JP7230328B2 - Reactive compositions and thermoplastic elastomers - Google Patents

Description

TECHNICAL FIELD The present invention relates to a reactive composition containing a monocyclic olefin ring-opening polymer and an isocyanate group-containing compound having two isocyanate groups in the molecule, and more specifically, it has high tensile strength, high elongation, and heat resistance. and a reactive composition that provides a thermoplastic elastomer with excellent ozone resistance.

Polyurethanes, which are obtained by polymerizing diols and diisocyanates through urethane bonds, are used as thermoplastic elastomers in a wide range of applications, including industrial materials such as shoe soles, clothing, soundproofing materials and adhesives, and automotive materials such as bumpers and headrests. .
Among them, when a liquid diene-based elastomer such as liquid polybutadiene or liquid polyisoprene having hydroxyl groups at both ends is used as the diol, it has a double bond in the polymer main chain and is excellent in rubber elasticity, mechanical strength and abrasion resistance. It becomes a polyurethane excellent in such as.

However, polyurethanes using such liquid diene-based elastomers have the problem of being inferior in heat resistance and ozone resistance. Therefore, liquid diene-based elastomers having excellent heat resistance and ozone resistance have been desired.

On the other hand, a technique for obtaining a cyclic olefin ring-opening polymer by metathesis ring-opening polymerization of a cyclic olefin in the presence of a chain transfer agent is known. discloses a technique for obtaining a cyclic olefin ring-opening polymer having a reactive group at the polymer chain end by metathesis ring-opening polymerization of a cyclic olefin using a ruthenium catalyst. This patent document 1 discloses that the introduction amount of reactive groups in the obtained cyclic olefin ring-opened polymer can be adjusted by adjusting the ratio of the reactive group-containing olefin and the cyclic olefin.

Further, Patent Document 2 discloses a cyclic olefin-opening polymer obtained by hydrogenating part of the carbon-carbon double bonds in the main chain structure of a cyclic olefin ring-opening polymer having a weight average molecular weight of 1,000 to 100,000. Ring polymer hydrides are disclosed.

However, the techniques described in Patent Documents 1 and 2 do not disclose a technique for obtaining a liquid cyclic olefin ring-opening polymer, and therefore cannot be applied as a substitute material for the liquid diene elastomer described above. there were. In particular, in the technique of Patent Document 2, a cyclic olefin ring-opening polymer is hydrogenated, but the hydrogenation reaction results in a resinous polymer having no rubber elasticity.

Further, Patent Document 3 discloses a liquid octenamer obtained by ring-opening polymerization of cyclooctene as a cyclic olefin. However, the technique of Patent Document 3 cannot obtain sufficient mechanical strength because it does not modify liquid octenamer to obtain a polymer.

Japanese Patent Publication No. 11-514043 JP-A-2002-317034 Special Table 2013-529695

The present invention has been made in view of such circumstances, and provides a reactive composition capable of providing a thermoplastic elastomer having high tensile strength, high elongation, and excellent heat resistance and ozone resistance. for the purpose.

The present inventors have conducted intensive studies to achieve the above object, and found that a monocyclic olefin ring-opening polymer having a reactive group at the polymer chain end and a predetermined molecular weight has an isocyanate group. The inventors have found that the above object can be achieved by a reactive composition containing an isocyanate group-containing compound having two in the molecule, and have completed the present invention.

That is, according to the present invention, a monocyclic olefin ring-opening polymer (A) having a reactive group at the polymer chain end and having a weight average molecular weight (Mw) of 1,000 to 50,000, A reactive composition containing a compound (B) having two isocyanate groups in the molecule is provided.

In the reactive composition of the present invention, the monocyclic olefin ring-opened polymer (A) is a polymer consisting only of monocyclic monoolefin-derived structural units, or a monocyclic monoolefin-derived structural unit and a monocyclic A copolymer composed of a monoolefin and a structural unit derived from a copolymerizable monomer is preferred.
In the reactive composition of the present invention, the monocyclic olefin ring-opening polymer (A) is a polymer consisting only of cyclopentene-derived structural units, or a cyclopentene-derived structural unit and a monomer copolymerizable with cyclopentene. It is preferably a copolymer composed of a structural unit derived from a polymer.
In the reactive composition of the present invention, the reactive group at the polymer chain end of the monocyclic olefin ring-opening polymer (A) is preferably a hydroxyl group.
The reactive composition of the present invention preferably further contains a chain extension compound (C) having two hydroxyl groups or two amino groups in the molecule and a molecular weight of 800 or less.

Further, according to the present invention, there is provided a thermoplastic elastomer obtained by reacting any one of the above reactive compositions.

According to the present invention, there is provided a reactive composition capable of providing a thermoplastic elastomer having high tensile strength, high elongation, excellent heat resistance and ozone resistance, and a composition obtained using such a reactive composition. It is possible to provide a thermoplastic elastomer having high tensile strength, high elongation, and excellent heat resistance and ozone resistance.

The reactive composition of the present invention comprises a monocyclic olefin ring-opening polymer (A) having a reactive group at the polymer chain end and a weight average molecular weight (Mw) of 1,000 to 50,000. , and a compound (B) having two isocyanate groups in the molecule.

<Monocyclic olefin ring-opening polymer (A)>
The monocyclic olefin ring-opening polymer (A) used in the present invention is a polymer containing a repeating unit obtained by ring-opening polymerization of a monocyclic olefin as a repeating unit constituting its main chain, It is a polymer having a reactive group at the end of the combined chain and having a weight average molecular weight (Mw) of 1,000 to 50,000.

In the monocyclic olefin ring-opening polymer (A) used in the present invention, the proportion of repeating units formed by ring-opening polymerization of monocyclic olefin is preferably 70 mol% or more with respect to all repeating units, and 75 mol. % or more, more preferably 80 mol % or more. However, as long as the characteristics of the monocyclic olefin ring-opening polymer are maintained, it may contain repeating units derived from other monomers copolymerizable with the monocyclic olefin, and may be derived from other monomers. The proportion of repeating units is preferably 30 mol % or less, more preferably 25 mol % or less, even more preferably 20 mol % or less, relative to all repeating units. A monocyclic olefin is a hydrocarbon compound consisting of one ring and having a carbon-carbon double bond in the ring, and the number of carbon-carbon double bonds may be one or more. (but does not contain an aromatic ring).

Specific examples of such monocyclic olefins include monocyclic monoolefins having one carbon-carbon double bond in the ring, such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene; 1,4-cyclohexadiene, 1 ,4-cycloheptadiene, 1,5-cyclooctadiene, and other monocyclic dienes with two carbon-carbon double bonds in the ring; 1,5,9-cyclododecatriene, and other carbon-carbon double bonds is a monocyclic triene having three in the ring; and the like. Among these, monocyclic monoolefins are preferred, and cyclopentene is more preferred. The monocyclic olefin may or may not have a substituent, and the substituent is not particularly limited. Examples of the monocyclic olefin include alkyl groups such as methyl and ethyl. mentioned.

