JP5614472B2 - Cyclopentene ring-opening polymer composition - Google Patents

Description

  The present invention relates to a cyclopentene ring-opening polymer composition, and more particularly to a cyclopentene ring-opening polymer composition containing inorganic particles such as carbon black and silica.

A cyclopentene ring-opening polymer obtained by metathesis ring-opening polymerization of cyclopentene is widely known as a rubber material, and is used as a rubber composition by blending with inorganic particles such as carbon black and silica. Generally, a cyclopentene ring-opening polymer is composed of a periodic table Group 6 transition metal compound such as WCl ₆ and MoCl ₅ and an organometallic compound such as an aluminum compound and a tin compound, as disclosed in, for example, Patent Document 1. The so-called Ziegler-Natta catalyst is used for bulk polymerization or solution polymerization. In some cases, α-olefin is added as a molecular weight modifier. Since the cyclopentene ring-opened polymer thus obtained consists of only carbon atoms and hydrogen atoms, it has a low affinity for inorganic particles such as carbon black and silica. Therefore, even if inorganic particles are blended with such a cyclopentene ring-opening polymer to form a composition, the effect of improving the mechanical properties by the inorganic particles is not sufficiently exhibited.

  As one of the techniques for improving the affinity of the polymer for inorganic particles, a technique of introducing a functional group containing a hetero atom at the end of the polymer chain is well known. A suitable technique for introducing a functional group has not been established. Patent Document 2 discloses a cyclic olefin in which a cyclic olefin such as cyclooctadiene and a bifunctional acyclic olefin are subjected to a metathesis reaction under conditions of 50 to 90 ° C. and functional groups are introduced at both ends of a polymer chain. Ring-opening polymers have been reported. However, according to studies by the present inventors, when cyclopentene is polymerized under the conditions described in these documents, there is a problem that the molecular weight of the resulting cyclopentene ring-opening polymer is too low. Furthermore, this method has a problem that the ratio of polymer chain ends into which functional groups can be introduced is low, and a high molecular weight cyclopentene ring-opening polymer in which functional groups are introduced into the polymer chain ends cannot be produced efficiently.

JP-A-54-50598 Japanese National Patent Publication No. 11-514043

  An object of the present invention is to provide a cyclopentene ring-opening polymer composition having improved mechanical properties and improved affinity with inorganic particles.

  As a result of intensive studies to achieve the above object, the present inventors have identified a ruthenium-carbene complex as a catalyst in the presence of a compound containing a functional group and an ethylenically unsaturated bond in the molecule. It was found that cyclopentene ring-opening polymer having a sufficient molecular weight and having a functional group introduced efficiently at the end of the polymer chain can be obtained by ring-opening polymerization of cyclopentene at the polymerization temperature of The present invention has been completed based on this finding.

Thus, according to the present invention, a functional group containing silicic MotoHara child to more than 25% of the polymer chain end all, and a number average molecular weight of Lupolen polystyrene conversion measured by gel permeation chromatography Cyclopentene ring-opening polymer having (Mn) of 10,000 to 1,000,000 (provided that when repeating units derived from monomers other than cyclopentene are included, the ratio of the repeating units is And 10% mol or less) , inorganic particles selected from silica and carbon black , and a rubber composition other than the cyclopentene ring-opening polymer blended as desired.

  According to the present invention, a cyclopentene ring-opening polymer composition having improved mechanical properties and improved affinity with inorganic particles is provided.

Cyclopentene ring-opened polymer for use in the present invention has a functional group containing a silicic MotoHara child to more than 25% of the polymer chain end all, and is measured by gel permeation chromatography Lupo polystyrene Conversion Cyclopentene ring-opening polymer having a number average molecular weight (Mn) of 10,000 to 1,000,000 (however, when it contains a repeating unit derived from a monomer other than cyclopentene, the proportion of the repeating unit is It is 10% mol or less with respect to the repeating unit) .

  This cyclopentene ring-opening polymer can be represented by the following general formula (1).

In the general formula (1), X and Y each independently represents a monovalent group, at least one of X and Y, is a functional group containing a silicic MotoHara child. N is a positive integer. However, in the general formula (1), the ratio of the cis type / trans type in the existing double bond may be arbitrary, and repeating units other than n repeating units (repeating units formed by ring-opening polymerization of cyclopentene) It may contain.

