Hydrogenated cyclic polymer, production method thereof, and resin composition

Abstract

Provided is a cyclic polymer hydride containing a cyclic chain comprising repeating units of a cyclic olefin ring-opening polymerization unit.

Description

[Technical field]

[0001] The present invention relates to a hydrogenated cyclic polymer, a method for producing the same, and a resin composition. [Background technology]

[0002] Conventionally, various methods for producing polymers, including a step of ring-opening metathesis polymerization of cyclic olefin monomers, have been studied for the purpose of obtaining polymers having industrially useful attributes. For example, Non-Patent Document 1 discloses a method for polymerizing norbornene by stereoselective ring expansion metathesis polymerization (REMP) as a method for producing cyclic polynorbornene having high configuration regularity of repeating units. In addition, Patent Document 1 discloses a metathesis polymerization method including a step of stimulating a reaction mixture containing a cyclic unsaturated monomer and an organic initiator to activate the organic initiator, and a step of polymerizing a cyclic unsaturated monomer via a four-membered carbon ring intermediate by the activated organic initiator. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2016 / 036976 [Non-patent literature]

[0004] [Non-Patent Document 1] Stella A. Gonzales et al, “Highly Tactic Cyclic Polynorbornene: Stereoselective Ring Expansion Metathesis Polymerization (REMP) of Norbornene Catalyzed By a New Tethered Tungsten-alkylidene Catalyst”, Journal of the American Chemical Society 138(15), April 2016, p. 1-51 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, polymers having novel structures have been required. Thus, an object of the present invention is to provide a hydrogenated cyclic polymer having a novel structure that has not existed before. Furthermore, an object of the present invention is to provide a resin composition containing the hydrogenated cyclic polymer having the novel structure. [Means for solving the problem]

[0006] The present inventors have conducted extensive research with the aim of solving the above problems, and have found that a novel structure that has never existed before can be created by ring-opening polymerization of a cyclic olefin monomer and then hydrogenating the resulting ring-opening polymer, thereby completing the present invention.

[0007] That is, the present invention has an object to advantageously solve the above problems, and the hydrogenated cyclic polymer of the present invention is characterized in that it is a hydrogenated cyclic polymer containing a cyclic chain composed of repeating units of cyclic olefin ring-opening polymerization units. Such a hydrogenated cyclic polymer has a novel structure. The structure of the cyclic polymer hydrogenated product can be analyzed by the method described in the Examples of this specification.

[0008] Here, in the hydrogenated cyclic polymer of the present invention, the cyclic chain of the cyclic polymer preferably contains an ether bond.

[0009] The present invention also aims to advantageously solve the above problems, and the method for producing a hydrogenated cyclic polymer of the present invention is characterized by comprising a ring-opening polymerization step of ring-opening polymerizing at least one cyclic olefin monomer in the presence of a cyclic vinyl ether compound to obtain a cyclic polymer containing a cyclic chain composed of repeating units of cyclic olefin ring-opening polymerized units, and a hydrogenation step of hydrogenating the cyclic polymer to obtain a hydrogenated cyclic polymer. According to this production method, the hydrogenated cyclic polymer of the present invention can be efficiently produced.

[0010] In the method for producing a hydrogenated cyclic polymer of the present invention, the cyclic chain of the cyclic polymer obtained in the ring-opening polymerization step preferably contains an ether bond.

[0011] Another object of the present invention is to advantageously solve the above problems, and the resin composition of the present invention is characterized by containing any one of the above-mentioned hydrogenated cyclic polymers. Effect of the Invention

[0012] According to the present invention, it is possible to provide a hydrogenated cyclic polymer having a novel structure. Also, according to the present invention, it is possible to provide a resin composition containing the hydrogenated cyclic polymer having the novel structure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described in detail. The hydrogenated cyclic polymer of the present invention is a polymer that can be used in various fields as a resin material constituting various molded articles. The hydrogenated cyclic polymer of the present invention is also suitably used as a constituent material of the resin composition of the present invention. The hydrogenated cyclic polymer of the present invention can be efficiently produced according to the method for producing a hydrogenated cyclic polymer of the present invention.

[0014] (Hydride Cyclic Polymers) The hydrogenated cyclic polymer of the present invention is a hydrogenated cyclic polymer containing a cyclic chain consisting of repeating units of cyclic olefin ring-opening polymerization units. In this specification, the term "cyclic chain" refers to a state in which a polymer chain formed by linking two or more monomers is in a cyclic shape. The cyclic polymer may have a side chain in addition to the cyclic chain that is the main chain. The hydrogenated cyclic polymer of the present invention is obtained by hydrogenating at least a part of the carbon-carbon double bonds contained in the cyclic chain and the side chain of the cyclic polymer.

[0015] <Cyclic chain> Here, the cyclic chain is composed of repeating units of cyclic olefin ring-opening polymerization units as described above. More specifically, the cyclic chain preferably contains only cyclic olefin ring-opening polymerization units as repeating units.

[0016] <<Cyclic olefin ring-opening polymerization unit>> The cyclic olefin monomer that can be used to form the cyclic olefin ring-opening polymerization unit is not particularly limited, and examples thereof include a monomer having a norbornene skeleton (hereinafter referred to as a "norbornene-based monomer") and a monocyclic cycloalkene monomer, etc. The monomer may be used alone or in combination of two or more kinds.

[0017] -Norbornene monomer- Here, examples of the norbornene-based monomer include norbornene, a norbornene-based monomer not having a ring condensed with a norbornene ring (hereinafter, sometimes referred to as a "non-condensed ring-forming norbornene-based monomer"), and a norbornene-based monomer having a ring condensed with a norbornene ring (hereinafter, sometimes referred to as a "condensed ring-forming norbornene-based monomer").

