage of] was calculated.

[Static elastic modulus (E)]
The polymer composition as a sample was press-molded at 150 ° C. for 20 minutes while pressurizing using a mold to obtain a columnar rubber crosslinked product (test piece) having a diameter of 6 mm and a thickness of 7.5 mm. .. Using the obtained columnar rubber crosslinked product, in accordance with JIS K6386: 1999, the deflection in the range of the deformation amount of 2 mm was applied three times at a test speed of 5 mm / min in the compression mode, and in the third loading process. The load (N) when a compressive strain of 5% was applied was measured. The static elastic modulus (E) was calculated by the following formula.
E = F / A ・ ε
E: Static elastic modulus (MPa)
F: Load (N) when a compressive strain of 5% is applied.
A: Original cross-sectional area of the test piece (mm ² )
ε: Compressive strain relative to the thickness of the test piece before compression. In the case of a compressive strain of 5%, it becomes 0.05.

[Dynamic storage modulus (E') and loss tangent (tan δ)]
The polymer composition as a sample was press-molded at 150 ° C. for 20 minutes while pressurizing using a mold to obtain a columnar rubber crosslinked product (test piece) having a diameter of 6 mm and a thickness of 7.5 mm. .. Using the obtained columnar rubber crosslinked product, measurement mode: compression mode, static strain: 5% using a dynamic viscoelastic device (manufactured by METRAVIB, DMA + 1000) in accordance with JIS K6394: 2007. , Dynamic strain: 0.2% or 2%, Measurement frequency: 100 Hz, dynamic storage elastic modulus (E') is measured, and measurement mode: compression mode, static strain: 5%, dynamic Loss tangent (tan δ) was measured under the conditions of target strain: 2% and measurement frequency: 10 Hz.

The loss tangent (tan δ) is one of the indexes for evaluating the vibration isolation characteristics of the vibration isolation material, and the larger the loss tangent value, the better the vibration isolation performance. Further, the loss tangent (tan δ) under the above measurement conditions (dynamic strain: 2%, measurement frequency: 10 Hz) has vibration isolation characteristics against low frequency vibration (for example, prevention of engine mount against low frequency idling and shaking of automobiles). Vibration performance) is evaluated.

[Dynamic magnification (E'/ E)]
The dynamic magnification (E'/ E) was obtained by calculating the ratio of the static elastic modulus (E) and the dynamic storage elastic modulus (E') measured according to the above method.

The dynamic magnification (E'/ E) is one of the indexes for evaluating the anti-vibration characteristics of the anti-vibration material, and the lower the value of the dynamic magnification, the better the anti-vibration performance. The dynamic magnification (E'/ E) under the above measurement conditions (dynamic strain: 0.2%, measurement frequency: 100 Hz) is the vibration isolation characteristic against high frequency vibration (for example, the prevention of the engine mount from the interior noise of an automobile). The vibration performance) is evaluated, and the dynamic magnification (E'/ E) under the above measurement conditions (dynamic strain: 2%, measurement frequency: 100 Hz) is the vibration isolation characteristic against high frequency vibration (for example, the interior noise of an automobile). , Vibration countermeasures Ride comfort, vibration isolation performance of suspension against steering stability, etc.) are evaluated.

[Reference Example 1] Preparation of diisobutylaluminum mono (n-hexanexide) / toluene solution (2.5%) 88 parts of toluene and 25.4% triisobutyl in a glass container containing a stir bar under a nitrogen atmosphere. 7.8 parts of an aluminum / n-hexane solution (manufactured by Toso Finechem) was added. Then, the container was cooled to −45 ° C., and 1.02 parts of n-hexanol (a molar amount relative 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%).