Other monomers copolymerizable with monocyclic olefins include polycyclic cyclic monoolefins, polycyclic cyclic dienes, and polycyclic cyclic trienes. Polycyclic cyclic monoolefins, polycyclic cyclic 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 . Norbornene compounds which may have substituents such as 0 ^2,7 ]dodeca-4-ene are exemplified. Among these, polycyclic cyclic monoolefins and polycyclic cyclic dienes are preferred, and 2-norbornene and dicyclopentadiene are more preferred.

Further, when the monocyclic olefin ring-opening polymer (A) is a copolymer, it is a copolymer of one type of monocyclic olefin and one or more types of monomers other than monocyclic olefins. Alternatively, a copolymer of two or more monocyclic olefins, or a copolymer of two or more monocyclic olefins and one or more monomers other than monocyclic olefins There may be. When the monocyclic olefin ring-opened polymer has two or more monocyclic olefin-derived structural units, the proportion of all monocyclic olefin-derived structural units contained in the monocyclic olefin ring-opened polymer is within the above range. And it is sufficient.

The monocyclic olefin ring-opening polymer (A) used in the present invention consists only of monocyclic monoolefin-derived structural units as repeating units constituting the main chain from the viewpoint of being superior in heat resistance and ozone resistance. A polymer or a structural unit derived from a monocyclic monoolefin and a structural unit derived from a monomer copolymerizable with the monocyclic monoolefin (including structural units derived from a monocyclic olefin other than the monocyclic monoolefin) A polymer consisting only of structural units derived from cyclopentene, or a structural unit derived from cyclopentene and a structural unit derived from a monomer copolymerizable with cyclopentene (monocyclic other than cyclopentene It also includes structural units derived from olefins.). Preferred monomers copolymerizable with cyclopentene are monocyclic diolefins, polycyclic cyclic monoolefins, and polycyclic cyclic dienes, including 1,5-cyclooctadiene, 2-norbornene, and dicyclopentadiene. more preferred.

When the monocyclic olefin ring-opened polymer (A) used in the present invention is a polymer containing a monocyclic monoolefin-derived structural unit, the ratio of the monocyclic monoolefin-derived structural unit to all repeating units is It is preferably 70 mol % or more, more preferably 75 mol % or more, and even more preferably 80 mol % or more. On the other hand, the proportion of structural units derived from monomers copolymerizable with monocyclic monoolefins is preferably 30 mol% or less, more preferably 25 mol% or less, relative to all repeating units. It is more preferably mol % or less.
Further, when the monocyclic olefin ring-opening polymer (A) used in the present invention is a polymer containing structural units derived from cyclopentene, the ratio of structural units derived from cyclopentene is 70 mol% or more with respect to all repeating units. , more preferably 75 mol % or more, and even more preferably 80 mol % or more. On the other hand, the proportion of structural units derived from a monomer copolymerizable with cyclopentene is preferably 30 mol% or less, more preferably 25 mol% or less, and 20 mol% or less, relative to all repeating units. is more preferable.

The weight-average molecular weight (Mw) of the monocyclic olefin ring-opening polymer (A) used in the present invention is a polystyrene-equivalent weight-average molecular weight (Mw) measured by gel permeation chromatography, and is 1,000 to 1,000. 50,000, preferably 1,500 to 45,000, more preferably 2,000 to 40,000. If the weight average molecular weight (Mw) is too low, the resulting thermoplastic elastomer will be inferior in mechanical strength such as tensile strength. The polymer becomes highly viscous and difficult to handle.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene, measured by gel permeation chromatography, of the monocyclic olefin ring-opening polymer (A) used in the present invention (Mw/Mn ) is not particularly limited, but is usually 4.0 or less, preferably 3.5 or less, more preferably 3.0 or less. By setting Mw/Mn within the above range, mechanical strength such as tensile strength of the resulting polymer can be further enhanced.

In addition, the monocyclic olefin ring-opening polymer (A) used in the present invention is a polymer having a liquid state (having fluidity at 60°C) at a temperature that can be generally handled, for example, 60°C. It is a polymer having fluidity at 60°C (that is, a liquid polymer) to the extent that the melt viscosity measured at a temperature of 60°C using a Brookfield viscometer is 1,000 Pa·s or less. In the present invention, by using such a monocyclic olefin ring-opening polymer (A), it is possible to improve the reactivity with the compound (B) having two isocyanate groups in the molecule, which will be described later. The resulting thermoplastic elastomer can have high tensile strength, high elongation, and excellent heat resistance and ozone resistance. Further, by using the monocyclic olefin ring-opening polymer (A), the reactive composition of the present invention and the thermoplastic elastomer obtained by using the It can be suitably used for applications that require fluidity in the state of the reactive composition) and applications where it is preferable to have fluidity before the reaction. The melt viscosity at a temperature of 60° C. of the monocyclic olefin ring-opening polymer (A) used in the present invention is preferably 900 Pa·s or less, more preferably 800 Pa·s or less.

In the double bonds present in the repeating units constituting the monocyclic olefin ring-opening polymer (A) used in the present invention, the cis/trans ratio is not particularly limited, but is usually in the range of 10/90 to 90/10. From the viewpoint that the heat resistance and ozone resistance can be further improved, it is preferably in the range of 15/85 to 60/40, more preferably in the range of 15/85 to 40/60. The cis/trans ratio can be measured by ¹³ C-NMR spectrum measurement of the monocyclic olefin ring-opening polymer (A).

The method for adjusting the cis/trans ratio of the monocyclic olefin ring-opening polymer (A) to the above range is not particularly limited. For example, a monocyclic olefin is polymerized to obtain a monocyclic olefin ring-opening polymer ( Examples thereof include a method of controlling the polymerization conditions in obtaining A). For example, the higher the polymerization temperature in polymerizing the monocyclic olefin, the higher the trans ratio, and the lower the monomer concentration in the polymerization solution, the higher the trans ratio.

The glass transition temperature (Tg) of the monocyclic olefin ring-opening polymer (A) used in the present invention is preferably −50° C. or lower from the viewpoint of making the resulting thermoplastic elastomer excellent in low-temperature properties. It is more preferably -60°C or lower, still more preferably -70°C or lower. The glass transition temperature of the monocyclic olefin ring-opening polymer (A) can be adjusted, for example, by adjusting the cis/trans ratio of the double bonds present in the repeating unit, or by adjusting the monocyclic olefin ring-opening polymer (A). is a copolymer, it can be adjusted by adjusting the content ratio of the structural unit derived from the monomer copolymerizable with the monocyclic olefin.

In addition, the monocyclic olefin ring-opening polymer (A) used in the present invention may have a melt viscosity in the above range measured at a temperature of 60 ° C. using a Brookfield viscometer, but a melting point of less than 60 ° C. and may be solid at room temperature (25° C.), for example. When the monocyclic olefin ring-opening polymer (A) has a melting point, the melting point (Tm) is preferably less than 60°C, more preferably less than 25°C. When the melting point (Tm) of the monocyclic olefin ring-opening polymer is less than 60°C, the monocyclic olefin ring-opening polymer becomes a liquid polymer at 60°C, thereby making it easier to obtain the effects of the present invention.