[0018] Examples of the norbornene monomers that do not form a condensed ring include norbornenes having an alkyl group such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene; norbornenes having an alkenyl group such as 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene, and 5-cyclopentenylnorbornene; norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, and 5-cyclopentylnorbornene. norbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanate, 5-hydroxymethylnorbornene, 5,6-di(hydroxymethyl)norbornene, 5,5-di(hydroxymethyl)norbornene, 5-hydroxyisopropylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene, and other norbornenes having a polar group containing an oxygen atom; and norbornenes having a polar group containing a nitrogen atom, such as 5-cyanonorbornene. These may be used alone or in combination of two or more.

[0019] Examples of the condensed ring-forming norbornene monomer include monomers represented by the following formulae (I) and (II).

[0020] [ka]

[0021] In the above formula (I), R 1 and R 2R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent containing a silicon atom, an oxygen atom, or a nitrogen atom (excluding those corresponding to a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent), and may be bonded to each other to form a ring. 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

[0022] [ka]

[0023] In the above formula (II), R 4 , R 5 , R 6 , R 7 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent containing a silicon atom, an oxygen atom, or a nitrogen atom (excluding those which fall under the category of a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent); R 4 and R 6 may be bonded to each other to form a ring. m is 1 or 2.

[0024] Examples of the monomer represented by the above formula (I) include dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, tricyclo[5.2.1.0 2,6 ]dec-8-ene, tetracyclo[9.2.1.0 2,10 .0 3,8 ]tetradeca-3,5,7,12-tetraene (also called 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene), tetracyclo[10.2.1.0 2,11 .0 4,9 ]pentadeca-4,6,8,13-tetraene (also called 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene). These may be used alone or in combination of two or more.

[0025] Examples of the monomer represented by the above formula (II) include tetracyclododecenes in which m is 1 and hexacycloheptadecenes in which m is 2.

[0026] Examples of tetracyclododecenes (m=1) include tetracyclododecene; tetracyclododecenes having an alkyl group such as 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene; tetracyclododecenes having a double bond outside the ring such as 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; Examples of the tetracyclododecene include tetracyclododecene having a substituent containing an oxygen atom, such as tetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, and tetracyclododecene-8,9-dicarboxylic anhydride; tetracyclododecene having a substituent containing a nitrogen atom, such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imide; tetracyclododecene having a substituent containing a halogen atom, such as 8-chlorotetracyclododecene; and tetracyclododecene having a substituent containing a silicon atom, such as 8-trimethoxysilyltetracyclododecene. These may be used alone or in combination of two or more.

[0027] Examples of hexacycloheptadecenes (m=2) include hexacycloheptadecene; hexacycloheptadecene having an alkyl group such as 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, and the like. Hexacycloheptadecenes having a double bond outside the ring, such as 12-hexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, and 12-cyclopentenylhexacycloheptadecene; hexacycloheptadecenes having an aromatic ring, such as 12-phenylhexacycloheptadecene; 12-methoxycarbonyl Examples of the hexacycloheptadecene include hexacycloheptadecene having a substituent containing an oxygen atom, such as hexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12,13-dicarboxylic acid, and hexacycloheptadecene 12,13-dicarboxylic anhydride; hexacycloheptadecene having a substituent containing a nitrogen atom, such as 12-cyanohexacycloheptadecene and hexacycloheptadecene 12,13-dicarboxylic imide; hexacycloheptadecene having a substituent containing a halogen atom, such as 12-chlorohexacycloheptadecene; and hexacycloheptadecene having a substituent containing a silicon atom, such as 12-trimethoxysilylhexacycloheptadecene.

[0028] Among these, norbornene-based monomers such as norbornene, dicyclopentadiene, and tetracyclododecene are preferred.

[0029] -Monocyclic cycloalkene monomer- Examples of the monocyclic cycloalkene monomer include cyclopentene, cyclohexene, cycloheptane, etc. Among them, the monocyclic cycloalkene monomer is preferably cyclopentene.

[0030] Furthermore, in the hydrogenated cyclic polymer of the present invention, the cyclic chain preferably contains an ether bond, more specifically, the cyclic chain preferably contains one ether bond.

[0031] <Hydrogenation rate> The hydrogenation rate of the hydrogenated cyclic polymer of the present invention (the ratio of hydrogenated carbon-carbon double bonds to all carbon-carbon double bonds contained in the precursor cyclic polymer) is usually 90% or more, preferably 95% or more, and more preferably 99% or more. The hydrogenation rate (molar basis) of the hydrogenated cyclic polymer is 1 It can be identified by H-NMR measurement. The hydrogenation rate of the hydrogenated cyclic polymer product can be adjusted, for example, by changing the conditions of the hydrogenation reaction.

[0032] <Weight average molecular weight> The hydrogenated cyclic polymer of the present invention preferably has a weight average molecular weight of 3,000 or more, more preferably 5,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less. The weight average molecular weight of the hydrogenated cyclic polymer can be adjusted by changing the method for producing the hydrogenated cyclic polymer, for example, by changing the type and / or amount of the cyclic vinyl ether compound and catalyst added when preparing the cyclic polymer, which is the precursor of the hydrogenated cyclic polymer.

[0033] <Metal content> The cyclic polymer hydrogenated product of the present invention preferably has a metal content of 10 ppm or less, more preferably 5 ppm or less, based on the total mass of the cyclic polymer hydrogenated product. The metal may be at least one selected from the group including Ru, Mo, W, and Ni. When the cyclic polymer hydrogenated product contains a plurality of metals, the total content of the metals is preferably equal to or less than the upper limit. These metals may remain in the cyclic polymer hydrogenated product due to catalytic components that may be optionally used during synthesis of the cyclic polymer, which is the precursor of the cyclic polymer hydrogenated product, and / or during hydrogenation of the cyclic polymer. In the cyclic polymer hydrogenated product of the present invention, if the metal content is equal to or less than the upper limit, high transparency can be obtained. The metal content in the cyclic polymer hydrogenated product can be obtained by ICP (Inductively Coupled Plasma) emission spectroscopy.