[Synthesis Example 1] Production of bi-terminal modified cyclopentene ring-opening polymer (a1) _{Prepared with 87 parts of 1.0% WCl 6} / toluene solution and Reference Example 1 in a glass container containing a stirrer under a nitrogen atmosphere. 43 parts of a 2.5% diisobutylaluminum mono (n-hexoxide) / toluene solution was added, and the mixture was 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 part was added, and the 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 an antiaging agent (trade name “Irganox 1520L”) was applied to 100 parts of the polymer obtained by the polymerization. 0.2 part of "Irganox" (registered trademark) manufactured by Chivas Specialty Chemicals Co., Ltd. was added. Next, the polymer was coagulated with a large amount of ethanol to recover the polymer, and the polymer was vacuum-dried at 40 ° C. for 3 days to introduce triethoxysilyl into both ends of the modified cyclopentene ring-opening polymer (a1) 78 at both ends. I got a part. The weight average molecular weight (Mw) of the obtained double-ended cyclopentene ring-opening polymer (a1) is 366,000, the glass transition temperature (Tg) is −106 ° C., and the cis / trans ratio is cis / trans = 55/45. The introduction rate of the oxysilyl group was 143%.

[Synthesis Example 2] Production of Unmodified Cyclopentene Ring-Opening Polymer (a2) Under a nitrogen atmosphere _{, prepared with 87 parts of 1.0% WCl 6} / toluene solution and Reference Example 1 in a glass container containing a stirrer. A catalytic solution was obtained by adding 43 parts of a 2.5% diisobutylaluminum mono (n-hexoxide) / toluene solution and stirring for 15 minutes. Then, under a nitrogen atmosphere, 300 parts of cyclopentene and 0.26 parts of 1-hexene were added to a pressure-resistant glass reaction vessel equipped with a stirrer, 130 parts of the catalyst solution prepared above was added thereto, and the mixture was polymerized at 0 ° C. for 4 hours. The reaction was carried out. 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 an antiaging agent (trade name "Irganox 1520L") was applied to 100 parts of the polymer obtained by the polymerization. 0.2 part (manufactured by Ciba Speciality Chemicals) was added. Then, the polymer was coagulated with a large amount of ethanol to recover the polymer, and vacuum dried at 40 ° C. for 3 days to obtain 74 parts of an unmodified cyclopentene ring-opening polymer (a2). The obtained weight average molecular weight (Mw) was 389,000, the glass transition temperature (Tg) was −110 ° C., and the cis / trans ratio was cis / trans = 81/19.

[Synthesis Example 3] Production of Unmodified Cyclopentene Ring-Opening Polymer (a3) Under a nitrogen atmosphere, 1000 parts of cyclopentene, 0.42 parts of 1-hexene, and 990 parts of toluene were placed in a pressure-resistant glass reaction vessel containing a magnetic stirrer. added. Next, 0.068 parts of (3-phenyl-1H-indene-1-iriden) bis (tricyclohexylphosphine) ruthenium dichloride dissolved in 10 parts of toluene was added, and the mixture was polymerized at room temperature for 3 hours. After the polymerization reaction for 3 hours, excess vinyl ethyl ether was added to the pressure-resistant glass reaction vessel to stop the polymerization, and then an antiaging agent (trade name "Irganox 1520L") was applied to 100 parts of the polymer obtained by the polymerization. , Made by Chivas Specialty Chemicals Co., Ltd.) 0.2 part was added. Then, the polymer was coagulated with a large amount of ethanol to recover the polymer, and vacuum dried at 50 ° C. for 24 hours to obtain 650 parts of an unmodified cyclopentene ring-opening polymer (a3). The weight average molecular weight of the obtained unmodified cyclopentene ring-opening polymer (a3) is 434,000 (Mw), the glass transition temperature (Tg) is −98 ° C., and the cis / trans ratio is cis / trans = 17/83. Met.

