Cyclic olefin polymer, method for producing the same, and optical element

Abstract

The object of the present invention is to provide a cyclic olefin polymer having a high refractive index, a low Abbe number and a low birefringence, a method for producing the same, and an optical element using the cyclic olefin polymer. The cyclic olefin polymer of the present invention comprises structural units derived from a naphthyl-containing alicyclic compound (A) represented by the following formula (1) at a predetermined ratio [wherein R 2a ~R 5a One of the groups is naphthyl, and the remaining groups and R 1a As described in the specification] or its hydrogenated product.

Description

Technical Field

[0001] The present invention relates to a cyclic olefin polymer, a method for producing the cyclic olefin polymer, and an optical element using the cyclic olefin polymer. Background Art

[0002] In recent years, polymers obtained by ring-opening or addition polymerization of cyclic olefins have attracted attention as materials for optical elements and medical containers.

[0003] Moreover, for example, in Patent Document 1, a norbornene-based ring-opening polymer (copolymer) having excellent transparency and heat resistance, high solubility in an organic solvent, and specific birefringence and wavelength dependence is disclosed. In addition, in Patent Document 2, a cycloolefin copolymer that effectively manifests the reverse wavelength dispersion of birefringence and a film formed of the copolymer are disclosed. In addition, in Patent Document 3, a cycloolefin-based copolymer having a high refractive index and capable of adjusting the Abbe number to a low level and a medical container having little discoloration caused by electron beam or gamma ray irradiation and excellent transparency are disclosed. In addition, in Patent Document 4, a norbornene-based polymer film capable of increasing the degree of wavelength dispersion for improving the color tone of a liquid crystal display device is disclosed.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-46615;

[0007] Patent Document 2: Japanese Patent Application Publication No. 2009-46614;

[0008] Patent document 3: International Publication No. 2019 / 107363;

[0009] Patent Document 4: Japanese Patent Application Publication No. 2008-31319. Summary of the invention

[0010] Problem that the invention aims to solve

[0011] Here, in order to increase the degree of freedom in designing optical elements such as optical lenses, there is a need for a resin having a high refractive index, a lower Abbe number than conventional cyclic olefin resins, and a small birefringence when used as an optical element.

[0012] However, the above-mentioned existing ring-opening or addition polymers cannot achieve high refractive index, low Abbe number and low birefringence (eg stress birefringence) at the same time.

[0013] Therefore, an object of the present invention is to provide a cyclic olefin polymer (polymer obtained by ring-opening polymerization or addition polymerization) having high refractive index, low Abbe number and low birefringence, a method for producing the same, and an optical element using the cyclic olefin polymer.

[0014] Solutions for solving problems

[0015] The present inventors have conducted intensive studies with the purpose of solving the above problems, and have newly discovered that a cyclic olefin polymer can have a high refractive index, a low Abbe number, and a low birefringence (low stress optical coefficient) at the same time if the cyclic olefin polymer is a polymer containing a structural unit derived from a naphthyl-containing alicyclic compound (A) as a structural unit in a predetermined ratio or a hydrogenated product thereof.

[0016] Then, the present inventors completed the present invention based on the above-mentioned new findings.

[0017] That is, the object of the present invention is to advantageously solve the above-mentioned problems. The cyclic olefin polymer of the present invention is characterized in that it is a polymer containing a structural unit derived from a naphthyl-containing alicyclic compound (A) represented by the following formula (1) and optionally containing a structural unit derived from other monomers, or a hydrogenated product thereof,

[0018] [Chemical formula 1]

[0019]

[0020] [Where R 2a ~R 5a Any one of them is naphthyl, and the remaining groups and R 1a Each independently is:

[0021] (i) Hydrogen atoms;

[0022] (ii) a halogen atom; or

[0023] (iii) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (excluding a hydrocarbon group containing an aromatic ring) which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom.]

[0024] The ratio of the structural unit derived from the compound (A) in all the structural units is 20 mol% or more and 100 mol% or less.

[0025] It is preferred that the ratio of the structural unit derived from the compound (A) in all structural units is 20 mol% or more and 90 mol% or less. 2a ~R 5a The remaining groups except the naphthyl group and R 1a A hydrogen atom.

[0026] The cyclic olefin polymer of the present invention is preferably a polymer comprising a structural unit derived from the compound (A) and one or more structural units derived from a norbornene-based monomer (B) different from the compound (A), and optionally comprising a structural unit derived from other monomers, or a hydrogenated product thereof.

[0027] Here, the norbornene-based monomer (B) is preferably:

[0028] (i) norbornenes which are unsubstituted or have an alkyl group, an alkenyl group, an aromatic ring group, a polar group containing an oxygen atom, or a polar group containing a nitrogen atom as a substituent;

[0029] (ii) A monomer represented by the following formula (3)

[0030] [Chemical formula 2]

[0031]

[0032] [In formula (3),

[0033] R 1b and R 2b Each independently represents: a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; or an organic group containing a silicon atom, an oxygen atom or a nitrogen atom,

[0034] R 1b and R 2b Bonded to each other to form a ring or not bonded,

[0035] R 3b is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ];

[0036] or

[0037] (iii) A monomer represented by the following formula (4)

[0038] [Chemical formula 3]

[0039]

[0040] [In formula (4),

[0041] R 4b ~R 7b Each independently represents: a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; or an organic group containing a silicon atom, an oxygen atom or a nitrogen atom,

[0042] R 4b and R 6b Bonded to each other to form a ring or not bonded,

[0043] m is 1 or 2. ].

[0044] The weight average molecular weight of the cyclic olefin polymer is preferably 20,000 or more and preferably 40,000 or less.

[0045] The refractive index of cyclic olefin polymers (n d ) is preferably 1.545 or more, preferably 1.640 or less. In addition, the Abbe number (ν d ) is preferably 20 or more, and preferably 50 or less. In addition, the stress birefringence (C R ) is preferably -500×10 -12 Pa -1 Above, preferably 1400×10 -12 Pa -1 If the refractive index, Abbe number and stress birefringence are within the above ranges, the degree of freedom in optical design can be increased when used as a material for an optical element.

[0046] In the present invention, the refractive index, the Abbe number and the stress birefringence can be measured by the methods described in the Examples of the present specification.

[0047] In addition, when the cyclic olefin polymer of the present invention is a polymer containing structural units derived from a naphthyl-containing alicyclic compound (A) and optionally other monomers, or a hydrogenated product thereof, the cyclic olefin polymer of the present invention can be easily produced using a production method comprising the following steps, in which a mixed monomer is polymerized (for example, ring-opening polymerization, addition polymerization), and the mixed monomer contains: a naphthyl-containing alicyclic compound (A) as a monomer, or a polymer containing structural units derived from the above-mentioned compound (A) and optionally other monomers; and optionally other monomers. In addition, when the cyclic olefin polymer of the present invention is a polymer or a hydrogenated product thereof comprising a structural unit derived from a naphthyl-containing alicyclic compound (A), one or more norbornene-based monomers (B) different from the above-mentioned compound (A), and optionally a structural unit derived from other monomers, the cyclic olefin polymer of the present invention can be easily produced using a production method comprising the following steps, in which a mixed monomer is polymerized (for example, ring-opening polymerization, addition polymerization), and the mixed monomer comprises: a naphthyl-containing alicyclic compound (A) as a monomer, or a polymer comprising a structural unit derived from the above-mentioned compound (A) and optionally a structural unit derived from other monomers; one or more norbornene-based monomers (B) different from the naphthyl-containing alicyclic compound (A), or a polymer comprising a structural unit derived from the above-mentioned norbornene-based monomer (B) and optionally a structural unit derived from other monomers; and optionally other monomers or polymers. The ring-opening polymerization can be carried out, for example, in the presence of a metathesis polymerization catalyst. The addition polymerization can be carried out in the presence of any one of a Ziegler-Natta catalyst, a metallocene catalyst, a nickel catalyst, and a palladium catalyst. In addition, the method for producing a cyclic olefin polymer may further include a step of hydrogenating the polymer.