[0034] (Method of producing hydrogenated cyclic polymer) The method for producing a hydrogenated cyclic polymer of the present invention is characterized by comprising a ring-opening polymerization step of ring-opening polymerizing at least one cyclic olefin monomer in the presence of a cyclic vinyl ether compound to obtain a cyclic polymer containing a cyclic chain composed of repeating units of cyclic olefin ring-opening polymerized units, and a hydrogenation step of hydrogenating the cyclic polymer to obtain a hydrogenated cyclic polymer. According to this production method, the above-mentioned hydrogenated cyclic polymer of the present invention can be efficiently produced. After the hydrogenation step, post-treatment may be performed as necessary.

[0035] <Ring-opening polymerization process> In the ring-opening polymerization step, at least one kind of cyclic olefin monomer is ring-opening polymerized in the presence of a cyclic vinyl ether compound to obtain a cyclic polymer containing a cyclic chain consisting of a repeating unit of a cyclic olefin ring-opening polymerization unit. More specifically, a monomer composition containing at least one of the above-mentioned cyclic olefin monomers is ring-opening polymerized in the presence of a cyclic vinyl ether compound. In addition, in the ring-opening polymerization step, a catalyst can be added to the polymerization system. In addition, the ring-opening polymerization step may be performed without a solvent or in the presence of a solvent.

[0036] <<Cyclic vinyl ether>> The cyclic vinyl ether compound is a component that can function as a polymerization initiator in the ring-opening polymerization step. Examples of the cyclic vinyl ether compound include compounds represented by the following general formula (X). [ka] In the above general formula (X), R and R', or one of R' and R'' and R''' form a ring structure. Here, in the above general formula (X), R to R''' can each independently be a substituted or unsubstituted alkyl group having 12 or less carbon atoms, a trialkylsilyl group (wherein each alkyl group is independently an alkyl group having 3 or less carbon atoms), or a substituted or unsubstituted alkoxy group having 12 or less carbon atoms.

[0037] Specifically, examples of cyclic vinyl ether compounds that can be used include 2,3-dihydrofuran and derivatives thereof, 3,4-dihydro-2H-pyran and derivatives thereof, 1-(trimethylsilyloxy)cyclohexene and derivatives thereof, 1-(trimethylsilyloxy)cyclopentene and derivatives thereof, 1-methoxycyclooctene and derivatives thereof, 2,3,4,5-tetrahydrooxepine and derivatives thereof, etc. Among these, from the viewpoint of increasing the yield, 3,4-dihydro-2H-pyran derivatives such as 3,4-dihydro-2-methoxy-2H-pyran and 3,4-dihydro-2-ethoxy-2H-pyran are preferred.

[0038] <<Catalyst>> As a catalyst that can be added to the polymerization system in the ring-opening polymerization step, a photoredox catalyst can be suitably used. Here, the photoredox catalyst is a compound that can generate radical species when irradiated with light in the ultraviolet-visible region, for example, visible light with a wavelength of 425 nm. As a photoredox catalyst that can be suitably used in the ring-opening polymerization step, for example, pyrylium salts and acridinium salts as described in International Publication No. 2016 / 036976 can be mentioned. In particular, a pyrylium salt can be suitably used as a photoredox catalyst in the ring-opening polymerization step. As a pyrylium salt, a pyrylium salt represented by the following formula (III) can be mentioned.

[0039] [ka]

[0040] In formula (III), R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group; X - represents a monovalent anion. The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, and the aryl group may have a substituent. Among them, several R 8 are all methoxy groups, and X - BF4 - That is, the pyrylium salt represented by formula (III) is preferably 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate.

[0041] The catalyst used in the ring-opening polymerization step preferably does not contain a metal.

[0042] <<Solvent>> The ring-opening polymerization step is preferably carried out in a solvent, particularly an organic solvent, from the viewpoint of being able to well control the reaction. The organic solvent to be used is not particularly limited as long as it can dissolve or disperse the obtained cyclic polymer and is inactive in the polymerization reaction.Specific examples thereof include aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, and cyclooctane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene (o-xylene, m-xylene, and p-xylene); halogenated aliphatic hydrocarbon solvents such as dichloromethane, chloroform, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene; nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile; ether solvents such as diethyl ether and tetrahydrofuran; aromatic ether solvents such as anisole and phenetole; and the like. The solvent may be used alone or in combination of two or more kinds. As the solvent, a halogenated aliphatic hydrocarbon solvent is particularly preferable.

[0043] The conditions for the ring-opening polymerization (such as the amounts of the above-mentioned components used, the polymerization time, and the polymerization temperature) are not particularly limited and can be appropriately set depending on the desired physical properties of the cyclic polymer and the hydrogenated cyclic polymer. The cyclic polymer obtained in the ring-opening polymerization step may be recovered from the reaction solution and subjected to the hydrogenation reaction, but the reaction solution containing the cyclic polymer may be subjected to the hydrogenation step as it is.

[0044] <<Ring-opening polymerization scheme>> In one example, when a photoredox catalyst is used as a catalyst and 3,4-dihydro-2H-pyran is used as a vinyl ether compound as a polymerization initiator, the ring-opening polymerization reaction is presumed to proceed according to the following scheme.