Such a cyclopentene ring-opening polymer has a functional group containing a silicon atom at the end of the polymer chain, and thus has high affinity with inorganic particles such as carbon black and silica .

The functional group containing silicic atom, an alkyl silyl group, alkoxysilyl group, a hydrocarbon group containing a silanol group or these groups are exemplified. Also, the functional group may be a functional group containing a plurality of groups mentioned above.

Examples of particularly preferred functional groups from the viewpoint of improving the affinity with the cyclopentene ring-opening polymer and inorganic particles, A alkoxysilyl group and a hydrocarbon group containing a silanol group or these groups.

In the general formula (1), X and Y are, in the case of silicic MotoHara terminal monovalent group other than a functional group containing, the monovalent group is not particularly limited, usually, a hydrogen atom or It is a C1-C20 hydrocarbon group.

  The cyclopentene ring-opening polymer used in the present invention is specific to both polymer chain ends (both ends) even if a specific functional group is introduced only at one polymer chain end (one end). A functional group may be introduced, or a mixture of these may be used. Furthermore, these may be mixed with a cyclopentene ring-opening polymer in which a specific functional group is not introduced at the end of the polymer chain.

In the cyclopentene ring-opening polymer used in the present invention, the introduction ratio of the specific functional group with respect to the polymer chain end is not particularly limited, but from the viewpoint of improving the affinity between the cyclopentene ring-opening polymer and the inorganic particles, The percentage value of the number of cyclopentene ring-opening polymer terminals / total number of cyclopentene ring-opening polymer chain terminals into which a specific functional group has been introduced) is preferably 25% or more, more preferably 30% or more, It is preferably ˜100%. In the cyclopentene ring-opening polymer of the present invention, the introduction rate of the specific functional group with respect to the polymer chain end can be measured by ¹ H-NMR spectrum measurement. Specifically, the cyclopentene ring-opening polymer main chain It can be determined by comparing the integrated value of the peak derived from the proton of the carbon-carbon double bond present therein, the integrated value of the peak derived from the specific functional group, and the number average molecular weight (Mn).

In the cyclopentene ring-opening polymer used in the present invention, the repeating unit may be composed only of a repeating unit obtained by ring-opening polymerization of cyclopentene, but is derived from another monomer copolymerizable with cyclopentene. It may contain repeating units. However, from the viewpoint of improving the characteristics of the cyclopentene ring-opening polymer, the proportion of the repeating unit derived from other monomers, Ru der 1 0% molar or less with respect to the total repeating units. Examples of other monomers copolymerizable with cyclopentene include monocyclic olefins other than cyclopentene and polycyclic olefins. Examples of the monocyclic olefin include cyclooctene and cyclooctadiene which may have a substituent, and examples of the polycyclic olefin include a norbornene compound which may have an arbitrary substituent.

  The molecular weight of the cyclopentene ring-opening polymer used in the present invention is 10,000 to 1,000,000 as the value of polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography, preferably It is 20,000-900,000, More preferably, it is 40,000-800,000. By having such a molecular weight, it becomes possible to provide a polymer composition having excellent mechanical properties.

  The ratio (Mw / Mn) of polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) of the cyclopentene ring-opening polymer used in the present invention, as measured by gel permeation chromatography, is particularly Although not limited, it is usually 3.0 or less, preferably 2.5 or less, and more preferably 2.0 or less. By having such Mw / Mn, a polymer composition having more excellent mechanical properties can be provided.

  The method for producing the cyclopentene ring-opening polymer used in the present invention is not particularly limited, but the production method suitably used is the method described below.

That is, in the presence of a compound containing a functional group and an ethylenically unsaturated bond containing silicic MotoHara element in the molecule, ruthenium - carbene complex as a catalyst, a cyclopentene polymerization temperature below 20 ° C. Ring-opening polymerization (along with other monomers copolymerizable with cyclopentene, if necessary).

In this method, silicic MotoHara child suitably compounds used functional group and an ethylenically unsaturated bond contained as the compound containing in the molecule is a compound represented by the following general formula (2).