The monocyclic olefin ring-opening polymer (A) used in the present invention has a reactive group at the polymer chain end, and such a reactive group is not particularly limited. , an atom of group 16 of the periodic table, a silicon atom, and a reactive group containing an atom selected from the group consisting of halogen atoms, and a compound having two isocyanate groups in the molecule (B ) and the heat resistance of the resulting polymer, a reactive group containing an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, a silicon atom, and a halogen atom is preferred. Among these, a reactive group containing an atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom is more preferred, and from the viewpoint of reactivity, a hydroxyl group, a carboxy group, and an amino group are more preferred. , hydroxyl groups are particularly preferred.

In the monocyclic olefin ring-opening polymer (A) used in the present invention, even if a reactive group is introduced only at one polymer chain end (one end), both polymer chain ends ( (both ends) may be introduced with a reactive group, or a mixture of these may be used. Furthermore, in the monocyclic olefin ring-opening polymer (A) used in the present invention, these may be mixed with a monocyclic olefin ring-opening polymer to which no reactive group has been introduced.

The introduction ratio of reactive groups at the polymer chain end of the monocyclic olefin ring-opening polymer (A) is not particularly limited, but the reactivity with the compound (B) having two isocyanate groups in the molecule described later and From the viewpoint of heat resistance of the resulting polymer, the percentage value of the number of reactive groups to the number of polymer chains in the monocyclic olefin ring-opening polymer (A) is preferably 100% or more, and more It is preferably 120% or more, more preferably 140% or more. The ^method for measuring the ratio of introduction of reactive groups to the polymer chain ends is not particularly limited. It can be determined from the number average molecular weight (Mn) obtained from ion chromatography.

The method for synthesizing the monocyclic olefin ring-opening polymer (A) used in the present invention is not particularly limited as long as the target polymer can be obtained, and it may be synthesized according to a conventional method. A method of ring-opening polymerization of a monomer containing a monocyclic olefin using a ring-opening polymerization catalyst that is resistant to reactive groups and does not generate insoluble components in the presence of an olefin compound having In the presence of an olefin compound having a reactive group protected by a protecting group, using a ring-opening polymerization catalyst that does not have resistance to the reactive group and does not produce an insoluble component, a monomer containing a monocyclic olefin is produced. A method of ring-opening polymerization and deprotection of the reactive group protected by the protecting group introduced at the end of the resulting polymer chain, and (III) the polymer synthesized in (I) or (II) above A method of converting a reactive group at the chain end to another reactive group is preferred.

(I) Reactivity used in a method for ring-opening polymerization of a monomer containing a monocyclic olefin in the presence of an olefin compound having a reactive group, using a ring-opening polymerization catalyst having resistance to the reactive group The olefin compound having a group is not particularly limited as long as it is a compound containing at least one ethylenically unsaturated bond and at least one reactive group in the molecule. Examples of reactive groups include amino groups, hydroxyl groups, carboxy groups, carboxylic acid anhydride groups, methacryloyloxy groups, epoxy groups, oxysilyl groups and halogen atoms.

Olefin compounds having an amino group include allylamine, N-allylaniline, N-allylbenzylamine, 4-aminostyrene, 2-butene-1,4-diamine, 3-hexene-2,5-diamine and the like. .

Olefin compounds having a hydroxyl group include, for example, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 4-hexene-1-ol, 4-hepten-1-ol, 5-decen-1 -ol, 5-hexen-1-ol, 5-octen-1-ol, 6-hepten-1-ol, 4-hydroxystyrene, 2-allylphenol, allyl 4-hydroxybenzoate, 1-cyclohexyl-2- buten-1-ol, ethylene glycol monoallyl ether, 3-allyloxy-1,2-propanediol, 2-butene-1,4-diol, 3-hexene-2,5-diol, 4-octene-1,8 - diols and the like.

Olefin compounds having a carboxy group include, for example, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, trans-3-pentenoic acid, vinylbenzoic acid, trans-3-hexenedioic acid and the like.

Olefin compounds having a carboxylic anhydride group include allylsuccinic anhydride and (2,7-octadien-1-yl)succinic anhydride.

Olefin compounds having a methacryloyloxy group include cis-1,4-dimethacryloyloxy-2-butene, allyl methacrylate and 5-hexenyl methacrylate.

Olefin compounds having an epoxy group include 1,3-butadiene monoepoxide, allyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, 1,2,9,10-diepoxy -5-decene and the like.

Olefin compounds having an oxysilyl group include vinyl(trimethoxy)silane, vinyl(triethoxy)silane, allyl(trimethoxy)silane, allyl(methoxy)(dimethyl)silane, allyl(triethoxy)silane, allyl(ethoxy)(dimethyl)silane. , styryl (trimethoxy) silane, styryl (triethoxy) silane, 2-styrylethyl (triethoxy) silane, allyl (triethoxysilylmethyl) ether, allyl (triethoxysilylmethyl) (ethyl) amine and other alkoxysilane compounds; vinyl ( Aryloxysilane compounds such as triphenoxy)silane, allyl(triphenoxy)silane, allyl(phenoxy)(dimethyl)silane; vinyl(triacetoxy)silane, allyl(triacetoxy)silane, allyl(diacetoxy)methylsilane, allyl(acetoxy)silane )(dimethyl)silane; alkylsiloxysilane compounds such as allyltris(trimethylsiloxy)silane; arylsiloxysilane compounds such as allyltris(triphenylsiloxy)silane; 1-allylheptamethyltrisiloxane, 1-allyl Polysiloxane compounds such as nonamethyltetrasiloxane, 1-allylnonamethylcyclopentasiloxane, 1-allylundecamethylcyclohexasiloxane; 1,4-bis(trimethoxysilyl)-2-butene, 1,4-bis( Alkoxysilane compounds such as triethoxysilyl)-2-butene and 1,4-bis(trimethoxysilylmethoxy)-2-butene; Aryloxysilane compounds such as 1,4-bis(triphenoxysilyl)-2-butene ; acyloxysilane compounds such as 1,4-bis(triacetoxysilyl)-2-butene; alkylsiloxysilane compounds such as 1,4-bis[tris(trimethylsiloxy)silyl]-2-butene; Arylsiloxysilane compounds such as bis[tris(triphenylsiloxy)silyl]-2-butene; 1,4-bis(heptamethyltrisiloxy)-2-butene, 1,4-bis(undecamethylcyclohexasiloxy) -polysiloxane compounds such as 2-butene;

Olefin compounds having a halogen atom include allyl chloride, crotyl chloride, 1,4-dichloro-2-butene, allyl bromide, allyl iodide, crotyl chloride, 1,4-dichloro-2-butene, 1, 4-dibromo-2-butene and the like are included.

The olefin compounds having these reactive groups may be used singly or in combination of two or more.

The amount of the olefin compound having a reactive group to be used is not particularly limited. Mw), preferably 0.1 to 20 parts by weight, more preferably 0.15 to 15 parts by weight, and further It is preferably 0.2 to 10 parts by weight. In addition, since the olefin compound having a reactive group acts as a molecular weight modifier in addition to the action of introducing a reactive group to the polymer chain end of the monocyclic olefin ring-opening polymer (A), Also from the viewpoint of controlling the weight average molecular weight (Mw) of the monocyclic olefin ring-opening polymer (A) within the above range, the amount of the olefin compound having a reactive group is preferably within the above range.