[0045] [ka]

[0046] First, a photoredox catalyst such as the pyrylium salt described above is excited by light irradiation and becomes capable of functioning as an electronic oxidant (not shown in the scheme). Then, 3,4-dihydro-2H-pyran is electronically oxidized by the electronic oxidant (scheme (1)) to form a radical cation (scheme (2)). Then, a four-membered ring structure is formed between the radical cation and the cyclic olefin monomer present in the polymerization system, and a radical cation intermediate is generated (scheme (3)). A ring-opening metathesis reaction occurs in the radical cation intermediate (3) thus generated, and the intermediate obtained becomes a further radical cation (scheme (4)). The further radical cation (4) reacts sequentially with n cyclic olefin monomers present in the polymerization system (scheme (5)), thereby extending the cyclic chain of the cyclic polymer. Then, by stopping the light irradiation to terminate the polymerization reaction, the radical cation is electronically reduced (scheme (6)). As a result of such a ring-opening polymerization reaction, a cyclic polymer having one vinyl ether bond derived from 3,4-dihydro-2H-pyran as a polymerization initiator in the cyclic chain is produced (Scheme (7)).

[0047] <<Hydrogenation process>> In the hydrogenation step, the cyclic polymer obtained through the ring-opening polymerization step is hydrogenated to obtain a hydrogenated cyclic polymer. More specifically, in the hydrogenation step, at least a part of the carbon-carbon double bonds in the cyclic chain of the cyclic polymer, and in the case where the cyclic polymer has carbon-carbon double bonds other than the cyclic chain, including these, are hydrogenated. In the hydrogenation step, the hydrogenation rate (molar basis) in the obtained hydrogenated product is preferably 90% or more, more preferably 95% or more, and more preferably 99% or more. In addition, when the carbon-carbon double bonds of the vinyl ether bond derived from the polymerization initiator contained in the cyclic polymer obtained through the ring-opening polymerization step are hydrogenated in the hydrogenation step, the obtained hydrogenated product contains a structural unit containing an ether bond represented by "-COC-".

[0048] Here, the hydrogenation step is not particularly limited, and the carbon-carbon double bonds present in the cyclic polymer can be hydrogenated by (a) adding a hydrogenating agent to a system containing the cyclic polymer obtained in the above step, followed by heating and reacting (hydrogen transfer hydrogenation reaction), or by (b) adding a hydrogenation catalyst, followed by adding hydrogen and reacting (catalytic hydrogenation reaction).

[0049] The hydrogenation agent used in the above-mentioned (a) hydrogen transfer hydrogenation reaction is not particularly limited, and any hydrogenation agent can be used as long as it is capable of hydrogenating the carbon-carbon double bonds present in the cyclic polymer. Examples of the hydrogenation agent include hydrazine and p-toluenesulfonyl hydrazide.

[0050] The hydrogenation catalyst used in the catalytic hydrogenation reaction of (b) above is not particularly limited, and any catalyst generally used in hydrogenation reactions of olefin compounds can be used. For example, Ziegler catalysts consisting of a combination of a transition metal compound and an alkali metal compound, such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, or tetrabutoxytitanate and dimethylmagnesium; dichlorotris(triphenylphosphine)rhodium, RuHCl(CO)(PPh3)3, RuHCl(CO)[P(p-Me-Ph)3]3, RuHCl(CO)(PCy3)2, RuHCl(CO)[P(n-Bu)3]3, RuHCl(CO)[P(i-Pr)3]2, RuH2(CO)(PP homogeneous catalysts such as precious metal complex catalysts composed of ruthenium compounds such as RuH(CO)[P(p-Me-Ph)3]3, RuH2(CO)(PCy3)3, RuH2(CO)[P(n-Bu)3]3, RuH(OCOCH3)(CO)(PPh3)2, RuH(OCOPh)(CO)(PPh3)2, RuH(OCOPh-CH3)(CO)(PPh3)2, RuH(OCOPh-OCH3)(CO)(PPh3)2, and RuH(OCOPh)(CO)(PCy3)2; supported heterogeneous catalysts in which metals such as nickel, palladium, platinum, rhodium, and ruthenium are supported on carriers such as carbon, silica, diatomaceous earth, alumina, and titanium oxide.

[0051] The hydrogenation catalyst may be used alone or in combination of two or more. A supported heterogeneous catalyst is preferable as the hydrogenation catalyst, because the hydrogenation catalyst can be easily removed by filtering the reaction solution after the hydrogenation reaction. Specific preferred examples of supported heterogeneous catalysts include combinations of nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

[0052] <<Conditions for hydrogenation process>> The conditions for the hydrogenation reaction (such as the amounts of hydrogenation agent and hydrogenation catalyst used, the reaction time, the reaction temperature, and the hydrogen pressure when carrying out the catalytic hydrogenation reaction according to the above (b)) are not particularly limited and can be appropriately set depending on the desired physical properties of the hydrogenated cyclic polymer (for example, the hydrogenation rate).

[0053] The solvent used in the hydrogenation step is not particularly limited, and for example, the solvents listed as the solvents (particularly organic solvents) that can be used in the ring-opening polymerization step described above can be used.

[0054] <Post-processing process> Following the above-mentioned ring-opening polymerization step and hydrogenation step, a post-treatment step can be carried out as necessary. In the post-treatment step, the reaction liquid containing the hydrogenated cyclic polymer obtained in the above-mentioned hydrogenation step can be subjected to a coagulation drying method or a direct drying method using a thin film dryer or the like, thereby allowing the desired hydrogenated cyclic polymer to be well isolated. The hydrogenated cyclic polymer can usually be obtained as a powder or pellet-like solid.

[0055] (Resin composition) The resin composition of the present invention contains the above-mentioned hydrogenated cyclic polymer of the present invention and may optionally contain known additives. Since the resin composition of the present invention contains the hydrogenated cyclic polymer of the present invention, it can be advantageously used as a material for a molded body.