[0048] The present invention also aims to solve the above problems advantageously, and the optical element of the present invention is characterized by comprising the above cyclic olefin polymer. If the above cyclic olefin polymer is contained, it can be advantageously used as a material for an optical element or the like.

[0049] Effects of the Invention

[0050] According to the present invention, a cyclic olefin polymer having a high refractive index, a low Abbe number, and a low birefringence (for example, stress birefringence), a method for producing the cyclic olefin polymer, and an optical element using the cyclic olefin polymer can be provided. DETAILED DESCRIPTION

[0051] Hereinafter, embodiments of the present invention will be described in detail.

[0052] (Cyclic olefin polymer)

[0053] The cyclic olefin polymer of the present invention is a polymer of a mixed monomer containing a naphthyl-containing alicyclic compound (A) and optionally other monomers (for example, a polymer obtained by ring-opening polymerization or addition polymerization) or a hydrogenated product thereof. The proportion of the naphthyl-containing alicyclic compound (A) in the mixed monomer is 20 mol% or more and 100 mol% or less. The cyclic olefin polymer of the present invention has any one of the excellent properties of high refractive index, low Abbe number, low birefringence (for example, stress birefringence) or high glass transition temperature. In addition, in this specification, a "polymer" may be a polymer composed of a single structural unit (for example, a homopolymer), or may be a copolymer.

[0054] In addition, the cyclic olefin polymer of the present invention is preferably a polymer of a mixed monomer containing a naphthyl-containing alicyclic compound (A) and one or more norbornene-based monomers (B) different from the naphthyl-containing alicyclic compound (A), and optionally containing other monomers (for example, a polymer obtained by ring-opening polymerization or addition polymerization) or a hydrogenated product thereof. The proportion of the naphthyl-containing alicyclic compound (A) in the mixed monomer is 20 mol% or more and 100 mol% or less. The cyclic olefin polymer of the present invention may be, for example, a random copolymer or a block copolymer. If the cyclic olefin polymer of the present invention is a copolymer containing a structural unit derived from the above-mentioned compound (A), a structural unit derived from the above-mentioned norbornene-based monomer (B), and optionally containing a structural unit derived from other monomers, it is preferred that the polymer obtained by polymerizing the naphthyl-containing alicyclic compound (A) as a single monomer has a higher refractive index, a lower Abbe number, a lower birefringence (for example, stress birefringence), or a higher glass transition temperature.

[0055] <Naphthyl-containing alicyclic compound>

[0056] The naphthyl group-containing alicyclic compound (A) is a compound represented by the following formula (1).

[0057] [Chemical formula 4]

[0058]

[0059] [Where R 2a ~R 5a Any one of them is naphthyl, and the remaining groups and R 1a Each independently is:

[0060] (i) Hydrogen atoms;

[0061] (ii) a halogen atom; or

[0062] (iii) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (excluding a hydrocarbon group containing an aromatic ring) which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom.]

[0063] The naphthyl group-containing alicyclic compound (A) may be a compound to which 1-naphthyl or 2-naphthyl is bonded as the naphthyl group, or a mixture thereof. As the bonding mode of the naphthyl group to the norbornene ring, there are exo bonding (bonding in the same direction as the methylene group at the bridgehead position) and endo bonding (bonding in the opposite direction to the methylene group at the bridgehead position) in stereoisomerism, and the naphthyl group-containing alicyclic compound (A) may be a compound (exo body or endo body) in which the naphthyl group is bonded to the norbornene ring by exo or endo bonding, or a mixture thereof. Therefore, the naphthyl group-containing alicyclic compound (A) may be a 1-naphthyl-exo type compound, a 2-naphthyl-exo type compound, a 1-naphthyl-endo type compound, a 2-naphthyl-endo type compound, or a mixture thereof.

[0064] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0065] Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, and propyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; and alkylene groups such as ethylene and propylene. These hydrocarbon groups may be substituted, and examples of the substituent include halogen atoms such as fluorine, chlorine, and bromine; benzenesulfonyl; and cyano.

[0066] In addition, the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure or may be bonded via a linking group. Examples of the linking group include: a divalent hydrocarbon group having 1 to 10 carbon atoms (e.g., -(CH2) q -(wherein q is an integer from 1 to 10)); a connecting group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom (for example, a carbonyl group (-CO-), a carbonyloxy group (-COO-), a sulfonyl group (-SO2-), a sulfonate group (-SO2-O-), an ether bond (-O-), a thioether bond (-S-), an imino group (-NH-), an amide bond (-NHCO-), a siloxane bond (-Si(R2)O-(wherein R is an alkyl group such as a methyl group or an ethyl group)); or a group formed by a combination of two or more of them.

[0067] R 2a ~R 5a The remaining groups except the naphthyl group and R 1a Preferably, they are all hydrogen atoms.

[0068] <Norbornene-based monomer>

[0069] The norbornene-based monomer (B) is a compound having a norbornene structure represented by formula (2).

[0070] [Chemical formula 5]

[0071]

[0072] Examples of the norbornene-based monomer (B) include norbornene-based monomers having no ring condensed with a norbornene ring in the molecule and polycyclic norbornene-based monomers having three or more rings.

[0073] Examples of the norbornene monomer having no ring condensed with the norbornene ring in the molecule include norbornene, 5-methyl norbornene, 5-ethyl norbornene, 5-butyl norbornene, 5-hexyl norbornene, 5-decyl norbornene, 5-cyclohexyl norbornene, 5-cyclopentyl norbornene and other unsubstituted or alkyl-containing norbornenes;

[0074] Norbornenes having an alkenyl group, such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene, and 5-cyclopentenyl norbornene;

[0075] Norbornenes having an aromatic ring, such as 5-phenylnorbornene;

[0076] Norbornenes having a polar group containing an oxygen atom, such as 5-methoxycarbonyl norbornene, 5-ethoxycarbonyl norbornene, 5-methyl-5-methoxycarbonyl norbornene, 5-methyl-5-ethoxycarbonyl norbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethyl norbornene, 5,6-bis(hydroxymethyl)norbornene, 5,5-bis(hydroxymethyl)norbornene, 5-hydroxy-isopropyl norbornene, 5,6-dicarboxynorbornene, and 5-methoxycarbonyl-6-carboxynorbornene;

[0077] Norbornenes having a polar group containing a nitrogen atom, such as 5-cyanonorbornene, and the like.

[0078] The polycyclic norbornene monomer having three or more rings refers to a norbornene monomer having a norbornene ring and one or more rings condensed with the norbornene ring in the molecule. Specific examples thereof include monomers represented by the following formula (3) or formula (4).