In the formula (2), X and Y each independently represents a monovalent group, at least one of X and Y, is a functional group containing a silicic MotoHara child. Further, X and Y are, silicic when MotoHara element is a monovalent group other than the functional group containing, but not limited thereof monovalent radical, especially, usually, a hydrogen atom or 1 to 20 carbon atoms It is a hydrocarbon group.

  In General Formula (2), preferable groups as X and Y are the same as preferable groups as X and Y in General Formula (1).

Of X and Y in the general formula (2), when using a compound which is a functional group containing only one of cliff Lee MotoHara element, that particular cyclopentene functional group introduced open at one end of the polymer chain A ring polymer is obtained. Specific examples of such compounds include A Lil trimethoxysilane, allyl triethoxysilane, allyl trichlorosilane, styryl trimethoxysilane.

When using a compound which is a functional group containing both cliff Lee MotoHara terminal of X and Y in the general formula (2), cyclopentene ring-opening polymer that particular functional group is introduced at both ends of the polymer chain Is obtained .

In the above production method, compound a functional group and an ethylenically unsaturated bond contained in the molecule containing silicic MotoHara child may be used alone, or two or more It can also be used together.

  In the above production method, the ruthenium-carbene complex used as the polymerization catalyst is represented by the following general formula (3).

In General Formula (3), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. X ¹ and X ² each independently represent an arbitrary anionic ligand. L ¹ and L ² represent any neutral electron-donating compound. In addition, 2, 3, 4, 5 or 6 of R ¹ , R ² , X ¹ , X ² , L ¹ and L ² are bonded to each other to form a multidentate chelating ligand. May be.

In the general formula (3), the anionic ligands X ¹ and X ² are ligands having a negative charge when separated from the central metal, for example, halogens such as F, Cl, Br, and I An atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxy group, an aryloxy group, a carboxyl group, etc. can be mentioned. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

The neutral electron-donating compounds L ¹ and L ² may be any ligand as long as it has a neutral charge when pulled away from the central metal. Specific examples thereof include carbonyl, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, thiocyanates, heteroatom-containing carbene compounds, and the like. It is done. Among these, phosphines, pyridines, and hetero atom-containing carbene compounds are preferable, and trialkylphosphine and N atom-containing carbene compounds are more preferable.

The ^R 1, ^{R 2} in the general formula (3), a hydrogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group, a carboxyl group, C2-C20 alkenyloxy group, C2-C20 alkynyloxy group, aryloxy group, C2-C20 alkoxycarbonyl group, C1-C20 alkylthio group, arylthio group, C1-C1 A 20 alkylsulfonyl group, a C1-C20 alkylsulfinyl group, etc. are mentioned.

  Specific examples of the ruthenium carbene complex include bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (triphenylphosphine) -3,3-diphenylpropenylidene ruthenium dichloride, bis (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride. Bis (1,3-diisopropylimidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazoline-2-ylidene) benzylidene ruthenium dichloride, (1,3-dimesitylimidazoline-2-ylidene) ( Tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene Ruthenium-carbene catalysts such as ruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride, (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride . The ruthenium-carbene complex may be used alone or in combination of two or more.

  The amount of ruthenium-carbene complex used is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1: 1, as the molar ratio of (metal ruthenium: cyclopentene in the catalyst). The range is 500,000, more preferably 1: 10,000 to 1: 1,000,000. If the amount of the polymerization catalyst used is too small, the polymerization reaction may not proceed sufficiently. On the other hand, if too much, removal of the catalyst residue from the resulting cyclopentene ring-opening polymer becomes difficult.

  The polymerization reaction may be performed in the absence of a solvent or in a solution. When polymerizing in solution, the solvent used is inactive in the polymerization reaction, and is not particularly limited as long as it is a solvent that can dissolve cyclopentene, ruthenium-carbene complex, etc. used in the polymerization, but it is a hydrocarbon solvent or halogen solvent. Is preferably used. Examples of hydrocarbon 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 methylcyclohexane. Alicyclic hydrocarbons; and the like. Examples of the halogen solvent include alkyl halogens such as dichloromethane and chloroform; aromatic halogens such as chlorobenzene and dichlorobenzene.

  In said manufacturing method, superposition | polymerization temperature is less than 20 degreeC, Preferably it is -100 degreeC or more and less than 15 degreeC, More preferably, it is -80 degreeC or more and less than 10 degreeC. If the polymerization temperature is too high, the molecular weight of the resulting cyclopentene ring-opening polymer is too low, and if the polymerization temperature is too low, the polymerization rate may be too low.