[0056] The known additives are not particularly limited, and examples thereof include polymers other than the hydrogenated cyclic polymer of the present invention (such as thermoplastic elastomers), fillers, antioxidants, release agents, flame retardants, antibacterial agents, wood flour, coupling agents, plasticizers, colorants, lubricants, silicone oils, foaming agents, surfactants, light stabilizers, dispersing aids, heat stabilizers, UV absorbers, antistatic agents, dispersants, chlorine scavengers, crystallization nucleating agents, antifogging agents, organic fillers, neutralizing agents, decomposers, metal deactivators, and stain inhibitors. These additives may be used alone or in combination of two or more.

[0057] The method for producing the resin composition is not particularly limited. For example, a method of kneading a hydrogenated cyclic polymer and additives added as needed to obtain a pellet-shaped resin composition, or a method of mixing a hydrogenated cyclic polymer and additives added as needed in a suitable solvent and removing the solvent to obtain a resin composition can be mentioned. EXAMPLES

[0058] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" expressing amounts are based on mass unless otherwise specified. In the examples and comparative examples, the hydrogenation rate and weight average molecular weight of the obtained products were measured by the following methods. The analysis and metal content of the products obtained in the examples and comparative examples were also measured as follows.

[0059] <Weight average molecular weight> The weight-average molecular weight of the hydrogenated cyclic polymer was measured in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent. The measuring device used was an HLC8320GPC (manufactured by Tosoh Corporation). The sample was prepared by dissolving the measurement specimen in tetrahydrofuran at room temperature so that the sample concentration became 1 mg / ml. The measurements were performed using four TSKgel SuperMultiporeHZ-H (Tosoh Corporation) columns connected in series under conditions of a flow rate of 0.35 ml / min, a sample injection amount of 50 μl, and a column temperature of 40°C. <Hydrogenation rate> 1 The calculations were based on H-NMR measurements. More specifically, the ring-opening polymer obtained through the ring-opening polymerization step and the hydrogenated ring-opening polymer obtained through the hydrogenation step were 1H-NMR measurement was performed to obtain the amount of carbon-carbon double bonds (on a molar basis) contained in each ring-opened polymer, and the ratio (%) of the amount of carbon-carbon double bonds contained in the hydrogenated ring-opened polymer was calculated, assuming the amount of carbon-carbon double bonds contained in the ring-opened polymer to be 100%. <Analysis of products> First, the obtained ring-opening polymer was used as a measurement sample. 1 H-NMR was measured. By such measurement, it was judged whether the measurement sample had a structure containing a cyclic olefin ring-opening polymerization unit as a repeating unit and a vinyl ether moiety. Next, the absolute molecular weight of the measurement sample was measured using a time-of-flight mass spectrometer (MALDI (Matrix Assisted Laser Desorption / Ionization)-TOF (Time of Flight)-MS (Mass Spectrometer)), and when it was confirmed that the molecular weight of the mass peak of each polymer chain contained in the measurement sample was (multiple of the molecular weight of the repeating unit) + (molecular weight of the polymerization initiator), the measurement sample was identified as a cyclic polymer. Next, the ring-opening polymer was hydrogenated to obtain a hydrogenated ring-opening polymer as a measurement sample, 1 H-NMR was measured. By such measurement, it was judged whether the measurement sample had a structure containing a cyclic olefin ring-opening polymerization hydrogenation unit as a repeating unit and an ether moiety. Next, the absolute molecular weight of the measurement sample was measured using a time-of-flight mass spectrometer, and when it was confirmed that the molecular weight of the mass peak of each polymer chain contained in the measurement sample was (multiple of the molecular weight of the hydrogenation of the repeating unit) + (molecular weight of the hydrogenation of the polymerization initiator), the measurement sample was identified as a cyclic polymer. In Example 5, in which a polymer with a relatively high molecular weight was obtained, in addition to the above analyses, analysis was performed using GPC-MALLS (Gel Permeation Chromatography-Multiangle Laser Light Scattering) to confirm that a cyclic polymer was obtained. <Metal content of product> In addition, the total content of Ru, Mo, W, and Ni (ppm; mass basis of the hydride) of the cyclic polymer hydrides obtained in the examples was obtained by ICP (Inductively Coupled Plasma) atomic emission spectrometry, and it was confirmed that it was 5 ppm or less in all examples.

[0060] Example 1 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of norbornene as a cyclic olefin monomer was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 34.6 mg of 3,4-dihydro-2H-pyran, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.01 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was 9,100. The obtained ring-opened polymer was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains a vinyl ether moiety of 3,4-dihydro-2H-pyran, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (molecular weight of 3,4-dihydro-2H-pyran as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the hydrogenated ring-opened polymer obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed precipitate was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the hydrogenated ring-opened polymer obtained was measured as described above, and was found to be 99% or more. The hydrogenated ring-opened polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the hydrogenated ring-opened polymer obtained had a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit obtained by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 3,4-dihydro-2H-pyran, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the hydrogenated ring-opened polymer as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of the hydrogenated norbornene as the cyclic olefin monomer) + (molecular weight of the hydrogenated 3,4-dihydro-2H-pyran as the polymerization initiator). From these results, it was confirmed that the hydrogenated ring-opened polymer obtained in this step was a cyclic polymer.

[0061] Example 2 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of norbornene as a cyclic olefin monomer was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 36.1 mg of 2,3-dihydrofuran, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.01 g. The weight average molecular weight of the obtained ring-opening polymer was measured according to the above and found to be 10,200. The obtained ring-opened polymer was subjected to <Product Analysis> according to the above. As a result, it was identified that the obtained ring-opened polymer has a structure containing cyclic olefin ring-opening polymerization units formed by ring-opening polymerization of cyclic olefin, and retains the vinyl ether moiety of 2,3-dihydrofuran, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (molecular weight of 2,3-dihydrofuran as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the ring-opened polymer hydrogenated product obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed product was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the obtained ring-opened polymer hydrogenated product was measured as described above, and was found to be 99% or more. The obtained ring-opened polymer hydrogenated product was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer hydrogenated product has a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 2,3-dihydrofuran, is hydrogenated and retains an ether moiety. Next, the absolute molecular weight of the ring-opened polymer hydrogenated product as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of the hydrogenated norbornene as the cyclic olefin monomer) + (molecular weight of the hydrogenated 2,3-dihydrofuran as the polymerization initiator). From these results, it was confirmed that the hydrogenated ring-opened polymer obtained in this step was a cyclic polymer.