In addition, ring-opening polymerization that has resistance to reactive groups and does not generate insoluble components can be used in a method for ring-opening polymerization of a monomer containing a monocyclic olefin in the presence of an olefin compound having a reactive group. Examples of catalysts include ruthenium carbene complexes.

The ruthenium carbene complex is not particularly limited as long as it serves as a ring-opening polymerization catalyst for monocyclic olefins. Specific examples of preferably used ruthenium carbene complexes include bis(tricyclohexylphosphine)benzylidene ruthenium dichloride, bis(triphenylphosphine)-3,3-diphenylpropenylidene ruthenium dichloride, dichloro-(3-phenyl-1H-indene -1-ylidene)bis(tricyclohexylphosphine)ruthenium (II), (3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium dichloride, bis(tricyclohexylphosphine)t-butylvinylideneruthenium dichloride , bis(1,3-diisopropylimidazolin-2-ylidene)benzylideneruthenium dichloride, bis(1,3-dicyclohexylimidazolin-2-ylidene)benzylideneruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene) ( tricyclohexylphosphine)benzylideneruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)benzylideneruthenium dichloride, bis(tricyclohexylphosphine)ethoxymethylideneruthenium dichloride, (1,3-di mesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)ethoxymethylideneruthenium dichloride;

The amount of the ruthenium carbene complex used is not particularly limited, but the molar ratio of (metallic ruthenium in the catalyst:monocyclic olefin-containing monomer) is usually 1:2,000 to 1:2,000. ,000, preferably 1:5,000 to 1:1,500,000, more preferably 1:10,000 to 1:1,000,000. If the amount of ruthenium carbene complex used is too small, the polymerization reaction may not proceed sufficiently. On the other hand, when it is too large, it becomes difficult to remove the catalyst residue from the obtained monocyclic olefin ring-opened polymer, and various properties may be deteriorated when the thermoplastic elastomer is produced.

The polymerization reaction may be carried out in the absence of a solvent or in a solution. When the polymerization is carried out in a solution, the solvent to be used is not particularly limited as long as it is inert in the polymerization reaction and can dissolve the monomer containing the monocyclic olefin used in the polymerization, the polymerization catalyst, and the like. Solvents, ether solvents, ester solvents, ketone solvents or halogen solvents are 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. Ether solvents include diethyl ether, cyclopentylmethyl ether, 1,2-dimethoxyethylene, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like. Examples of ester solvents include methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate and the like. Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Examples of halogen-based solvents include alkyl halogens such as dichloromethane and chloroform; aromatic halogens such as chlorobenzene and dichlorobenzene; and the like.

The polymerization temperature is not particularly limited, but is usually set in the range of -50 to 100°C. The polymerization reaction time is preferably 1 minute to 72 hours, more preferably 5 hours to 20 hours. After the polymerization conversion reaches a predetermined value, the polymerization reaction can be terminated by adding a known polymerization terminator to the polymerization system.

As described above, a polymer solution containing the monocyclic olefin ring-opening polymer (A) having a reactive group at the polymer chain end can be obtained. As a method for recovering the polymer from the polymer solution, a known recovery method may be adopted. For example, by mixing a polymer solution with an excess of a poor solvent for the polymer to precipitate the polymer, recovering the precipitated polymer, and drying it, a monocyclic olefin ring-opened polymer (A ) can be obtained. Alternatively, the polymer solution can be directly dried to evaporate off the unreacted monocyclic olefin and the solvent to obtain the monocyclic olefin ring-opened polymer (A).

(II) When ring-opening polymerization of a monomer containing a monocyclic olefin is performed using a ring-opening polymerization catalyst that does not have resistance to reactive groups, the polymerization reaction is carried out with an olefin having a reactive group protected by a protecting group. It is carried out in the presence of a compound. The reactive group to be protected includes the same reactive groups contained in the olefin compounds having a reactive group as described above. may be carried out using a known protecting group. For example, specific examples of protecting groups for amino group, hydroxyl group and carboxy group include alkyl group, acyl group, RC(O)- group (where R is a saturated hydrocarbon group having 1 to 10 carbon atoms), silyl group, metal Alkoxide and the like can be mentioned. Alternatively, an olefin compound having a protected reactive group may be obtained by reacting an olefin compound having an amino group, hydroxyl group or carboxy group with a trialkylaluminum compound. When using a reaction product of an olefin compound having an amino group, a hydroxyl group, or a carboxy group and a trialkylaluminum compound, this reaction product may function as an organometallic compound used as a co-catalyst, which will be described later. can. On the other hand, methacryloyloxy groups, carboxylic anhydride groups, and epoxy groups do not have suitable protective groups for protecting them. When it has an oxy group, a carboxylic acid anhydride group, or an epoxy group, it is preferably produced by the method (I). Olefin compounds having an oxysilyl group and olefin compounds having a halogen atom do not require protective groups because they are resistant to polymerization catalysts other than (I), which will be described later.

Monocyclic olefin-containing monomers have been developed as ring-opening polymerization catalysts that do not have resistance to reactive groups and do not produce insoluble components in the presence of olefin compounds having reactive groups protected by protective groups. Preferred ring-opening polymerization catalysts include molybdenum compounds and tungsten compounds, although they are not limited as long as they are capable of ring polymerization. Specific examples of molybdenum compounds that can be used as ring-opening polymerization catalysts include molybdenum pentachloride, molybdenum oxotetrachloride, and molybdenum (phenylimide) tetrachloride. Further, specific examples of the tungsten compound include tungsten hexachloride, tungsten oxotetrachloride, tungsten (phenylimide) tetrachloride, tungsten monocatecholate tetrachloride, bis(3,5-ditertiarybutyl) catecholate tungsten dichloride, bis Mention may be made of (2-chloroetherate)tetrachloride, tungsten oxotetraphenolate.

When a molybdenum compound or a tungsten compound is used as a ring-opening polymerization catalyst, an organometallic compound may be used in combination as a co-catalyst. Organometallic compounds that can be used as the promoter include organometallic compounds of Groups 1, 2, 12, 13, or 14 metal atoms of the periodic table having a hydrocarbon group of 1 to 20 carbon atoms. Among them, organolithium compounds, organomagnesium compounds, organozinc compounds, organoaluminum compounds, and organotin compounds are preferably used, with organolithium compounds, organotin compounds, and organoaluminum compounds being more preferably used, and organoaluminum compounds being particularly preferred. Used. The amount of the organometallic compound used is not particularly limited, but the molar ratio of (molybdenum compound or tungsten compound:organometallic compound) is preferably 1:0.1 to 10, and 1:0.5 to 5. is more preferred.

The polymerization reaction conditions in the case of using a molybdenum compound or a tungsten compound as a ring-opening polymerization catalyst may be appropriately set within the range of the conditions described in the case of using a ruthenium carbene complex.

Deprotection of the monocyclic olefin ring-opening polymer having an amino group, a hydroxyl group, or a carboxy group protected by a protecting group at the polymer chain end obtained as described above can be carried out according to the known protecting group used. method. Specific examples include methods such as deprotection by heating and deprotection by hydrolysis or alcoholysis.