  The polymerization reaction time is preferably 1 minute to 72 hours, more preferably 5 hours to 20 hours. After the polymerization conversion rate reaches a predetermined value, a cyclopentene ring-opened polymer can be produced by adding a known polymerization terminator to the polymerization system and stopping the polymerization.

  If desired, an anti-aging agent such as a phenol-based stabilizer, a phosphorus-based stabilizer, or a sulfur-based stabilizer may be added to the obtained polymer solution. What is necessary is just to determine suitably the addition amount of an anti-aging agent according to the kind etc. Furthermore, you may mix | blend extension oil if desired.

  The method for obtaining the polymer from the polymer solution may be a known method. For example, after separating the solvent by steam stripping or the like, the solid is filtered off and further dried to obtain a solid rubber. The acquisition method can be adopted.

The polymer composition of the present invention is a polymer composition comprising the cyclopentene ring-opening polymer and inorganic particles. The inorganic particles are silica or carbon black is preferably used.

  Specific examples of silica that can be used as inorganic particles in the polymer composition of the present invention are disclosed in, for example, dry method white carbon, wet method white carbon, colloidal silica, and JP-A-62-62838. Examples include precipitated silica. Among these, wet method white carbon mainly containing hydrous silicic acid is preferable. Alternatively, a carbon-silica dual phase filler in which silica is supported on the carbon black surface may be used. These silicas can be used alone or in combination of two or more.

The nitrogen adsorption specific surface area (measured by the BET method according to ASTM D3037-81) of silica is preferably 50 to 400 m ² / g, more preferably 100 to 220 m ² / g. Moreover, it is preferable that the pH of a silica is less than pH 7, and it is more preferable that it is pH 5-6.9. Within these ranges, the affinity between the cyclopentene ring-opening polymer and silica is particularly good.

  Although the compounding quantity of a silica is not specifically limited, Preferably it is 10-150 weight part with respect to 100 weight part of all the polymer components in a polymer composition, More preferably, it is 20-120 weight part, Most preferably, it is 40-100. Parts by weight.

  When silica is used as the inorganic particles, it is preferable to add a silane coupling agent to the polymer composition for the purpose of improving the adhesion between the cyclopentene ring-opening polymer and silica. Examples of the silane coupling agent include vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, bis (3- (Triethoxysilyl) propyl) tetrasulfide, bis (3- (triethoxysilyl) propyl) disulfide and the like, and γ-trimethoxysilylpropyldimethylthiocarbamyltetrasulfide described in JP-A-6-248116, Examples thereof include tetrasulfides such as γ-trimethoxysilylpropylbenzothiazyl tetrasulfide. Of these, tetrasulfides are preferable. These silane coupling agents can be used alone or in combination of two or more. The blending amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of silica.

  Examples of carbon black that can be used as inorganic particles in the polymer composition of the present invention include furnace black, acetylene black, thermal black, channel black, and graphite. Among these, furnace black is preferable, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, and FEF. These carbon blacks can be used alone or in combination of two or more. The compounding amount of carbon black is usually 150 parts by weight or less with respect to 100 parts by weight of all polymer components of the polymer composition. When silica and carbon black are used in combination, the total amount of silica and carbon black is preferably 10 to 150 parts by weight with respect to 100 parts by weight of the total polymer component of the polymer composition. .

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 5 to 200 m ² / g, more preferably 80 to 130 m ² / g, and the dibutyl phthalate (DBP) adsorption amount is preferably 5 to 300 ml / g. 100 g, more preferably 80 to 160 ml / 100 g.

  The polymer composition of the present invention may further contain a rubber other than the cyclopentene ring-opening polymer. Examples of the rubber other than the polymer of the present invention include natural rubber (NR), polyisoprene rubber (IR), emulsion polymerization SBR (styrene-butadiene copolymer rubber), and solution polymerization random SBR (bound styrene 5 to 50% by weight). , Butadiene portion 1,2-bond content 10-80%), high trans SBR (butadiene portion trans bond content 70-95%), low cis BR (polybutadiene rubber), high cis BR, high trans BR ( Trans bond content of butadiene part 70 to 95%), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, emulsion polymerization styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, high vinyl SBR-low Vinyl SBR block copolymer rubber, polyisoprene-SBR block copolymer Beam, polystyrene - polybutadiene - polystyrene block copolymer, acrylic rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, ethylene - propylene rubber, and urethane rubber. Of these, NR, BR, IR, and SBR are preferably used. These rubbers can be used alone or in combination of two or more.