[0079] [Chemical formula 6]

[0080]

[0081] (In formula (3),

[0082] R 1band R 2b Each independently represents: a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms (such as an alkyl group) which may have a substituent; or a substituent containing a silicon atom, an oxygen atom or a nitrogen atom, R 1b and R 2b can bond to each other to form a ring,

[0083] R 3b It is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (for example, an alkylene group).

[0084] [Chemical formula 7]

[0085]

[0086] (In formula (4),

[0087] R 4b ~R 7b Each independently represents: a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms (such as an alkyl group) which may have a substituent; or a substituent containing a silicon atom, an oxygen atom or a nitrogen atom, R 4b and R 6b can bond to each other to form a ring,

[0088] m is 1 or 2. )

[0089] Examples of the monomer represented by formula (3) include dicyclopentadiene, methyldicyclopentadiene, tricyclo[5.2.1.0 2,6 ] dec-8-ene and other norbornene monomers that do not contain an aromatic ring structure. In addition, tetracyclic [9.2.1.0 2,10 .0 3,8 ]tetradeca-3,5,7,12-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene), tetracyclo[10.2.1.0 2 ,11 .0 4,9 ] norbornene derivatives having an aromatic ring, such as 1,4-dimethano-1,4,4a,9,9a,10-hexahydroanthracene.

[0090] Examples of the monomer represented by the formula (4) include tetracyclododecenes in which m is 1 and hexacycloheptadecenes in which m is 2.

[0091] Examples of the tetracyclododecene include unsubstituted or alkyl-containing tetracyclododecene such as tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene, and 8-methoxycarbonyl-8-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene;

[0092] Tetracyclododecenes having a double bond outside the ring, such as 8-methylenetetracyclododecene, 8-ethylenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, and 8-cyclopentenyltetracyclododecene;

[0093] Tetracyclododecenes having an aromatic ring, such as 8-phenyltetracyclododecene;

[0094] Tetracyclododecenes having a substituent containing an oxygen atom, such as 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, and tetracyclododecene-8,9-dicarboxylic anhydride;

[0095] Tetracyclododecenes having a substituent containing a nitrogen atom, such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboximide;

[0096] Tetracyclododecenes having a substituent containing a halogen atom, such as 8-chlorotetracyclododecene; tetracyclododecenes having a substituent containing a silicon atom, such as 8-trimethoxysilyltetracyclododecene; and the like.

[0097] As the hexacycloheptadecene, any of the Diels-Alder adducts of the above-mentioned tetracyclododecene and cyclopentadiene can be used.

[0098] Among them, from the viewpoint of improving the refractive index, Abbe number, birefringence (e.g., stress birefringence), or glass transition temperature, the norbornene-based monomer (B) is preferably a non-polar norbornene-based monomer among the above-mentioned norbornene-based monomers, and more preferably unsubstituted or alkyl-containing norbornenes (e.g., norbornene (NB), 8-ethyltetracyclododecene), alkenyl-containing norbornenes (e.g., ethylenetetracyclododecene (8-ethylenetetracyclododecene, ETD)), dicyclopentadiene (DCPD), norbornene derivatives having an aromatic ring (e.g., tetracyclo[9.2.1.0 2,10 .0 3,8] tetradeca-3,5,7,12-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene (MTF))), unsubstituted or alkyl-containing tetracyclododecenes (e.g. tetracyclododecene (TCD), 8-methoxycarbonyl-8-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene (MTCD)).

[0099] The norbornene monomers can be used alone or in combination of two or more. The polycyclic norbornene monomers having three or more rings include isomers such as endo isomers and exo isomers, and any one of them can be used, or a mixture of isomers can be used.

[0100] Unless the effects of the present invention are impaired, other copolymerizable monomers may be used in combination. When all monomers are 100 mol %, the other copolymerizable monomers are preferably 50 mol % or less.

[0101] Examples of other copolymerizable monomers include cycloolefins such as cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, and 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene; and non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene. These copolymerizable monomers may be used alone or in combination of two or more.

[0102] <Content ratio of naphthyl group-containing alicyclic compound (A)>

[0103] The proportion of the alicyclic compound (A) containing a naphthalene ring in the mixed monomer may be 20 mol% or more, preferably 25 mol% or more, more preferably 30 mol% or more, for example, 100 mol% or less, 95 mol% or less, or 90 mol% or less, preferably 87 mol% or less, more preferably 85 mol% or less. However, from the viewpoint of further improving the high refractive index, it is preferred that the mixed monomer contains the alicyclic compound (A) containing a naphthyl group and the norbornene-based monomer (B), and the total content of the alicyclic compound (A) containing a naphthyl group and the norbornene-based monomer (B) contained in the mixed monomer is 100 mol%, that is, the monomers as the raw materials of the cyclic olefin polymer of the present invention are composed only of the compound (A) and the monomer (B), and the cyclic olefin polymer of the present invention is composed only of the structural units derived from the compound (A) and the monomer (B).

[0104] <Hydrogenation rate>

[0105] In order to improve stability and suppress coloration and degradation caused by heat, the cyclic olefin polymer of the present invention is preferably a hydrogenate, and more preferably fully hydrogenated. The hydrogenation rate of the cyclic olefin polymer of the present invention is preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 99 mol% or more. If the value of the hydrogenation rate is above the above lower limit, the heat resistance of the cyclic olefin polymer can be improved. In addition, the hydrogenation rate of the polymer is the hydrogenation rate of the carbon-carbon double bond in the main chain. In addition, the naphthalene in the structure of the naphthyl-containing alicyclic compound (A) is usually not hydrogenated.

[0106] <Structure of Cyclic Olefin Polymer>

[0107] The cyclic olefin polymer of the present invention is a polymer formed by polymerizing the above-mentioned naphthyl-containing alicyclic compound (A) and other monomers optionally contained. In addition, it is preferred that the cyclic olefin polymer of the present invention can be a polymer formed by polymerizing the above-mentioned naphthyl-containing alicyclic compound (A), one or more norbornene-based monomers (B), and other monomers optionally contained. The polymerization can be any one of ring-opening polymerization and addition polymerization, and both ring-opening polymerization and addition polymerization can also be included in one cyclic olefin polymer. The polymerization is preferably ring-opening polymerization. The cyclic olefin polymer of the present invention can be represented as a polymer comprising structural units from compound (A) and optionally comprising structural units from other monomers. In addition, it is preferred that the cyclic olefin polymer of the present invention is represented as a polymer comprising structural units from compound (A), structural units from norbornene-based monomers (B), and optionally comprising structural units from other monomers. The proportion of the structural unit derived from the compound (A) in the total structural units may be 20 mol% or more, preferably 25 mol% or more, more preferably 30 mol% or more, for example, 100 mol% or less, 95 mol% or less, or 90 mol% or less, preferably 87 mol% or less, more preferably 85 mol% or less. It is preferred that the total proportion of the structural units derived from the compound (A) and the structural units derived from the norbornene-based monomer (B) contained in the total structural units is 100%, that is, the cyclic olefin polymer of the present invention is composed only of the structural units derived from the compound (A) and the monomer (B).

[0108] When the polymerization is a ring-opening polymerization, the cyclic olefin polymer of the present invention can be represented as, for example, a polymer comprising a structural unit (a) derived from the compound (A) and optionally a structural unit derived from other monomers. In addition, preferably, when the polymerization is a ring-opening polymerization, the cyclic olefin polymer of the present invention can be represented as, for example, a polymer comprising a structural unit (a) derived from the compound (A), a structural unit (b) derived from a norbornene-based monomer (B), and optionally a structural unit derived from other monomers.