As described above, a polymer solution containing the monocyclic olefin ring-opening polymer (A) having a reactive group at the polymer chain end can be obtained. As a method for recovering the polymer from the polymer solution, the known recovery method described in the case of using the ruthenium carbene complex may be employed.

(III) A known method can be used to convert the specific functional group at the end of the polymer chain synthesized in (I) or (II) above to another specific functional group. For example, by reacting a monocyclic olefin ring-opening polymer having a hydroxyl group at the polymer chain end with an isocyanate compound having an oxysilyl group, a monocyclic olefin ring-opening polymer having an oxysilyl group at the polymer chain end (A ). Examples of isocyanate compounds having an oxysilyl group include 3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, 3-(methyldimethoxysilyl)propyl isocyanate and the like.

The monocyclic olefin ring-opening polymer (A) used in the present invention can be obtained by the production method as described above. If desired, anti-aging agents such as phenol-based stabilizers, phosphorus-based stabilizers, and sulfur-based stabilizers may be added to the resulting monocyclic olefin ring-opening polymer (A). The amount of the anti-aging agent to be added may be appropriately determined depending on the type of anti-aging agent. Further, if desired, an extender oil may be blended.

<Compound (B) having two isocyanate groups in the molecule>
The reactive composition of the present invention contains a compound (B) having two isocyanate groups in the molecule in addition to the monocyclic olefin ring-opening polymer (A) described above. Compound (B) having two isocyanate groups in the molecule is not particularly limited as long as it has two isocyanate groups in one molecule, for example, hexamethylene diisocyanate, aliphatic diisocyanate such as lysine diisocyanate; Aromatic diisocyanates such as p-phenylene diisocyanate, tolylene diisocyanate (TDI), naphthylene diisocyanate (NDI), tolidine diisocyanate (TODI), 4,4'-diphenylmethane diisocyanate (MDI); xylylene diisocyanate (XDI), tetramethyl araliphatic diisocyanates such as xylylene diisocyanate (TMXDI); alicyclic diisocyanates such as cyclohexyl diisocyanate (CHPI), hydrogenated xylylene diisocyanate (hydrogenated XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI); and aromatic diisocyanates are preferred.

As the compound (B) having two isocyanate groups in the molecule, one type may be used alone, or two or more types may be used in combination.

In the reactive composition of the present invention, one isocyanate of the compound (B) having two isocyanate groups in the molecule reacts with one reactive group of the monocyclic olefin polymer (A). It will happen. Therefore, the amount of the compound (B) having two isocyanate groups in the molecule to be used is defined as "the reactive group at the polymer chain end of the monocyclic olefin ring-opened polymer (A): having two isocyanate groups in the molecule The molar ratio of "isocyanate group of compound (B)" is preferably in the range of 1:0.9 to 1:1.1, and is in the range of 1:0.95 to 1:1.05. Quantity is more preferable. By setting the amount of the compound (B) having two isocyanate groups in the molecule to the above range, the tensile strength and elongation of the resulting thermoplastic elastomer can be further increased, and the heat resistance and ozone resistance can be further improved. can be improved.

<Chain extension compound (C)>
The reactive composition of the present invention has two hydroxyl groups or amino groups in the molecule in addition to the above-described monocyclic olefin ring-opening polymer (A) and the compound (B) having two isocyanate groups in the molecule. However, it is preferable to further contain a chain extension compound (C) having a molecular weight of 800 or less (hereinafter simply referred to as "chain extension compound (C)"). By containing the chain extension compound (C), the production of the thermoplastic elastomer using the reactive composition of the present invention can be facilitated, and the resulting thermoplastic elastomer has a tensile strength of can be higher and the elongation can be greater.

The chain extension compound (C) may be a compound having two hydroxyl groups or amino groups in the molecule and a molecular weight of 800 or less. is preferably from 50 to 700, more preferably from 60 to 600.

Examples of the chain extension compound (C) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 2,3-butanediol, 1 , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and other carbon-carbon double bond-free diols having 2 to 10 carbon atoms; ethylenediamine, propylene diamines having 2 to 10 carbon atoms and having no carbon-carbon double bond, such as diamine, hexamethylenediamine and isophoronediamine; Among these, diols having 2 to 10 carbon atoms and no carbon-carbon double bond are preferred, and can facilitate the production of thermoplastic elastomers using the reactive composition of the present invention. Therefore, 1,4-butanediol is particularly preferred. The chain extension compounds (C) may be used singly or in combination of two or more.

The content of the chain extension compound (C) in the reactive composition of the present invention is not particularly limited. The amount is preferably 0.1 to 10 times, more preferably 0.2 to 5 times, and still more preferably 0.3 to 2 times.

In the case of using the chain extension compound (C), the compound (B) having two isocyanate groups in the molecule in the reactive composition of the present invention is the reaction of the monocyclic olefin polymer (A). In addition to reacting with the functional group, it also reacts with the active hydrogen atoms contained in the chain extension compound (C) (active hydrogen atoms contained in hydroxyl groups or amino groups). Specifically, one isocyanate of the compound (B) having two isocyanate groups in the molecule reacts with one active hydrogen atom contained in the chain extension compound (C). Therefore, in the case of using the chain extension compound (C), the amount of the compound (B) having two isocyanate groups in the molecule is determined according to the "reaction of the polymer chain end of the monocyclic olefin ring-opening polymer (A) active hydrogen atom contained in the functional group + chain extension compound (C): the isocyanate group of the compound (B) having two isocyanate groups in the molecule" at a molar ratio of 1:0.9 to 1:1.1. It is preferable to set the amount within the range, and more preferable to set the amount within the range of 1:0.95 to 1:1.05.

<Reactive composition>
The reactive composition of the present invention includes the monocyclic olefin ring-opening polymer (A) described above, a compound (B) having two isocyanate groups in the molecule, and a chain extension compound (C ) can be produced by mixing. The mixing method is not particularly limited, and known methods can be used without limitation. Moreover, in the case of mixing, you may mix in a solvent. The solvent to be used is not particularly limited, but hydrocarbons such as toluene and cyclohexane; ethers such as tetrahydrofuran and anisole; esters such as ethyl acetate and ethyl benzoate; ketones such as acetone, 2-butanone and acetophenone; , dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and other aprotic polar solvents. One of these solvents may be used alone, or two or more of them may be used as a mixed solvent.

Further, in the reactive composition, the monocyclic olefin ring-opening polymer (A) described above, a compound (B) having two isocyanate groups in the molecule, and a chain extension compound ( In addition to C), it may contain other components. Other components include, for example, polymerization accelerators, heat stabilizers (eg, antioxidants), stabilizers such as light stabilizers, and the like.

As the polymerization accelerator, metal catalysts such as organotin compounds (dibutyltin dilaurate, dioctyltin dilaurate, etc.) and bismuth compounds; base catalysts such as organic amines; urethane reaction catalysts such as DMC catalysts; The amount of the polymerization accelerator used in the reactive composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 10 parts by weight, per 100 parts by weight of the monocyclic olefin ring-opening polymer (A). 02 to 5 parts by weight.