  When the polymer composition of the present invention contains a rubber other than the cyclopentene ring-opening polymer, the proportion of the cyclopentene ring-opening polymer is preferably 10% by weight or more based on the total amount of the polymer components. The range is more preferably 20 to 90% by weight, and particularly preferably 30 to 80% by weight. If this ratio is too low, the physical properties of the polymer composition may be inferior.

  In addition to the above components, the polymer composition of the present invention includes a crosslinking agent, a crosslinking accelerator, a crosslinking activator, an anti-aging agent, an activator, a process oil, a plasticizer, a lubricant, a filler and the like according to a conventional method. Each compounding agent can be blended in the required amount.

  Examples of crosslinking agents include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; dicumyl peroxide and ditertiary butyl peroxide. Organic peroxides; quinone dioximes such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime; organics such as triethylene tetramine, hexamethylene diamine carbamate and 4,4'-methylene bis-o-chloroaniline A polyhydric amine compound; an alkylphenol resin having a methylol group; and the like. Among these, sulfur is preferable, and powdered sulfur is more preferable. These crosslinking agents are used alone or in combination of two or more. The amount of the crosslinking agent 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 total polymer components.

  Examples of the crosslinking accelerator include N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N- Sulfenamide-based crosslinking accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N′-diisopropyl-2-benzothiazole sulfenamide; guanidines such as diphenylguanidine, diortolylguanidine, orthotolylbiguanidine Thiourea-based crosslinking accelerators such as diethylthiourea; thiazole-based crosslinking accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt; tetramethylthiuram monosulfide, Thiuram-based crosslinking accelerators such as tramethylthiuram disulfide; Dithiocarbamate-based crosslinking accelerators such as sodium dimethyldithiocarbamate and zinc diethyldithiocarbamate; Xanthogenic acid-based crosslinking such as sodium isopropylxanthate, zinc isopropylxanthate and zinc butylxanthate And a crosslinking accelerator such as an accelerator. Of these, those containing a sulfenamide-based crosslinking accelerator are particularly preferred. These crosslinking accelerators are 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 with respect to 100 parts by weight of the total polymer components.

  As the crosslinking activator, for example, higher fatty acids such as stearic acid, zinc oxide and the like can be used. Zinc oxide preferably has a high surface activity particle size of 5 μm or less, and examples thereof include activated zinc flower having a particle size of 0.05 to 0.2 μm and zinc flower having a particle size of 0.3 to 1 μm. Moreover, as zinc oxide, what was surface-treated with an amine-based dispersant or wetting agent can also be used. The blending amount of the crosslinking activator is appropriately selected, but the blending amount of the higher fatty acid is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 5 parts per 100 parts by weight of the total polymer components. The blending amount of zinc oxide is preferably 0.05 to 10 parts by weight, more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the total polymer components.

  Mineral oil or synthetic oil may be used as the process oil. As the mineral oil, aroma oil, naphthenic oil, paraffin oil and the like are usually used. Examples of other compounding agents include activators such as diethylene glycol, polyethylene glycol, and silicone oil; fillers such as calcium carbonate, talc, and clay; tackifiers such as petroleum resins and coumarone resins; and waxes.

  The polymer composition of the present invention can be obtained by kneading each component according to a conventional method. For example, a compounding composition excluding a crosslinking agent and a crosslinking accelerator and a cyclopentene ring-opening polymer are kneaded, and then the kneaded product is mixed with a crosslinking agent and a crosslinking accelerator to obtain a polymer composition. The kneading temperature of the compounding agent excluding the crosslinking agent and the crosslinking accelerator and the cyclopentene ring-opening polymer is preferably 80 to 200 ° C., more preferably 120 to 180 ° C., and the kneading time is preferably 30 seconds to 30 minutes. It is. Mixing of the crosslinking agent and the crosslinking accelerator is usually performed after cooling to 100 ° C. or lower, preferably 80 ° C. or lower.