[0062] Example 3 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of norbornene as a cyclic olefin monomer was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 35.2 mg of 3,4-dihydro-2-methoxy-2H-pyran, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.25 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was found to be 14,700. The obtained ring-opened polymer was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains the vinyl ether moiety of 3,4-dihydro-2-methoxy-2H-pyran, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (molecular weight of 3,4-dihydro-2-methoxy-2H-pyran as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the hydrogenated ring-opened polymer obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed precipitate was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the hydrogenated ring-opened polymer obtained was measured as described above, and was found to be 99% or more. The hydrogenated ring-opened polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the hydrogenated ring-opened polymer obtained had a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit obtained by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 3,4-dihydro-2-methoxy-2H-pyran, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the hydrogenated ring-opened polymer as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of the hydrogenated norbornene as the cyclic olefin monomer) + (molecular weight of the hydrogenated 3,4-dihydro-2-methoxy-2H-pyran as the polymerization initiator). From these results, it was confirmed that the hydrogenated ring-opened polymer obtained in this step was a cyclic polymer.

[0063] Example 4 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of norbornene as a cyclic olefin monomer was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 32.9 mg of 3,4-dihydro-2-ethoxy-2H-pyran, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.36 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was found to be 10,600. The obtained ring-opened polymer was subjected to the <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains the vinyl ether moiety of 3,4-dihydro-2-ethoxy-2H-pyran, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (molecular weight of 3,4-dihydro-2-ethoxy-2H-pyran as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the hydrogenated ring-opened polymer obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed precipitate was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the hydrogenated ring-opened polymer obtained was measured as described above, and was found to be 99% or more. The hydrogenated ring-opened polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the hydrogenated ring-opened polymer obtained had a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit obtained by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 3,4-dihydro-2-ethoxy-2H-pyran, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the ring-opening polymer hydrogenated product as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (a multiple of the molecular weight of the norbornene hydrogenated product as the cyclic olefin monomer) + (the molecular weight of the 3,4-dihydro-2-ethoxy-2H-pyran hydrogenated product as the polymerization initiator). From these results, it was confirmed that the ring-opening polymer hydrogenated product obtained in this process was a cyclic polymer.

[0064] Example 5 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution of 1.75 g of norbornene as a cyclic olefin monomer dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 1.65 mg of 3,4-dihydro-2-ethoxy-2H-pyran, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.36 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was found to be 113,000. The obtained ring-opened polymer was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains the vinyl ether moiety of the polymerization initiator, 3,4-dihydro-2-ethoxy-2H-pyran. Next, the obtained ring-opened polymer was compared with linear polynorbornene by GPC-MALLS, and it was confirmed that the obtained ring-opened polymer was cyclic. From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> This hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the ring-opening polymer hydrogenated product obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed product was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the obtained ring-opening polymer hydrogenated product was measured as described above, and was found to be 99% or more. The obtained ring-opening polymer hydrogenated product was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opening polymer hydrogenated product has a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 3,4-dihydro-2-ethoxy-2H-pyran, was hydrogenated and retained an ether moiety. Next, the obtained ring-opening polymer hydrogenated product was compared with a linear polynorbornene hydrogenated product by GPC-MALLS, and it was confirmed that the obtained ring-opening polymer hydrogenated product was cyclic. From these results, it was confirmed that the ring-opening polymer hydrogenated product obtained in this process was a cyclic polymer.

[0065] Example 6 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution of 1.75 g of norbornene as a cyclic olefin monomer dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 3.9 mg of 1-(trimethylsilyloxy)cyclohexene, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.28 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was found to be 13,200. The obtained ring-opened polymer was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains a vinyl ether moiety of 1-(trimethylsilyloxy)cyclohexene, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (molecular weight of 1-(trimethylsilyloxy)cyclohexene as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> This hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the ring-opening polymer hydrogenated product obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed product was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the obtained ring-opening polymer hydrogenated product was measured as described above, and was found to be 99% or more. The obtained ring-opening polymer hydrogenated product was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opening polymer hydrogenated product has a structure containing a hydrogenated product of a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 1-(trimethylsilyloxy)cyclohexene, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the ring-opening polymer hydrogenated product as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of the hydrogenated product of norbornene as the cyclic olefin monomer) + (molecular weight of the hydrogenated product of 1-(trimethylsilyloxy)cyclohexene as the polymerization initiator). From these results, it was confirmed that the hydrogenated ring-opened polymer obtained in this step was a cyclic polymer.

[0066] Example 7 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of norbornene as a cyclic olefin monomer was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 3.5 mg of 1-(trimethylsilyloxy)cyclopentene, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.41 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was found to be 11,000. The obtained ring-opened polymer was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains a vinyl ether moiety of 1-(trimethylsilyloxy)cyclopentene, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (molecular weight of 1-(trimethylsilyloxy)cyclopentene as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> This hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the ring-opening polymer hydrogenated product obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed product was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the obtained ring-opening polymer hydrogenated product was measured as described above, and was found to be 99% or more. The obtained ring-opening polymer hydrogenated product was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opening polymer hydrogenated product has a structure containing a hydrogenated product of a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 1-(trimethylsilyloxy)cyclopentene, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the ring-opening polymer hydrogenated product as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of the hydrogenated product of norbornene as the cyclic olefin monomer) + (molecular weight of the hydrogenated product of 1-(trimethylsilyloxy)cyclopentene as the polymerization initiator). From these results, it was confirmed that the hydrogenated ring-opened polymer obtained in this step was a cyclic polymer.