[0109] <Structural Unit (a) Derived from Compound (A)>

[0110] In the case of ring-opening polymerization, by subjecting compound (A) (compound represented by formula (1)) to a ring-opening reaction, a structural unit represented by formula (5) can be produced. Furthermore, by performing a hydrogenation reaction, the carbon-carbon double bond in the main chain of the structural unit represented by formula (5) is hydrogenated, and a structural unit represented by formula (6) can be produced. Therefore, the structural unit (a) from compound (A) in the case of ring-opening polymerization can be represented by a structural unit represented by formula (5) when no hydrogenation reaction is performed, and can be represented by a structural unit represented by formula (6) or a mixture of a structural unit represented by formula (5) and a structural unit represented by formula (6) when a hydrogenation reaction is performed (the mixing ratio can vary depending on the degree of hydrogenation).

[0111] [Chemical formula 8]

[0112]

[0113] [Where R 1a ~R 5a As above.]

[0114] <Structural Unit (b) Derived from Norbornene-Based Monomer (B)>

[0115] In the case of ring-opening polymerization, by subjecting the norbornene monomer (B) (a compound having a main structure represented by formula (2)) to a ring-opening reaction, a structural unit having a main structure represented by formula (7) can be produced. Furthermore, by performing a hydrogenation reaction, the carbon-carbon double bond in the main chain of the structural unit having the main structure represented by formula (7) is hydrogenated, and a structural unit having a main structure represented by formula (8) can be produced. Therefore, the structural unit (b) from the norbornene monomer (B) in the case of ring-opening polymerization can be represented as a structural unit having a main structure represented by formula (7) when no hydrogenation reaction is performed, and can be represented as a mixture of a structural unit having a main structure represented by formula (8), a structural unit having a main structure represented by formula (7), and a structural unit having a main structure represented by formula (8) when a hydrogenation reaction is performed (the mixing ratio can vary depending on the degree of hydrogenation). In the case where the norbornene monomer (B) contains a substituent and / or forms a fused ring with other rings, the structural unit (b) also contains a substituent and / or forms a fused ring at the corresponding position. Examples of the substituents and fused rings are as described above.

[0116] [Chemical formula 9]

[0117]

[0118] For example, when the norbornene monomer (B) is a monomer represented by the above formula (3), the structural unit (b) derived from the norbornene monomer (B) in the case of ring-opening polymerization can be represented by a structural unit represented by the formula (9), a structural unit represented by the formula (10), or a mixture thereof, depending on the presence or absence of hydrogenation or the degree of hydrogenation. 1b ~R 3b As mentioned above.

[0119] [Chemical formula 10]

[0120]

[0121] In addition, for example, when the norbornene monomer (B) is a monomer represented by the above formula (3) or (4), the structural unit (b) derived from the norbornene monomer (B) in the case of ring-opening polymerization is represented by the following formula (9) or (10). 1b ~R 7b and m as described above.

[0122] In addition, for example, when the norbornene monomer (B) is a monomer represented by the above formula (4), the structural unit (b) derived from the norbornene monomer (B) in the case of ring-opening polymerization can be represented by a structural unit represented by the formula (11), a structural unit represented by the formula (12), or a mixture thereof, depending on the presence or absence of hydrogenation or the degree of hydrogenation. 4b ~R 7b and m are as described above.

[0123] [Chemical formula 11]

[0124]

[0125] Specific examples of the structural unit (b) derived from the norbornene-based monomer (B) in the case of ring-opening polymerization are structural units produced by ring-opening polymerization of the compounds listed as specific examples of the norbornene-based monomer (B) and optionally hydrogenation.

[0126] As long as the effect of the present invention is not impaired, the cyclic olefin polymer may contain other structural units. As other structural units, structural units from other copolymerizable monomers mentioned above can be cited. Other structural units can be one or more. When the number of all structural units is 100%, the number of other structural units is preferably less than 50%.

[0127] <Average Molecular Weight of Cyclic Olefin Polymer>

[0128] The average molecular weight of the cyclic olefin polymer of the present invention can be expressed as a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The above-mentioned weight average molecular weight (Mw) can usually be 18,000 or more, preferably 19,000 or more, and more preferably 20,000 or more. In addition, the above-mentioned weight average molecular weight (Mw) can usually be 100,000 or less, preferably 50,000 or less, and more preferably 40,000 or less.

[0129] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) may be generally 4.0 or less, preferably 3.7 or less, and more preferably 3.5 or less. The ratio (Mw / Mn) may be 1.0 or more, and may be 1.0.

[0130] (Method for producing cyclic olefin polymer)

[0131] <Method for producing monomer>

[0132] The monomers used as raw materials for the cyclic olefin polymer of the present invention can be produced, for example, by known synthesis methods. The naphthyl-containing alicyclic compound (A) can be produced, for example, by palladium coupling (e.g., reaction of norbornadiene with bromonaphthalene) or Diels-Alder reaction (e.g., reaction of cyclopentadiene with vinylnaphthalene). As a method for producing the naphthyl-containing alicyclic compound (A), specifically, the method described in the examples can be cited. The naphthyl-containing alicyclic compound (A) can be selectively obtained as an exo-body or an endo-body, or as a mixture of an exo-body and an endo-body.

[0133] <Method for producing polymer>

[0134] When the cyclic olefin polymer of the present invention is a polymer comprising structural units derived from the naphthyl-containing alicyclic compound (A) and optionally other monomers, or a hydrogenated product thereof, the cyclic olefin polymer of the present invention can be produced by a method comprising the following steps (polymerization step) in which a raw material for polymerization is polymerized (e.g., ring-opening polymerization, addition polymerization) to obtain a polymer.

[0135] The above-mentioned polymerization raw material contains the naphthyl group-containing alicyclic compound (A) or a polymer containing a structural unit derived from the compound (A), and optionally contains other monomers or a polymer containing a structural unit derived from the monomers.

[0136] Furthermore, when the cyclic olefin polymer of the present invention is a polymer comprising structural units derived from a naphthyl group-containing alicyclic compound (A), one or more norbornene-based monomers (B) different from the compound (A), and optionally structural units derived from other monomers, or a hydrogenated product thereof, the cyclic olefin polymer of the present invention can be produced by a method comprising the following steps (polymerization step) in which a polymer raw material is polymerized (e.g., ring-opening polymerization, addition polymerization) to obtain a polymer,

[0137] The above-mentioned polymerization raw material comprises: a naphthyl-containing alicyclic compound (A) or a polymer comprising a structural unit derived from the compound (A); one or more norbornene-based monomers (B) different from the compound (A) or a polymer comprising a structural unit derived from the norbornene-based monomer (B); and optionally contains other monomers or a polymer comprising a structural unit derived from the monomer; or,

[0138] The polymerization raw material includes a polymer, and the polymer includes a structural unit derived from the compound (A), a structural unit derived from the norbornene-based monomer (B), and optionally includes a structural unit derived from other monomers.