<Thermoplastic elastomer>
The thermoplastic elastomer of the present invention comprises the monocyclic olefin ring-opening polymer (A), the compound (B) having two isocyanate groups in the molecule, and the necessary obtained by reacting with a chain extension compound (C) used according to

When the chain extension compound (C) is used, the method for producing the thermoplastic elastomer of the present invention is not particularly limited. It may have a step of reacting the compound (B) possessed by itself to obtain a prepolymer, and a step of reacting the thus obtained prepolymer with the chain extension compound (C). Alternatively, as a method for producing the thermoplastic elastomer of the present invention, a monocyclic olefin ring-opening polymer (A), a compound (B) having two isocyanate groups in the molecule, and a chain extension compound (C) It may have a step of reacting after mixing together. More specifically, the monocyclic olefin (A) and the compound (B) having two isocyanate groups in the molecule are pre-reacted to produce a prepolymer having a terminal isocyanate group, and then the chain extension compound (C ), the thermoplastic elastomer of the present invention can be produced. Alternatively, after uniformly mixing the monocyclic olefin ring-opening polymer (A) and the chain extension compound (C), the compound (B) having two isocyanate groups in the molecule is added and stirred for a short time with a rotary mixer. The thermoplastic elastomer of the present invention can also be produced by supplying to a continuous polymerization apparatus having a twin-screw and reacting continuously.

The reaction temperature for reacting the reactive composition of the present invention is not particularly limited, but is preferably 60 to 250°C, more preferably 70 to 200°C. The reaction temperature is also not particularly limited, and is selected, for example, in the range of 1 minute to 5 hours. As a heating method, methods such as press heating, oven heating, steam heating, hot air heating, and microwave heating may be appropriately selected.

The weight-average molecular weight (Mw) of the thermoplastic elastomer of the present invention is not particularly limited, but is the weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography, preferably 10,000 to 1,000. 000,000, more preferably 20,000 to 700,000, still more preferably 50,000 to 500,000.

Various additives such as antioxidants, plasticizers, inorganic fillers, lubricants, colorants, silicone oils, foaming agents and flame retardants may be added to the thermoplastic elastomer of the present invention, if necessary. good.

When the reactive composition of the present invention is reacted to obtain a thermoplastic elastomer, and the reaction of the reactive composition of the present invention is carried out in a solvent, a method of recovering by distilling off the polymerization solvent from the reaction solution; Alternatively, the thermoplastic elastomer of the present invention can be formed into a molded article having a desired shape by a method in which the reaction solution is directly poured into a mold and then dried. Alternatively, the reaction solution is added and mixed with a poor solvent for the thermoplastic elastomer of the present invention, such as methanol, ethanol, etc., to coagulate and precipitate the thermoplastic elastomer, separated by filtration, dried, and subjected to a molding process. A molded body having a desired shape may be used. Molding methods include, for example, extrusion molding, injection molding, calendar molding and blow molding.

The thermoplastic elastomer of the present invention can be obtained as described above. Further, the thermoplastic elastomer of the present invention can be made into a molded article having a desired shape as described above.
In particular, the thermoplastic elastomer of the present invention is obtained by using the reactive composition of the present invention described above, and the reactive composition of the present invention comprises the monocyclic olefin ring-opening polymer (A) described above. Since it is used, it has good fluidity at 60 ° C., and when it is reacted to make a thermoplastic elastomer, it has high tensile strength, large elongation, and excellent heat resistance. and ozone resistance. Therefore, the reactive composition of the present invention and the thermoplastic elastomer obtained using the reactive composition of the present invention are in the state of the reactive composition before reaction (that is, the state of the reactive composition before being converted into a thermoplastic elastomer by reaction). It can be suitably used in applications where fluidity is required in and applications where it is preferable to have fluidity before the reaction and where heat resistance and ozone resistance are required. Further, since the thermoplastic elastomer of the present invention has rubber elasticity, it can be suitably used for applications requiring elasticity. Specifically, the adhesives, sealing materials, coating agents used in the soles of sports shoes, textiles for clothing, artificial leather, construction and civil engineering fields, automotive and electronic equipment fields, aerospace fields, and medical fields, and paint, and furthermore, it can be suitably used as a coating material for electric insulation such as electric wires and connectors used in the fields of automobiles and electronic equipment.

The present invention will be described below based on more detailed examples, but the present invention is not limited to these examples. In the following, "parts" are by weight unless otherwise specified. Various tests and evaluations were conducted according to the following methods.

[Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn) of Monocyclic Olefin Ring-Opening Polymer]
Using a gel permeation chromatography (GPC) system HLC-8220 (manufactured by Tosoh Corporation), two H-type columns HZ-M (manufactured by Tosoh Corporation) are connected in series, tetrahydrofuran is used as a solvent, and the column temperature is 40. °C, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the monocyclic olefin ring-opening polymer were measured. A differential refractometer RI-8320 (manufactured by Tosoh Corporation) was used as a detector. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the monocyclic olefin ring-opening polymer were measured as polystyrene equivalent values.

[Glass transition temperature (Tg) and melting point (Tm) of monocyclic olefin ring-opening polymer]
A differential scanning calorimeter (DSC, product name “X-DSC7000”, manufactured by Hitachi High-Tech Science) was used to measure from −150° C. to 60° C. at a temperature increase of 10° C./min.

[Monomer unit composition ratio in monocyclic olefin ring-opening polymer]
The monomer unit composition ratio in the monocyclic olefin ring-opening polymer was obtained from ¹ H-NMR spectrum measurement.

[Melt Viscosity of Monocyclic Olefin Ring-Opening Polymer]
The melt viscosity at 60° C. was measured with a Brookfield viscometer DV-II+Pro (manufactured by Brookfield). The shear rate during measurement was adjusted between 1.2 and 10 sec ^-1 according to the viscosity.

[Introduction rate of reactive group at polymer chain end of monocyclic olefin ring-opening polymer]
A monocyclic olefin ring-opening polymer is dissolved in heavy chloroform, and ¹ H-NMR spectrum measurement of the heavy chloroform solution in which the monocyclic olefin ring-opening polymer is dissolved reveals peak integral values specific to reactive groups and olefin-derived peaks. was measured for the ratio of the peak integral values of . Then, the reactive group introduction rate at the polymer chain end was calculated based on the ratio of the measured peak integral values and the measurement result of the number average molecular weight (Mn) by GPC described above. The introduction rate of reactive groups at the ends of polymer chains was defined as the ratio of the number of reactive groups to the number of monocyclic olefin ring-opened polymer chains. That is, the reactive group introduction rate = 100% indicates a state in which one reactive group is introduced with respect to one molecule of the monocyclic olefin ring-opened polymer chain, and the reactive group introduction rate = 200. % indicates the state in which reactive groups are introduced at both ends of one monocyclic olefin ring-opening polymer chain.

[Tensile strength and elongation at break of thermoplastic elastomer]
A dumbbell-shaped test piece was obtained by punching out a sheet-shaped thermoplastic elastomer with a dumbbell-shaped No. 6 shape in a direction parallel to the grain direction. Then, the obtained dumbbell-shaped test piece was tested using a tensile tester (product name "TENSOMETER 10K", manufactured by ALPHA TECHNOLOGIES) as a testing machine, and under the conditions of 23°C and 500 mm/min in accordance with JIS K6251. , a tensile test was performed to measure the tensile strength and elongation at break.