[0067] Example 8 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of norbornene as a cyclic olefin monomer was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 3.2 mg of 1-(methoxy)cyclooctene, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.75 g. The weight average molecular weight of the obtained ring-opening polymer was measured according to the above and found to be 9,400. The obtained ring-opened polymer was subjected to <Product Analysis> according to the above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains a vinyl ether moiety of 1-(methoxy)cyclooctene, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (a multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (the molecular weight of 1-(methoxy)cyclooctene as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the hydrogenated ring-opened polymer obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed precipitate was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the hydrogenated ring-opened polymer obtained was measured as described above, and was found to be 99% or more. The hydrogenated ring-opened polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the hydrogenated ring-opened polymer obtained had a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 1-(methoxy)cyclooctene, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the hydrogenated ring-opened polymer as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of the hydrogenated norbornene as the cyclic olefin monomer) + (molecular weight of the hydrogenated 1-(methoxy)cyclooctene as the polymerization initiator). From these results, it was confirmed that the hydrogenated ring-opened polymer obtained in this step was a cyclic polymer.

[0068] Example 9 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of norbornene as a cyclic olefin monomer was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 2.2 mg of 2,3,4,5-tetrahydrooxepin, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.75 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was found to be 9,400. The obtained ring-opened polymer was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains the vinyl ether moiety of the polymerization initiator, 2,3,4,5-tetrahydrooxepin. Next, the absolute molecular weight of the ring-opened polymer as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (molecular weight of 2,3,4,5-tetrahydrooxepin as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the hydrogenated ring-opened polymer obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed precipitate was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the hydrogenated ring-opened polymer obtained was measured as described above, and was found to be 99% or more. The hydrogenated ring-opened polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the hydrogenated ring-opened polymer obtained had a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 2,3,4,5-tetrahydrooxepin, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the hydrogenated ring-opened polymer as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of the hydrogenated norbornene as the cyclic olefin monomer) + (molecular weight of the hydrogenated 2,3,4,5-tetrahydrooxepin as the polymerization initiator). From these results, it was confirmed that the hydrogenated ring-opened polymer obtained in this step was a cyclic polymer.

[0069] Example 10 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of dicyclopentadiene, which is a cyclic olefin monomer, was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 32.9 mg of 3,4-dihydro-2-ethoxy-2H-pyran, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.36 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was found to be 4,300. The obtained ring-opened polymer was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing cyclic olefin ring-opening polymerization units formed by ring-opening polymerization of cyclic olefin, and retains the vinyl ether moiety of 3,4-dihydro-2-ethoxy-2H-pyran, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of dicyclopentadiene as a cyclic olefin monomer) + (molecular weight of 3,4-dihydro-2-ethoxy-2H-pyran as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the hydrogenated ring-opened polymer obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed precipitate was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the hydrogenated ring-opened polymer obtained was measured as described above, and was found to be 99% or more. The hydrogenated ring-opened polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the hydrogenated ring-opened polymer obtained had a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit obtained by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 3,4-dihydro-2-ethoxy-2H-pyran, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the ring-opening polymer hydrogenated product as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (a multiple of the molecular weight of the hydrogenated product of dicyclopentadiene as a cyclic olefin monomer) + (the molecular weight of the hydrogenated product of 3,4-dihydro-2-ethoxy-2H-pyran as a polymerization initiator). From these results, it was confirmed that the ring-opening polymer hydrogenated product obtained in this process was a cyclic polymer.

[0070] Example 11 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution of 1.0 g of norbornene as a cyclic olefin monomer and 0.75 g of dicyclopentadiene dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 32.9 mg of 3,4-dihydro-2-ethoxy-2H-pyran, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.36 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above, and was found to be 5,900. The obtained ring-opened polymer was subjected to <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing cyclic olefin ring-opening polymerization units formed by ring-opening polymerization of cyclic olefin, and retains the vinyl ether moiety of 3,4-dihydro-2-ethoxy-2H-pyran, which is a polymerization initiator. Next, the absolute molecular weight of the ring-opened polymer as a measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (the sum of the multiple of the molecular weight of norbornene as a cyclic olefin monomer and the multiple of the molecular weight of dicyclopentadiene) + (the molecular weight of 3,4-dihydro-2-ethoxy-2H-pyran as a polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the hydrogenated ring-opened polymer obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed precipitate was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the hydrogenated ring-opened polymer obtained was measured as described above, and was found to be 99% or more. The hydrogenated ring-opened polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the hydrogenated ring-opened polymer obtained had a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit obtained by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 3,4-dihydro-2-ethoxy-2H-pyran, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the ring-opened polymer hydrogenated product as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (the sum of the multiple of the molecular weight of the norbornene hydrogenated product and the multiple of the molecular weight of the dicyclopentadiene hydrogenated product) + (the molecular weight of the 3,4-dihydro-2-ethoxy-2H-pyran hydrogenated product as the polymerization initiator). From these results, it was confirmed that the ring-opened polymer hydrogenated product obtained in this process was a cyclic polymer.