[0139] The ratio of the total number of moles of compound (A) and the structural unit derived from compound (A) to the total number of moles of all monomers and structural units in the raw material for polymerization can be adjusted according to the ratio of the structural unit derived from compound (A) in all structural units of the target cyclic olefin polymer. For example, in order to produce a cyclic olefin polymer in which the ratio of the structural unit derived from compound (A) in all structural units is 20 mol% or more and 100 mol% or less, preferably 20 mol% or more and 90 mol% or less, the ratio of the total number of moles of compound (A) and the structural unit derived from compound (A) to the total number of moles of all monomers and structural units in the raw material for polymerization can be 20 mol% or more, preferably 20 mol% or more and 90 mol% or less.

[0140] In addition, the method for producing the cyclic olefin polymer of the present invention may further include a step of hydrogenating the polymer to obtain a hydride of the polymer (hydrogenation step). By hydrogenation, the heat resistance, weather resistance, light resistance, solvent resistance, chemical resistance, water resistance and other properties of the cyclic olefin polymer are improved.

[0141] Furthermore, the method for producing a cyclic olefin polymer of the present invention may further include a step of recovering the polymer (recovery step).

[0142] <Polymerization process>

[0143] The polymerizable unit compound contained in the raw material for polymerization may be any of a monomer or a polymer (including a copolymer). The polymer as the polymerizable unit compound can be prepared by the same polymerization reaction as in the polymerization step.

[0144] Examples of the polymerization reaction used in the polymerization step and in producing a polymer as a polymerization unit compound include ring-opening polymerization and addition polymerization. The polymerization reaction in the polymerization step will be described below.

[0145] Ring-opening polymerization can be carried out by subjecting the polymerization raw material to ring-opening metathesis polymerization in the presence of a metathesis polymerization catalyst. Ring-opening metathesis polymerization can be carried out in a reaction system in which the polymerization raw material and the metathesis polymerization catalyst are mixed in a solvent (e.g., an organic solvent). In order to improve the polymerization efficiency, the reaction system may further include an activator, a chain transfer agent, and other auxiliary agents (e.g., a Lewis base). The following describes the reagents such as the catalyst used for the ring-opening polymerization and the various conditions of the reaction.

[0146] <Metathesis Polymerization Catalyst>

[0147] As the metathesis polymerization catalyst, a transition metal imide complex represented by formula (1) is used.

[0148] M(NR a )X 4-p (OR b ) p ·L q (1)

[0149] (Where,

[0150] M is a metal atom selected from transition metal atoms of Group 6 of the Periodic Table of Elements,

[0151] R a is a phenyl group or -CH2R which may have a substituent at at least one of the 3-position, 4-position and 5-position c The group represented by c is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent,

[0152] R b is an alkyl group which may have a substituent or an aryl group which may have a substituent,

[0153] X is a halogen atom, an alkyl group, an aryl group, an aralkyl group or an alkylsilyl group,

[0154] L is an electron-donating neutral ligand,

[0155] p is 0 or 1,

[0156] q is an integer from 0 to 2,

[0157] When there are multiple Xs, the multiple Xs may be the same or different.

[0158] When there are multiple L, the multiple L may be the same or different. )

[0159] 《Transition Metal Imidide Complexes》

[0160] M in formula (1) is a transition metal atom of Group 6 of the periodic table and can be selected from chromium, molybdenum and tungsten. Among them, molybdenum and tungsten are preferred, and tungsten is more preferred.

[0161] The transition metal imide complex of formula (1) comprises a metal imide bond (N=R a ). a It is a substituent on the nitrogen atom constituting the metal imide bond.

[0162] R in formula (1) a is a phenyl group or -CH2R which may have a substituent at at least one of the 3-position, 4-position and 5-position c The group represented.

[0163] As R a The substituents of the phenyl group which may have a substituent at at least one of the 3-position, 4-position and 5-position include:

[0164] Alkyl group (for example, alkyl group having 1 to 4 carbon atoms such as methyl group and ethyl group);

[0165] Halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.);

[0166] Alkoxy (for example, alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, isopropoxy, etc.),

[0167] The substituents at at least two of the 3-position, 4-position and 5-position may be bonded to each other.

[0168] Examples of the phenyl group which may have a substituent at at least one of the 3-position, 4-position and 5-position include: a phenyl group;

[0169] Monosubstituted phenyl groups such as 4-methylphenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-cyclohexylphenyl, and 4-methoxyphenyl;

[0170] Disubstituted phenyl groups such as 3,5-dimethylphenyl, 3,5-dichlorophenyl, 3,4-dimethylphenyl and 3,5-dimethoxyphenyl;

[0171] Trisubstituted phenyl groups such as 3,4,5-trimethylphenyl and 3,4,5-trichlorophenyl;

[0172] 2-Naphthyl, 3-methyl-2-naphthyl, 4-methyl-2-naphthyl, and the like, which are 2-naphthyl groups which may have a substituent.

[0173] R a -CH2R c R in the group represented c The number of carbon atoms of the alkyl group which may have a substituent is not particularly limited, and is generally 1 to 20, preferably 1 to 10, and more preferably 1 to 4. The alkyl group may be linear or branched. The substituent is not particularly limited, and examples thereof include: phenyl, phenyl which may have a substituent (e.g., 4-methylphenyl); alkoxy (e.g., methoxy, ethoxy, and other alkoxy groups having 1 to 4 carbon atoms).

[0174] As R c The aryl group which may have a substituent includes phenyl, 1-naphthyl, 2-naphthyl, etc. The substituent is not particularly limited, and examples thereof include phenyl, phenyl which may have a substituent (such as 4-methylphenyl, etc.); alkoxy (such as methoxy, ethoxy, etc., alkoxy groups having 1 to 4 carbon atoms).

[0175] As R c , preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, decyl, etc.

[0176] In formula (1), (4-p) is 4 or 3, and formula (1) has 4 or 3 Xs. Xs are halogen atoms, alkyl groups, aryl groups, aralkyl groups, or alkylsilyl groups. Xs may be the same or different.

[0177] As X, examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a neopentyl group.

[0178] Examples of the aryl group include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0179] Examples of the aralkyl group include a benzyl group and a 2-methyl-2-phenylpropyl group (neophyl group).

[0180] Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

[0181] In formula (1), p is 0 or 1, and formula (1) may have a metal alkoxy bond or a metal aryloxy bond (OR b ). b It is a substituent on the oxygen atom constituting the metal alkoxy bond or the metal aryloxy bond.

[0182] R b is an alkyl group which may have a substituent or an aryl group which may have a substituent, and as the above R c As for the alkyl group which may have a substituent and the aryl group which may have a substituent, examples and preferred examples can be applied.

[0183] In the formula (1), q is an integer of 0 to 2, and the formula (1) may have one or two electron-donating neutral ligands (L).

[0184] Examples of L include electron-donating compounds containing atoms of Group 14 or Group 15 of the periodic table,

[0185] Examples include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine;

[0186] Ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran, tetrahydropyran, etc.;

[0187] Amines such as trimethylamine, triethylamine, pyridine, and dimethylpyridine.

[0188] Among them, ethers are preferred.

[0189] As the transition metal imide complex of formula (1), a tungsten imide complex having a phenylimide group (in formula (1), M is a tungsten atom, R is a The tungsten imide complex preferably comprises a phenyl group, and more preferably tungsten tetrachloride phenylimide (tetrahydrofuran) or tungsten tetrachloride phenylimide (tetrahydropyran).