[Synthesis Example 4] Production of Terminally Modified Butadiene Rubber (a4) After charging 5670 g of cyclohexane and 700 g of 1,3-butadiene in an autoclave with a stirrer under a nitrogen atmosphere, n-butyllithium was added to cyclohexane and 1,3-butadiene. An amount necessary for neutralizing the impurities that inhibit the polymerization contained in and was added, and 8.33 mmol was added as the amount of n-butyllithium used for 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 rate 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 the molar amount of n-butyllithium used for polymerization) was added in a 40% cyclohexane solution and reacted for 30 minutes. Then, 2.92 mmol of polyorganosiloxane represented by the following formula (3) (corresponding to 0.35 times the molar amount of n-butyllithium used for polymerization) was further added in a 20% xylene solution, and the reaction was carried out for 30 minutes. Then, 8.33 mmol of tetramethoxysilane (corresponding to 1 times the molar amount of n-butyllithium used for polymerization) was added in a 25% cyclohexane solution, and the mixture was reacted 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 the terminal-modified butadiene rubber (a4). Then, 0.2 part of an antiaging agent (trade name "Irganox 1520L", manufactured by Ciba Speciality Chemicals Co., Ltd.) was added to the obtained solution per 100 parts of the rubber component, and the solvent was removed by steam stripping. The terminal-modified butadiene rubber (a4) was obtained by vacuum drying at 60 ° C. for 24 hours. The weight average molecular weight of the obtained terminally modified butadiene rubber (a4) was 553,000 (Mw), and the vinyl / cis / trans ratio was vinyl / cis / trans = 10/45/45.

[Example 1]
In a Banbury-type mixer, 70 parts of the double-ended cyclopentene ring-opening polymer (a1) and 30 parts of natural rubber (SMR-CV60) obtained in Synthesis Example 1 were kneaded for 30 seconds, and then 2 parts of stearic acid, 5 parts of zinc oxide, carbon black (trade name "Seast SO (FEF)", manufactured by Tokai Carbon Co., Ltd., "Seast" is a registered trademark, nitrogen adsorption specific surface area (BET method): 42 m ² / g) 50 parts, naphthen oil ( Product name "Diana Process Oil NS-100", manufactured by Idemitsu Kosan Co., Ltd.) 5 parts, and N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine (trade name "Nocrack 6C") as an anti-aging agent , Manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., "Nocrack" is a registered trademark), kneaded at 100 ° C. for 180 seconds, cleaned the compounding agent remaining on the top of the ram, and then 150 more. Kneading was performed for seconds, and the kneaded product was discharged from the mixer. The kneaded product was then cooled to room temperature and then rolled on an open roll at 60 ° C. to obtain 1.4 parts of sulfur and N- (tert-butyl) -2-benzothia as a cross-linking accelerator. After kneading 1.2 parts of zolyl sulfeneamide (trade name "Noxeller NS-P", manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., "Noxeller" is a registered trademark), 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 the static elastic modulus, dynamic storage elastic modulus, loss tangent, and dynamic magnification were calculated and evaluated. The results are shown in Table 1.

[Example 2]
This was carried out except that 70 parts of the unmodified cyclopentene ring-opening polymer (a2) obtained in Synthesis Example 2 was used instead of 70 parts of the double-ended cyclopentene ring-opening polymer (a1) obtained in Synthesis Example 1. 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.

[Example 3]
This was carried out except that 70 parts of the unmodified cyclopentene ring-opening polymer (a3) obtained in Synthesis Example 3 was used instead of 70 parts of the double-ended cyclopentene ring-opening polymer (a1) obtained in Synthesis Example 1. 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]
Instead of 70 parts of the double-ended cyclopentene ring-opening polymer (a1) obtained in Synthesis Example 1, unmodified butadiene rubber (trade name "Nipol BR1220", manufactured by Nippon Zeon, "Nipol" contains a registered trademark, cis. A polymer composition was obtained in the same manner as in Example 1 except that 70 parts (amount of 97% or more) was used, and the evaluation was carried out in the same manner. The results are shown in Table 1.

[Comparative Example 2]
Example 1 and Example 1 except that 70 parts of the terminal-modified butadiene rubber (a4) obtained in Synthesis Example 4 was used instead of 70 parts of the double-ended cyclopentene ring-opening polymer (a1) 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.