[0071] Example 12 <Ring-opening polymerization process> In a glass reactor equipped with a stirrer, 5 mg of 2,4,6-tris(4-methoxyphenyl)pyrylium tetrafluoroborate, which is a pyrylium salt as a photoredox catalyst, and 5 ml of dichloromethane as a solvent were placed and stirred. Next, a solution in which 1.75 g of tetracyclododecene, which is a cyclic olefin monomer, was dissolved in 1.75 g of dichloromethane as a solvent was added and stirred. Next, 32.9 mg of 3,4-dihydro-2-ethoxy-2H-pyran, which is a cyclic vinyl ether compound as a polymerization initiator, was added and stirred, and then light irradiation (wavelength 425 nm) by an LED lamp was started to start the ring-opening metathesis polymerization reaction. After reacting for 15 hours at room temperature, a large amount of acetone was poured into the polymerization reaction solution containing the ring-opening polymer as the reaction product to flocculate the precipitate, and the flocculate containing the ring-opening polymer was filtered. The filtered product was washed with methanol and then dried under reduced pressure at 40°C for 24 hours. The yield of the obtained ring-opening polymer was 0.11 g. The weight average molecular weight of the obtained ring-opened polymer was measured as described above and found to be 3,200. The obtained ring-opened polymer was subjected to the <Product Analysis> as described above. As a result, it was identified that the obtained ring-opened polymer has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains the vinyl ether moiety of the polymerization initiator, 3,4-dihydro-2-ethoxy-2H-pyran. Next, the absolute molecular weight of the ring-opened polymer as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of tetracyclododecene as the cyclic olefin monomer) + (molecular weight of 3,4-dihydro-2-ethoxy-2H-pyran as the polymerization initiator). From these results, it was confirmed that the ring-opened polymer obtained in this process was a cyclic polymer. <Hydrogenation process> Next, 0.1 g of the ring-opened polymer (i.e., cyclic polymer) obtained in the ring-opening polymerization step and 0.8 g of paratoluenesulfonyl hydrazide as a hydrogenating agent were added to a glass reactor equipped with a stirrer, and 30 ml of p-xylene was added as a solvent, and the hydrogenation reaction was carried out at 125°C for 5 hours to obtain a hydrogenation reaction liquid containing a ring-opened polymer hydrogenate (i.e., a cyclic polymer hydrogenate). <Post-processing process> The hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate the hydrogenated ring-opened polymer obtained through the hydrogenation process, and the precipitate was filtered and washed. The filtered and washed precipitate was then dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the hydrogenated ring-opened polymer obtained was measured as described above, and was found to be 99% or more. The hydrogenated ring-opened polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the hydrogenated ring-opened polymer obtained had a structure containing a hydrogenated cyclic olefin ring-opening polymerization unit obtained by ring-opening polymerization of a cyclic olefin, and that the vinyl group of the polymerization initiator, 3,4-dihydro-2-ethoxy-2H-pyran, was hydrogenated and retained an ether moiety. Next, the absolute molecular weight of the ring-opening polymer hydrogenated product as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that the molecular weight of the mass peak of each polymer chain was (a multiple of the molecular weight of the hydrogenated product of tetracyclododecene as a cyclic olefin monomer) + (the molecular weight of the hydrogenated product of 3,4-dihydro-2-ethoxy-2H-pyran as a polymerization initiator). From these results, it was confirmed that the ring-opening polymer hydrogenated product obtained in this process was a cyclic polymer.

[0072] Comparative Example 1 The ring-opening polymerization step, hydrogenation step, and post-treatment step were carried out in the same manner as in Example 1, except that 8.85 mg of ethyl propenyl ether, a linear vinyl ether compound, was added instead of the cyclic vinyl ether compound as the polymerization initiator. The yield of the ring-opening polymer obtained in the ring-opening polymerization step was 1.0 g. The weight average molecular weight of the ring-opening polymer obtained in the ring-opening polymerization step was 44,000, as measured as described above. The ring-opening polymer obtained was subjected to <Product Analysis> as described above. As a result, it was identified that the ring-opening polymer obtained has a structure containing a cyclic olefin ring-opening polymerization unit formed by ring-opening polymerization of a cyclic olefin, and retains the vinyl ether moiety of the polymerization initiator ethyl propenyl ether. Next, the absolute molecular weight of the ring-opening polymer as the measurement sample was measured using a time-of-flight mass spectrometer, and it was confirmed that it was a chain polymer because the molecular weight of the mass peak of each polymer chain was (multiple of the molecular weight of norbornene as a cyclic olefin monomer) + (molecular weight of ethyl propenyl ether as a polymerization initiator). Furthermore, the hydrogenation rate of the hydrogenated product obtained through the hydrogenation step and the post-treatment step was 99% or more. The solid content obtained by drying under reduced pressure in the post-treatment step did not contain any hydrogenated cyclic polymer, and the proportion of hydrogenated cyclic polymer was 0%.

[0073] According to Examples 1 to 12, it is seen that hydrogenated cyclic polymers containing cyclic chains composed of repeating units of cyclic olefin ring-opening polymerization units were obtained. Moreover, according to Comparative Example 1, it is understood that when a linear vinyl ether compound was used as a polymerization initiator instead of a cyclic vinyl ether compound, a hydrogenated cyclic polymer could not be obtained. [Industrial Applicability]

[0074] According to the present invention, it is possible to provide a hydrogenated cyclic polymer having a novel structure. Also, according to the present invention, it is possible to provide a resin composition containing the hydrogenated cyclic polymer having the novel structure.

Claims

1. A hydrogenated cyclic polymer comprising a cyclic chain consisting of repeating units of cyclic olefin ring-opening polymerization units, A hydride, wherein the cyclic chains of the cyclic polymer contain ether bonds.

2. a ring-opening polymerization step of ring-opening polymerizing at least one cyclic olefin monomer in the presence of a cyclic vinyl ether compound to obtain a cyclic polymer having a cyclic chain composed of repeating units of cyclic olefin ring-opening polymerized units; a hydrogenation step of hydrogenating the cyclic polymer to obtain a hydrogenated cyclic polymer; Including, The cyclic chain of the cyclic polymer obtained in the ring-opening polymerization step contains an ether bond. Method for producing cyclic polymer hydrides.

3. A resin composition comprising the hydride according to claim 1.

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