[0190] The transition metal imide complex of formula (1) may be used alone or in combination of two or more.

[0191] The transition metal imide complex of formula (1) can be synthesized by mixing an oxyhalide of a transition metal of Group 6, a phenyl isocyanate or a monosubstituted methyl isocyanate which may have a substituent at at least one of the 3-position, 4-position and 5-position, with an electron-donating neutral ligand (L), alcohols, metal alkoxides, and metal aryloxides as required (for example, the method described in Japanese Patent Application Laid-Open No. 5-345817). The synthesized transition metal imide complex can be purified and separated by crystallization or the like and then used in a ring-opening polymerization reaction, or the obtained mixed solution can be used directly as a catalyst solution without purification.

[0192] The amount of the transition metal imide complex of formula (1) can be 0.00005 mol% to 1 mol%, preferably 0.0001 mol% to 0.2 mol%, more preferably 0.0002 mol% to 0.1 mol%, relative to 100 mol% of the norbornene monomer. If the amount is within the above range, it is possible to fully avoid the catalyst from becoming difficult to remove and obtain sufficient polymerization activity.

[0193] Activator

[0194] The transition metal imide complex of formula (1) exhibits catalytic activity alone, but can become a polymerization catalyst with higher activity by combining it with an activator.

[0195] Examples of the activator include compounds of Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group (e.g., an alkyl group) having 1 to 20 carbon atoms. Among them, organolithium, organomagnesium, organozinc, organoaluminum, or organotin is preferred, and organoaluminum or organotin is particularly preferred.

[0196] Examples of the organic lithium include methyl lithium, n-butyl lithium, and phenyl lithium.

[0197] Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, and allylmagnesium bromide.

[0198] Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc.

[0199] Examples of the organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethyldiethoxidealuminum, and isobutyldiisobutoxidealuminum.

[0200] Examples of the organic tin include tetramethyltin, tetra(n-butyl)tin, and tetraphenyltin.

[0201] The activators may be used alone or in combination of two or more.

[0202] When using an activator, the amount of the activator used can be 0.1 mole times or more and 100 mole times or less, preferably 0.2 mole times or more and 50 mole times or less, more preferably 0.5 mole times or more and 20 mole times or less relative to the transition metal imide complex of formula (1). If the amount used is within the above range, the improvement of the polymerization activity brought about by the use of the activator can be fully obtained, and the occurrence of side reactions can be fully avoided.

[0203] 《Other additives》

[0204] In order to control the polymerization rate and the molecular weight distribution of the obtained polymer, a Lewis base may be further added.

[0205] Lewis bases include ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone and cyclohexanone; nitriles such as acetonitrile and benzonitrile; amines such as triethylamine and N,N-diethylaniline; pyridines such as pyridine and lutidine; phosphines such as triphenylphosphine; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; phosphine oxides such as triphenylphosphine oxide; esters such as ethyl acetate, etc. Among them, ethers, pyridines, and nitriles are preferred. The Lewis base may be used alone or in combination of two or more.

[0206] When a Lewis base is used, the amount of the Lewis base used can be 0.1 to 1000 times, preferably 0.2 to 500 times, and more preferably 0.5 to 200 times, relative to the transition metal imide complex of formula (1).

[0207] <Chain transfer agent>

[0208] A chain transfer agent may be used in the polymerization reaction. By using a chain transfer agent, the molecular weight of the obtained ring-opening polymer can be adjusted, and the content of dimers and the like can be effectively reduced.

[0209] Examples of the chain transfer agent include α-olefins, internal olefins, and aromatic vinyl compounds. Internal olefins are compounds that do not have a double bond at the end of an olefin chain but have a double bond inside. Aromatic vinyl compounds include compounds that have a substituent (eg, an alkyl group) on the vinyl group.

[0210] Examples of the α-olefin include alkenes having 2 to 20 carbon atoms and having a double bond at the α-position, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0211] Examples of the internal olefin include 2-butene and 3-hexene.

[0212] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, and 4-tert-butylstyrene.

[0213] Among them, 1-hexene, styrene, and 1-decene are preferred, and 1-hexene and styrene are more preferred, from the viewpoint of reactivity and molecular weight controllability.

[0214] The chain transfer agent may be used alone or in combination of two or more.

[0215] When a chain transfer agent is used, the amount of the chain transfer agent used can be 0.1 mol% or more and less than 15 mol% relative to 100 mol% of the norbornene-based monomer. If it is within the above range, the effect brought by the use of the chain transfer agent can be fully obtained. From the aspect of reducing the content of dimers, the chain transfer agent is preferably 0.3 mol% or more and less than 10 mol%, more preferably 0.5 mol% or more and 9 mol% or less, and further preferably 1 mol% or more and 6 mol% or less.

[0216] <Organic Solvents>

[0217] The polymerization reaction is usually carried out in an organic solvent.

[0218] The organic solvent is not particularly limited as long as it can dissolve or disperse the norbornene-based monomer and the target norbornene-based polymer and is inactive to the reaction, and examples thereof include:

[0219] Aliphatic hydrocarbons such as pentane, hexane, and heptane;

[0220] Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindene, and cyclooctane;

[0221] Aromatic hydrocarbons such as benzene, toluene, and xylene;

[0222] Halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane;

[0223] Halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene;

[0224] Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene, and acetonitrile;

[0225] Ethers such as diethyl ether and tetrahydrofuran, or mixed solvents thereof. Among these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and ethers are preferably used.

[0226] The organic solvent may be used alone or in combination of two or more.

[0227] The organic solvent can be used in an amount such that the concentration of the norbornene-based monomer is 1% by mass or more and 50% by mass or less, preferably 2% by mass or more and 45% by mass or less, and more preferably 3% by mass or less and 40% by mass or less. If it is within the above range, the productivity is sufficient and the handling is also convenient.

[0228] <Polymerization Reaction Conditions>

[0229] The polymerization reaction can generally be carried out by stirring the norbornene monomer, the transition metal imide complex of formula (1), and optionally an activator and a chain transfer agent in an organic solvent. However, the present invention is characterized in that at least a portion of the norbornene monomer is added continuously.

[0230] Components other than the continuously added norbornene-based monomer may be previously charged into the reactor and stirred in advance. The polymerization reaction can be carried out by continuing to stir the reaction solution in the reactor even during the continuous addition of the norbornene-based monomer.

[0231] The norbornene monomer added continuously may be the whole amount or a part. From the aspects of reaction selectivity and reaction stability, it is preferred that the norbornene monomer added continuously is a part, and the remainder is pre-loaded into the reactor. When the total amount of the norbornene monomer is 100% by mass, the amount of the norbornene monomer pre-loaded into the reactor can be 0.1% by mass or more and 70% by mass or less, preferably 0.5% by mass or more and 50% by mass or less, and more preferably 1% by mass or more and 35% by mass or less. If within the above range, the weight average molecular weight of the obtained polymer becomes easy to control.

[0232] The continuous addition of the norbornene monomer can be carried out by preparing a liquid dissolved or dispersed in the above-mentioned organic solvent and continuously dropping it. The concentration of the norbornene monomer in the liquid can be 1% by mass or more and 50% by mass or less, preferably 2% by mass or more and 45% by mass or less, and more preferably 3% by mass or more and 40% by mass or less. If it is within this range, the productivity is sufficient and it is also convenient in terms of handling.