[Change rate of tensile strength of thermoplastic elastomer before and after heat treatment]
A dumbbell-shaped test piece was obtained in the same manner as in the above tensile test, and the obtained dumbbell-shaped test piece was subjected to aging at 100 ° C. and 72 degrees Celsius with a gear aging tester (product name “AG-1110”, manufactured by Ueshima Seisakusho Co., Ltd.). A heat treatment was performed under the condition of time to obtain a test piece after the heat treatment. Then, the test piece after heat treatment was subjected to a tensile test in the same manner as the above tensile test, and the tensile strength _S1 of the test piece after heat treatment was measured. Then, from the obtained measurement results and the tensile strength _S0 before heat treatment measured above, the change rate ΔS of the tensile strength before and after heat treatment was determined according to the following formula. Note that the smaller the absolute value of the rate of change ΔS in the tensile strength before and after the heat treatment, the smaller the change due to the heat treatment, and thus is preferable.
Rate of change in tensile strength before and after heat treatment ΔS (%)={(Tensile strength S ₁ (MPa) after heat treatment−Tensile strength S ₀ (MPa) before heat treatment)/Tensile strength S ₀ (MPa) before heat treatment}× 100

[Static ozone deterioration test]
A dumbbell-shaped test piece was obtained by punching out a sheet-shaped thermoplastic elastomer with a dumbbell-shaped No. 1 shape. Dumbbell-shaped test pieces were tested according to JIS K6259 with an ozone weather meter (product name "OMS HN", manufactured by Suga Test Instruments Co., Ltd.) at a test temperature of 40°C, an ozone concentration of 50 pphm, a tensile strain of 20%, and a test time of 24 hours. A static ozone degradation test was performed at After the ozone deterioration test, the ozone resistance of the test piece was evaluated by observing the crack size of the test piece according to JIS K 6259 according to the crack state observation method.
The size of the row of the test piece was evaluated according to the following criteria.
1: The swelling is not visible to the naked eye, but visible with a 10x magnifying glass.
2: A row can be confirmed with the naked eye.
3: The crack is deep and relatively large (less than 1 mm).
4: Deep and large crack (1 mm or more and less than 3 mm).
5: Those with cracks of 3 mm or more, or those that are likely to break.

[Synthesis Example 1]
Synthesis of monocyclic olefin ring-opening polymer (A-1) having hydroxyl groups at both ends Under a nitrogen atmosphere, 1000 parts of cyclopentene and cis-2-butene-1,4- were placed in a pressure-resistant glass reaction vessel equipped with a magnetic stirrer. 28.2 parts of diol and 990 parts of tetrahydrofuran were added. Then, 0.068 part of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium (II) dissolved in 10 parts of tetrahydrofuran was added, and the polymerization reaction was carried out at room temperature for 3 hours. . After the polymerization reaction for 3 hours, excess vinyl ethyl ether was added to terminate the polymerization, and a large amount of methanol was added to precipitate the polymer. Next, after collecting the precipitate by removing the supernatant liquid, the collected precipitate is subjected to vacuum drying at 50 ° C. for 24 hours after removing the remaining solvent with an evaporator, thereby obtaining a monovalent compound having hydroxyl groups at both ends. 700 parts of a cyclic olefin ring-opening polymer (A-1) was obtained. The resulting liquid monocyclic olefin ring-opening polymer (A-1) having hydroxyl groups at both ends has Mw = 7,100, Mn = 4,600, a terminal reactive group introduction rate of 200%, and Tg = - 92°C, Tm = 23°C. Moreover, the melt viscosity measured at 60° C. was 0.6 Pa·s.

[Synthesis Example 2]
Synthesis of monocyclic olefin ring-opening polymer (A-2) having hydroxyl groups at both ends Synthesis Example 1, except that the amount of cyclopentene used was changed from 1000 parts to 850 parts and 150 parts of dicyclopentadiene was further used. 750 parts of a monocyclic olefin ring-opening polymer (A-2) having hydroxyl groups at both ends was obtained in the same manner as above. The resulting monocyclic olefin ring-opening polymer (A-2) having hydroxyl groups at both ends has Mw = 7,700, Mn = 4,200, and is a monomer derived from cyclopentene in the monocyclic olefin ring-opening polymer. The unit content was 92 mol%, the dicyclopentadiene-derived monomer unit content was 8 mol%, the terminal reactive group introduction rate was 200%, Tg = -81°C, and Tm was not observed. . Moreover, the melt viscosity measured at 60° C. was 1.5 Pa·s.

[Synthesis Example 3]
Synthesis of monocyclic olefin ring-opening polymer having hydroxyl groups at both ends (A-3) Hydroxyl groups at both ends in the same manner as in Synthesis Example 1, except that 1000 parts of cyclooctadiene was used instead of 1000 parts of cyclopentene. 850 parts of a monocyclic olefin ring-opening polymer (A-3) having The resulting monocyclic olefin ring-opening polymer (A-3) having hydroxyl groups at both ends has Mw = 11,000, Mn = 6,500, a terminal reactive group introduction rate of 200%, and Tg = -104°C. and no Tm was observed. Moreover, the melt viscosity measured at 60° C. was 2.4 Pa·s.

[Synthesis Example 4]
Synthesis of monocyclic olefin ring-opening polymer (A'-4) having no reactive group at the end In Synthesis Example 1, instead of 28.2 parts of cis-2-butene-1,4-diol, 1- A liquid monocyclic olefin ring-opening polymer (A'-4) having no reactive groups at the terminals was obtained in the same manner as in Synthesis Example 1, except that 21.5 parts of hexene was used. The resulting monocyclic olefin ring-opening polymer (A'-4) having no reactive group at the end had Mw = 13,200, Mn = 7,700, Tg = -93°C, and Tm = 23°C. there were. Moreover, the melt viscosity measured at 60° C. was 1.2 Pa·s.

[Reference Example 1]
100 parts of the monocyclic olefin ring-opening polymer (A-1) having hydroxyl groups at both ends obtained in Synthesis Example 1 was added to a glass reactor and dried under reduced pressure at 80° C. for 2 hours to remove moisture. Then, 11.1 parts of 4,4′-diphenylmethane diisocyanate (MDI) (an amount that makes the OH/MDI NCO of the polymer (A-1) = 1/2.04 (molar ratio)) is stirred under a nitrogen atmosphere. A prepolymer was obtained by adding while stirring and reacting at 80° C. for 2 hours. Then, 1.95 parts of 1,4-butanediol (1,4-BD) (an amount that makes OH of 1,4-BD/NCO of MDI = 1/2.04 (molar ratio)) was added and stirred. After that, the mixture was transferred to a kneading tester (product name “Plastograph ECPlus”, manufactured by Brabender) and kneaded at 160° C. and 30 rpm for 10 minutes in a nitrogen atmosphere to obtain a thermoplastic elastomer. The resulting thermoplastic elastomer had Mw=125,000 and Mn=68,000. The obtained thermoplastic elastomer was vacuum heat-pressed at 120° C. for 1 hour to form a sheet-like thermoplastic elastomer having a thickness of 1 mm. Then, using the obtained sheet-like thermoplastic elastomer, each measurement of tensile strength, elongation at break, change rate of tensile strength before and after heat treatment, and a static ozone deterioration test were performed according to the above method. Table 1 shows the results.