[Comparative Example 3]
In a Banbury-type mixer, 70 parts of the terminal-modified butadiene rubber (a4) and 30 parts of natural rubber (SMR-CV60) obtained in Synthesis Example 4 are kneaded for 30 seconds, and then silica (trade name "NIPSIL AQ", Tosoh). -Silica, "NIPSIL" is a registered trademark) 30 parts, Naften oil (trade name "Diana Process Oil NS-100", manufactured by Idemitsu Kosan Co., Ltd.) 15 parts, Bis (3- (triethoxysilyl) as a silane coupling agent ) Propyl) Tetrasulfide (trade name "Si69", manufactured by Degussa, "Si69" is a registered trademark) is added and kneaded at 100 ° C. for 90 seconds, then 1 part of stearic acid and 5 parts of zinc oxide. , And 2 parts of N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine (trade name "Nocrack 6C", manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) as an anti-aging agent, and further 180 Kneading was performed for 2 seconds, and the kneaded product was discharged from the mixer. Then, after cooling to room temperature, in an open roll at 50 ° C., the obtained kneaded product, 1.4 parts of sulfur and N-tert-butyl-2-benzothiazolyl sulphenamide as a cross-linking accelerator (trade name "" Knead a mixture of 1.2 parts of Noxeller NS-P (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) and 1.2 parts of 1,3-phenylguanidine (trade name" Noxeller D "manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.). After that, a sheet-shaped polymer composition was obtained. Then, the obtained polymer composition was used for evaluation in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 4]
Similar to Comparative Example 3 except that 70 parts of the unmodified cyclopentene ring-opening polymer (a2) obtained in Synthesis Example 2 was used instead of 70 parts of the terminal-modified butadiene rubber (a4) obtained in Synthesis Example 4. The polymer composition was obtained and evaluated in the same manner. The results are shown in Table 1.

表１に示すように、シクロペンテン開環重合体および炭素系材料を含有する重合体組成物を架橋して得られたゴム架橋物（実施例１〜３）は、シクロペンテン開環重合体に代えて、ブタジエンゴムを用いた場合（比較例１、２）に比べて、動倍率が低く、かつ損失正接が高くなり、防振ゴムとして優れるものであった。また炭素系材料に代えて、シリカを用いた場合（比較例３、４）は、動倍率が高く、損失正接が低くなり、高い防振性能は得られなかった。

As shown in Table 1, the rubber crosslinked product (Examples 1 to 3) obtained by cross-linking the cyclopentene ring-opening polymer and the polymer composition containing a carbon-based material is replaced with the cyclopentene ring-opening polymer. Compared with the case where butadiene rubber was used (Comparative Examples 1 and 2), the dynamic ratio was low and the loss tangent was high, which was excellent as a vibration-proof rubber. Further, when silica was used instead of the carbon-based material (Comparative Examples 3 and 4), the dynamic magnification was high, the loss tangent was low, and high vibration isolation performance could not be obtained.

Further, the rubber crosslinked product (Examples 1 to 3) obtained by cross-linking a polymer composition containing a cyclopentene ring-opening polymer and a carbon-based material is excellent in both high-frequency and low-frequency vibrations. It shows anti-vibration performance and is suitable as a highly versatile anti-vibration rubber.

Although the embodiments of the present invention have been described above with reference to examples, the present invention is not limited to the specific embodiments and examples, and various within the scope of the invention described in the claims. Can be transformed and changed.

Claims (4)

A rubber component containing a cyclopentene ring-opening polymer and
Contains carbon-based materials with a nitrogen adsorption specific surface area of 200 m ^{2 / g or less.}
A polymer composition for anti-vibration rubber in which the content of the carbon-based material is 30 to 100 parts by mass with respect to 100 parts by mass of the rubber component. A rubber crosslinked product obtained by cross-linking the polymer composition for anti-vibration rubber according to claim 1. An anti-vibration rubber using the crosslinked rubber product according to claim 2. The anti-vibration rubber according to claim 3, which is used for an engine mount member or a suspension member.