[0233] The time for continuous addition can be 20 minutes to 200 minutes. From the viewpoint of controlling stereochemistry, it is preferably 40 minutes to 180 minutes, and more preferably 60 minutes to 160 minutes.

[0234] The polymerization temperature can be 20° C. to 60° C. From the viewpoint of controlling stereochemistry, it is preferably 25° C. to 55° C., and more preferably 30° C. to 50° C.

[0235] The temperature of the norbornene-based monomer to be continuously added can be 20° C. to 60° C. From the viewpoint of controlling stereochemistry, it is preferably 22.5° C. to 50° C., and more preferably 25° C. to 45° C.

[0236] From the perspective of controlling the molecular weight, the continuous addition of norbornene monomers is preferably carried out in the following manner: in the polymerization reaction system at the end of the continuous addition, the polymerization conversion rate of the norbornene monomers is 40% or more. The polymerization conversion rate is more preferably 60% or more. The polymerization conversion rate can be controlled by adjusting the addition conditions such as the addition rate of the norbornene monomers, the polymerization reaction conditions such as the polymerization temperature, etc. When the conditions other than the speed at the time of addition are the same, there is a tendency that when the speed is increased, the polymerization conversion rate increases, when the speed is reduced, the polymerization conversion rate decreases, when the temperature is high, the polymerization conversion rate increases, and when the temperature is low, the polymerization conversion rate decreases. The upper limit of the polymerization conversion rate is not particularly limited, and is usually 99% or less.

[0237] After the continuous addition is completed, the reaction solution is continuously stirred to terminate the polymerization reaction. The time of the mixed stirring after termination can be more than 15 minutes and less than 300 minutes. From the aspect of polymerization conversion rate and productivity, it is preferably more than 20 minutes and less than 270 minutes, more preferably more than 30 minutes and less than 240 minutes.

[0238] About transition metal imide complex, at least a part can also be added continuously. Thus, reaction selectivity can be expected. The transition metal imide complex added continuously can be made into a liquid dissolved or dispersed in the above-mentioned organic solvent and added continuously. The concentration of the transition metal imide complex in the liquid can be 0.01 mass % or more and 20 mass % or less. From the aspect of the solution stability of the complex, it is preferably 0.1 mass % or more and 15 mass % or less, more preferably 0.5 mass % or more and 10 mass % or less. The timing of continuous addition can be the same as the timing of continuous addition of norbornene-based monomers, or it can be different.

[0239] When a chain transfer agent is used, the amount of norbornene-based polymer continuously added can be 0.060 mol / min or more, preferably 0.080 mol / min or more, and can be 2.000 mol / min or less, preferably 1.000 mol / min or less, relative to 1 mol of the chain transfer agent, from the perspective of controlling stereochemistry and reducing the content of dimers, etc.

[0240] The addition polymerization can be carried out in the presence of any one of a Ziegler-Natta catalyst, a metallocene catalyst, a nickel catalyst, and a palladium catalyst. The addition polymerization can also be carried out under reaction conditions obtained by appropriately modifying known reaction conditions.

[0241] <Hydrogenation process>

[0242] The norbornene polymer obtained in the polymerization process has a carbon-carbon double bond in the main chain. In addition, depending on the type of monomer used for polymerization, sometimes a substituent bonded to the main chain or the 5-membered ring or a fused ring (hereinafter referred to as a side chain) with a 5-membered ring also has a carbon-carbon double bond. By hydrogenating the norbornene polymer, a hydrogenated product in which these carbon-carbon double bonds are hydrogenated to become a saturated bond can be obtained. By making a hydrogenated product, properties such as heat resistance, weather resistance, light resistance, solvent resistance, chemical resistance, and water resistance are improved. As a method of hydrogenation, a known method can be used, for example, hydrogen can be supplied to a solution of a norbornene polymer in the presence of a hydrogenation catalyst, and an addition reaction occurs, thereby proceeding. The hydrogenation catalyst preferably hydrogenates the carbon-carbon double bond in the main chain and does not hydrogenate the naphthalene ring of the naphthyl group. As such a hydrogenation catalyst, for example, a ruthenium catalyst (carbonyl chlorohydrotris (triphenylphosphine) ruthenium) and a palladium catalyst can be cited. The supply of hydrogen can be performed by, for example, applying high pressure (for example, 1 MPa or more) to hydrogen and stirring at high temperature (for example, 120° C. or more).

[0243] <Recycling Process>

[0244] The norbornene-based polymer obtained in the polymerization step or the hydrogenated product obtained in the hydrogenation step can be recovered as a cyclic olefin polymer. For example, the cyclic olefin polymer can be precipitated by mixing the reaction solution with a precipitant (e.g., a poor solvent such as isopropanol or methanol), and the cyclic olefin polymer can be recovered as a precipitate. The recovered cyclic olefin polymer can be dried (e.g., vacuum dried).

[0245] (Physical Properties of Cyclic Olefin Polymers)

[0246] <Refractive Index>

[0247] The refractive index depends on wavelength and temperature and can be measured under any wavelength and temperature conditions. In this specification, the refractive index is the refractive index (n d In order to exert the optical function of the optical element, the refractive index (n d ) is preferably 1.545 or more, more preferably 1.550 or more. In order to exert the function of an optical element, the refractive index (n d ) is preferably 1.640 or less, more preferably 1.635 or less.

[0248] <Abbe number>

[0249] The Abbe number is a value calculated based on the refractive index at three wavelengths. There are various definitions depending on the combination of wavelengths. In this specification, the Abbe number defined by the following formula (1) is used as the Abbe number (ν d ).

[0250] ν d =(n d -1) / (n F -n C ) (1)

[0251] In formula (1), n d 、n C and n F The refractive indices at wavelengths of 587.6 nm, 656.3 nm, and 486.1 nm at 25°C are shown respectively.

[0252] The Abbe number (ν d ) is preferably 20 or more, more preferably 21 or more. In order to reduce the chromatic aberration of the optical element, the Abbe number (ν d ) is preferably 50 or less, more preferably 49 or less.

[0253] <Stress Birefringence>

[0254] About stress birefringence (C R ), stress (F) is applied to the measurement sample, and then the in-plane retardation (Re(b)[nm]) and thickness (T(b)[mm]) of the central part of the measurement sample at a specific wavelength (for example, a wavelength of 543nm) are measured. The δn value can be calculated using the following formulas (X1) and (X2).

[0255] δn=Re(b)×(1 / T(b))×10 -6 (X1)

[0256] C R =δn / F (X2)

[0257] The closer the δn value is to 0, the smaller the birefringence is. In addition, when the slow axis is in the stretching direction, it is expressed as a positive value, and when the slow axis is orthogonal to the stretching direction, it is expressed as a negative value. The stress birefringence (C R ) is preferably -500×10 -12 Pa -1 More preferably -400×10 -12 Pa -1 In order to suppress the quality deviation of the optical element, the stress birefringence (C R ) is preferably 1400×10 -12 Pa -1Below, more preferably 900×10 - 12 Pa -1 the following.

[0258] <Glass transition temperature>

[0259] The glass transition temperature of the cyclic olefin polymer of the present invention can be, for example, 40° C. to 200° C. The glass transition temperature can be controlled, for example, by adjusting the composition of the monomer composition used when synthesizing the cyclic olefin polymer of the present invention.