  The polymer composition of the present invention is usually used as a crosslinked product. The crosslinking method is not particularly limited, and may be selected according to the shape, size, etc. of the crosslinked product. The mold may be filled with a crosslinkable rubber composition and heated to crosslink simultaneously with molding, or a preliminarily molded crosslinkable polymer composition may be heated to crosslink. 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.

  In addition, as a method for evaluating the affinity of the cyclopentene ring-opening polymer for the inorganic particles, when the polymer composition is kneaded and then immersed in toluene, it does not dissolve in toluene but adheres to the inorganic particles. This can be confirmed by measuring the amount of polymer (cyclopentene ring-opening polymer). It can be said that the greater the amount of polymer adhering to the inorganic particles, the better the affinity of the cyclopentene ring-opening polymer for the inorganic particles, and the better the mechanical properties of the polymer composition.

  Since the polymer composition of the present invention is excellent in affinity with inorganic particles, it gives a rubber cross-linked product having excellent mechanical properties, low exothermic properties, wet grip properties and wear resistance. Therefore, various applications that make use of the characteristics, for example, use in tire parts such as treads, carcass, sidewalls, and bead parts, or rubber products such as hoses, window frames, belts, shoe soles, anti-vibration rubber, and automobile parts. Further, it can be used as a resin reinforced rubber such as impact-resistant polystyrene and ABS resin. It is particularly excellent as a tire tread for a fuel-efficient tire, and is also suitable as a material for tire treads such as all-season tires, high-performance tires, studless tires, sidewalls, undertreads, carcass, and beat parts.

  Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples. In the following, “part” is based on weight unless otherwise specified. The test and evaluation were as follows.

[Molecular weight]
The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the polymer were measured as polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

[Introduction rate of functional group]
About the cyclopentene ring-opening polymer, ¹ H-NMR spectrum was measured, and the integrated value of the peak attributed to the carbon-carbon double bond in the main chain from the obtained spectrum and the polymer chain end were introduced. From the integrated value of the peak attributed to the functional group and the number average molecular weight (Mn), it is assumed that one polymer chain has two ends (a cyclopentene ring-opening polymer having a specific functional group introduced). The percentage of terminal number / cyclopentene ring-opening polymer chain terminal total number) was calculated as the functional group introduction rate.

[Affinity evaluation for inorganic particles]
After 2 parts of the kneaded polymer composition was immersed in 1000 parts of toluene for 72 hours, the polymer composition was filtered through a 100 mesh filter, and the weight of the remaining part of the filter (filtered material remaining on the filter) was measured. Filter residual part when using cyclopentene ring-opening polymer, which is the object of measurement, when filter residual part weight when using cyclopentene ring-opening polymer with no functional group introduced at the polymer chain end is 100 The weight was determined and used as an index of inorganic particle affinity.

[Polymer Production Example 1]
Under a nitrogen atmosphere, 100 parts of cyclopentene and 0.10 parts of allyltrimethoxysilane were added to a pressure resistant glass reaction vessel containing a magnetic stir bar. Next, 0.062 part of (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride dissolved in 10 parts of toluene was added, and polymerization was carried out at a polymerization temperature of 0 ° C. for 10 hours. Excess vinyl ethyl ether was added to terminate the polymerization, and then poured into a large excess of isopropanol containing 2,6-di-t-butyl-p-cresol (BHT). Then, the precipitated polymer was collected, washed with isopropanol, and vacuum-dried at 40 ° C. for 3 days to obtain 25 parts of a cyclopentene ring-opening polymer. The obtained cyclopentene polymer was Mn = 45,600 and Mw / Mn = 1.89. Introduction rate of functional group to polymer chain end is 49% [Since a compound containing one functional group (allyltrimethoxysilane) is used, the theoretical maximum value is 50%. 〕Met.

[Polymer Production Example 2]
Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature was 10 ° C. and the polymerization time was 20 hours to obtain 89 parts of a cyclopentene ring-opened polymer. The obtained cyclopentene polymer was Mn = 137,200 and Mw / Mn = 1.50. The introduction ratio of the functional group to the polymer chain terminal was 47%.