[Example 2]
100 parts of the monocyclic olefin ring-opening polymer (A-2) having hydroxyl groups at both ends obtained in Synthesis Example 2, and 12 parts of 4,4′-diphenylmethane diisocyanate (MDI) (polymer (A-2) An amount of OH/MDI (NCO = 1/2.04 (molar ratio)) was added to a glass reactor equipped with a stirrer and dried under reduced pressure for 2 hours to remove moisture. In a nitrogen atmosphere, 400 parts of toluene was added to the glass reactor and stirred to dissolve the monocyclic olefin ring-opening polymer (A-2) and 4,4′-diphenylmethane diisocyanate in toluene. Then, 3.1 parts of dibutyltin dilaurate (0.1 molar equivalent with respect to NCO of MDI) was added and reacted at 80° C. for 1 hour while stirring. Then, as the chain extension compound (C), 2.2 parts of 1,4-butanediol (1,4-BD) (OH of 1,4-BD/NCO of MDI = 1/2.04 (molar ratio) amount) was added and reacted at 80° C. for 1 hour while stirring. The resulting reaction solution was added to a large amount of methanol and stirred, and the precipitate was collected and vacuum-dried at 50° C. for 3 days to obtain a thermoplastic elastomer. The resulting thermoplastic elastomer had Mw=203,000 and Mn=71,000. The obtained thermoplastic elastomer was vacuum heat-pressed at 120° C. for 1 hour to form a sheet-like thermoplastic elastomer having a thickness of 1 mm. Then, using the obtained sheet-like thermoplastic elastomer, each measurement of tensile strength, elongation at break, change rate of tensile strength before and after heat treatment, and a static ozone deterioration test were performed according to the above method. Table 1 shows the results.

[ Reference example 2 ]
100 parts of the monocyclic olefin ring-opening polymer (A-3) having hydroxyl groups at both ends obtained in Synthesis Example 3 and 7.9 parts of 4,4′-diphenylmethane diisocyanate (MDI) (polymer (A-3) OH/MDI NCO = 1/2.04 (molar ratio)) was added to a glass reactor equipped with a stirrer and dried under reduced pressure for 2 hours to remove moisture. In a nitrogen atmosphere, 400 parts of toluene was added to the glass reactor and stirred to dissolve the monocyclic olefin ring-opening polymer (A-3) and 4,4′-diphenylmethane diisocyanate in toluene. Then, 2.0 parts of dibutyltin dilaurate (0.1 molar equivalent with respect to NCO of MDI) was added and reacted at 80° C. for 1 hour while stirring. Then, as the chain extension compound (C), 1.4 parts of 1,4-butanediol (1,4-BD) (OH of 1,4-BD/NCO of MDI = 1/2.04 (molar ratio) amount) was added and reacted at 80° C. for 1 hour while stirring. The obtained reaction solution was added to a large amount of methanol and stirred, and the precipitate was collected and vacuum-dried at 50° C. for 3 days to obtain a thermoplastic elastomer. The resulting thermoplastic elastomer had Mw=153,000 and Mn=62,000. Further, the obtained thermoplastic elastomer was vacuum heat-pressed at 120° C. for 1 hour to obtain a sheet-like thermoplastic elastomer having a thickness of 1 mm. Then, using the obtained sheet-like thermoplastic elastomer, each measurement of tensile strength, elongation at break, change rate of tensile strength before and after heat treatment, and a static ozone deterioration test were performed according to the above method. Table 1 shows the results.

[Comparative Example 1]
In place of 100 parts of the monocyclic olefin ring-opening polymer (A-1) having hydroxyl groups at both ends, liquid polybutadiene (A'-5) having hydroxyl groups at both ends (trade name "Krasol LBH-P3000", clay Valley Corporation) 100 parts, the amount of 4,4'-diphenylmethane diisocyanate (MDI) used is 31.9 parts (OH of polybutadiene (A'-5)/NCO of MDI = 1/2.04 (molar ratio ), and the amount of 1,4-butanediol (1,4-BD) used is 5.6 parts (OH of 1,4-BD/NCO of MDI = 1/2.04 (molar ratio) A thermoplastic elastomer was obtained in the same manner as in Reference Example 1 , except that the amount was set to The resulting thermoplastic elastomer had Mw=137,000 and Mn=72,000. Then, in the same manner as in Reference Example 1 , a sheet-like thermoplastic elastomer having a thickness of 1 mm was obtained and evaluated in the same manner as in Reference Example 1 . Table 1 shows the results.

[Comparative Example 2]
Instead of 100 parts of the monocyclic olefin ring-opening polymer (A-1) having hydroxyl groups at both ends, the monocyclic olefin ring-opening polymer having no reactive groups at the ends obtained in Synthesis Example 4 (A' -4) was carried out in the same manner as in Reference Example 1, the reaction between the monocyclic olefin ring-opening polymer (A'-4) and 4,4'-diphenylmethane diisocyanate did not proceed. Therefore, it has not been possible to obtain a thermoplastic elastomer that can be molded into a sheet.

As shown in Table 1, a monocyclic olefin ring-opening polymer (A) having a reactive group at the polymer chain end and a weight average molecular weight (Mw) of 1,000 to 50,000, and isocyanate The thermoplastic elastomer obtained using the reactive composition containing the compound (B) having two groups in the molecule has high tensile strength, large elongation, and excellent heat resistance and ozone resistance. There was (Example 2 ).
On the other hand, when a liquid polybutadiene having hydroxyl groups at both ends is used instead of the monocyclic olefin ring-opened polymer (A), the absolute value of the rate of change ΔS in tensile strength before and after the heat treatment is large, and the heat resistance is poor. Furthermore, it was inferior in ozone resistance (Comparative Example 1).
On the other hand, when a liquid monocyclic olefin ring-opening polymer having no reactive group at the polymer chain end is used, the reaction does not proceed and a thermoplastic elastomer that can be molded into a sheet cannot be obtained. No (Comparative Example 2).

Claims (3)

A monocyclic olefin ring-opening polymer (A) having a reactive group that reacts with an isocyanate group at the polymer chain end and having a weight average molecular weight (Mw) of 1,000 to 50,000; containing a compound (B) having two in the molecule and a chain extension compound (C) having two hydroxyl groups or amino groups in the molecule and a molecular weight of 800 or less,
The monocyclic olefin ring-opening polymer (A) is a copolymer comprising a structural unit derived from cyclopentene and a structural unit derived from a monomer copolymerizable with cyclopentene,
The ratio of structural units derived from cyclopentene is 70 mol% or more with respect to all repeating units,
The reactive composition, wherein the monomer copolymerizable with cyclopentene is dicyclopentadiene. 2. The reactive composition according to claim 1, wherein the reactive group at the polymer chain end of the monocyclic olefin ring-opening polymer (A) is a hydroxyl group. A thermoplastic elastomer obtained by reacting the reactive composition according to claim 1 or 2.