[ Reference Polymer Production Example 3]
Polymerization was conducted in the same manner as in Example 1 except that 0.10 parts of allyltrimethoxysilane was replaced with 0.09 parts of 2-butene-1,4-dicarboxylic acid to obtain 20 parts of a cyclopentene ring-opened polymer. It was. The obtained cyclopentene polymer was Mn = 36,800 and Mw / Mn = 1.68. The introduction rate of the functional group at the polymer chain end is 95% [the compound having two functional groups (2-butene-1,4-dicarboxylic acid) is used, so the theoretical maximum value is 100%. . 〕Met.

[Comparative Polymer Production Example 1]
A polymerization reaction was carried out in the same manner as in Example 1 except that the polymerization temperature was 80 ° C., to obtain 15 parts of a cyclopentene ring-opened polymer. The obtained cyclopentene polymer was Mn = 3,800 and Mw / Mn = 1.68. The introduction ratio of the functional group to the polymer chain terminal was 5% or less.

[Comparative Polymer Production Example 2]
Polymerization was carried out in the same manner as in Example 1 except that 0.051 part of 1-hexene was added instead of 0.10 parts of allyltrimethoxysilane, and cyclopentene was not introduced with a functional group at the end of the polymer. A ring polymer was synthesized. The yield of the obtained cyclopentene polymer was 21 parts, and Mn = 37,800 and Mw / Mn = 1.87.

[Examples 1 and 2 and Comparative Example 1]
In a Brabender type mixer with a capacity of 250 ml, 100 parts of the cyclopentene ring-opened polymer obtained in Polymer Production Examples 1 and 2 and Comparative Polymer Production Example 2 was masticated for 30 seconds, and then processed with process oil (Fucol M. Ferex). M: 10 parts by Fuji Kosan Co., Ltd., 40 parts of carbon-silica dual phase filler (CRX2000, made by Cabot) and 2.5 parts of silane coupling agent (Si69, made by Degussa) were added, and 110 ° C. was started. After mixing for 2 minutes as a temperature, 20 parts of carbon-silica dual phase filler (CRX2000, manufactured by Cabot), 3 parts of zinc oxide (Zinc Hana # 1, manufactured by Honjo Chemical Co., Ltd., particle size 0.4 μm), 2 parts of stearic acid and aging 2 parts of an inhibitor (NOCRACK 6C, manufactured by Ouchi Shinsei Co., Ltd.) was added and further kneaded for 2 minutes. After 2 parts of the kneaded polymer composition was immersed in 1000 parts of toluene for 72 hours, it was filtered through a 100 mesh filter, and the weight of the remaining part of the filter was measured. When the polymer of Comparative Polymer Production Example 2 is used (Comparative Example 1) and the residual part weight is 100, the polymer of Polymer Production Example 1 is used (Example 1), and the polymer When the polymer of Production Example 2 was used (Example 2), the residual amounts were 115 and 108, respectively.

  As can be seen from the comparison between Examples 1 and 2 and Comparative Example 1, the cyclopentene ring-opened polymer having a functional group introduced at the end of the polymer chain is compared with the cyclopentene ring-opened polymer having no functional group introduced. It was excellent in affinity for inorganic particles.

Claims (6)

A functional group containing silicic MotoHara child to more than 25% of the polymer chain end all, and a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (Mn) is 10,000 to Cyclopentene ring-opening polymer that is 1,000,000 (provided that when repeating units derived from monomers other than cyclopentene are included, the proportion of the repeating units is 10% mol or less with respect to all repeating units) And a polymer composition comprising inorganic particles selected from silica and carbon black , and a rubber other than the cyclopentene ring-opening polymer blended as desired. The number average molecular weight of cyclopentene ring-opened polymer (Mn) is polymer composition of claim 1 Symbol placement is 20,000～1,000,00 0. The polymer composition according to claim 1 or 2 , wherein the proportion of the inorganic particles is 10 to 150 parts by weight with respect to 100 parts by weight of the total amount of the polymer components . The polymer composition according to any one of claims 1 to 3, wherein the inorganic particles are composed of silica alone or both silica and carbon black. Furthermore, the polymer composition of Claim 4 containing 0.1-30 weight part silane coupling agent with respect to 100 weight part of silica. The polymer composition according to any one of claims 1 to 5, wherein the ratio of the cyclopentene ring-opening polymer is 10% by weight or more based on the total amount of the polymer components.