[0260] (Application of Cyclic Olefin Polymers)

[0261] <Composition>

[0262] The cyclic olefin polymer of the present invention can be used as a composition. The composition contains the cyclic olefin polymer of the present invention and optionally contains additives such as weather stabilizers, heat stabilizers, antistatic agents, flame retardants, slip agents, anti-blocking agents, anti-fogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers, and solvents.

[0263] In addition, the cyclic olefin polymer of the present invention and the additive or solvent can be mixed using a known mixing method.

[0264] Here, as the additive, specifically, for example, the additives exemplified in Japanese Patent Application Laid-Open No. 2005-330465 can be used. Also, as the solvent, a known solvent such as the above-mentioned organic solvent can be used.

[0265] The cyclic olefin polymer of the present invention or a composition comprising the cyclic olefin polymer of the present invention can be advantageously used as a material for optical elements and the like.

[0266] <Molding>

[0267] The cyclic olefin polymer of the present invention can be used as a molded product. The molded product is obtained by molding the cyclic olefin polymer of the present invention or a composition containing the cyclic olefin polymer of the present invention. Furthermore, the molded product obtained from the cyclic olefin polymer of the present invention can be advantageously used as an optical element or the like.

[0268] In addition, as a molding method for the molded body, for example, the following can be used: injection molding, extrusion blow molding, injection blow molding, two-stage blow molding, multi-layer blow molding, connected blow molding, stretch blow molding, rotational molding, vacuum molding, extrusion molding, calendering molding, solution casting, hot press molding, inflation method, etc.

[0269] Example

[0270] Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples.

[0271] <Evaluation Methods of Physical Properties>

[0272] The measurement of various physical properties was carried out according to the following methods.

[0273] (Method for measuring weight average molecular weight Mw)

[0274] The weight average molecular weight Mw is measured by gel permeation chromatography (GPC) using cyclohexane as the eluent, and is obtained as a standard polyisoprene conversion value. As the standard polyisoprene, a standard polyisoprene manufactured by Tosoh Corporation is used. When the sample is insoluble in cyclohexane, tetrahydrofuran (THF) is used as the eluent and measured by GPC, and is obtained as a standard polystyrene conversion value. As the standard polystyrene, a standard polystyrene manufactured by Tosoh Corporation is used.

[0275] (Measurement method of glass transition temperature)

[0276] The glass transition temperature (Tg) was measured using a differential scanning calorimeter (manufactured by Nanotechnology, product name: DSC6220SII) in accordance with JIS K 6911 at a temperature increase rate of 10° C. / min.

[0277] (Stress birefringence of polymer C R Determination method of

[0278] The polymer was molded into a sheet of 35 mm long × 10 mm wide × 1 mm thick to obtain a sample sheet. After fixing the two ends of the sample sheet with a clamp, a 55 g weight was fixed on one of the clamps. Next, in an oven set to the glass transition temperature (Tg) of the polymer + 15°C, the sample sheet was suspended for 1 hour from a clamp without a fixed weight as the starting point for stretching. Then, the sample sheet was slowly cooled and returned to room temperature to obtain a test sample.

[0279] For the measurement sample, the in-plane retardation (Re(b) [nm]) of the central portion of the measurement sample was measured at a measurement wavelength of 543 nm using a birefringence meter ("WPA-100" manufactured by Photonic Lattice, Inc.). In addition, the thickness (T(b) [mm]) of the central portion of the measurement sample was measured. Using these measured values ​​Re(b) and T(b), the δn value was calculated by the following formula (X1).

[0280] δn=Re(b)×(1 / T(b))×10 -6 (X1)

[0281] Using this δn value and the stress (F) applied to the sample, the stress birefringence (C R ).

[0282] C R =δn / F[Pa -1 ] (X2)

[0283] The closer the δn value is to 0, the smaller the birefringence is. In addition, when the slow axis is in the stretching direction, it is expressed as a positive value, and when the slow axis is orthogonal to the stretching direction, it is expressed as a negative value.

[0284] (Refractive index measurement)

[0285] The sheet was formed into a sheet with a thickness of 5 mm and left to stand in an environment of [glass transition temperature (Tg) - 15]°C for 20 hours to prepare a measurement sample.

[0286] The obtained measurement sample was measured using a precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-200, light source = He lamp (wavelength: 587.6 nm), H2 lamp (wavelength: 656.3 nm and 486.1 nm)) to measure the refractive index (n) at 25°C. d 、n C and n F ). The table shows the refractive index of light with a wavelength of 587.6 nm.

[0287] (Abbe number determination)

[0288] The refractive index at 25°C (n d 、n C and n F ), and the Abbe number (ν d ).

[0289] ν d =(n d -1) / (n F -n C ) (1)

[0290] In formula (1), n d 、n C and n F They represent the refractive indices at wavelengths of 587.6nm, 656.3nm, and 486.1nm respectively.

[0291] <Synthesis Example 1: Method for producing exo-1-naphthylnorbornene monomer>

[0292] 458 g of 1-bromonaphthalene (Wako Pure Chemical Industries, Ltd.), 500 mL of dimethylformamide (Wako Pure Chemical Industries, Ltd.), 455 mL of norbornadiene (Tokyo Chemical Industry Co., Ltd.), 656 mL of piperidine (Wako Pure Chemical Industries, Ltd.), 220 mL of formic acid (99%, Wako Pure Chemical Industries, Ltd.), and 2.75 g of palladium catalyst (bistriphenylphosphine palladium dichloride, Tokyo Chemical Industry Co., Ltd., product code: B1667) were added, and stirred at 90°C for 6.5 hours. The reaction solution was extracted with ethyl acetate / water, and the organic layer was dried with magnesium sulfate. It was filtered and evaporated. The residue was subjected to column chromatography (developing solvent: hexane) to remove palladium residue. The obtained solution was evaporated, and the residual liquid was distilled under reduced pressure (1.2 mmHg / 135-152°C). 269 ​​g of colorless transparent liquid exo-1-naphthylnorbornene (exo-1-NaphNB) represented by the following formula was obtained. The peak purity was measured by gas chromatography and found to be 95.0%.

[0293] [Chemical formula 12]

[0294]

[0295] <Synthesis Example 2: Method for producing exo-2-naphthylnorbornene monomer>

[0296] 458 g of 2-bromonaphthalene (Wako Pure Chemical Industries, Ltd.), 500 mL of dimethylformamide (Wako Pure Chemical Industries, Ltd.), 455 mL of norbornadiene (Tokyo Chemical Industry Co., Ltd.), 656 mL of piperidine (Wako Pure Chemical Industries, Ltd.), 220 mL of formic acid (99%, Wako Pure Chemical Industries, Ltd.), and 2.75 g of palladium catalyst (bistriphenylphosphine palladium dichloride, Tokyo Chemical Industry Co., Ltd., product code: B1667) were added and stirred at 90°C for 6.5 hours. The reaction solution was extracted with ethyl acetate / water, and the organic layer was dried with magnesium sulfate. It was filtered and evaporated. The residue was subjected to column chromatography (developing solvent: hexane) to remove palladium residue. The obtained solution was evaporated, and the residual liquid was distilled under reduced pressure (1.2 mmHg / 135-152°C). 269 ​​g of colorless transparent liquid exo-2-naphthylnorbornene (exo-2-NaphNB) represented by the following formula was obtained. The peak purity was measured by gas chromatography and found to be 95.0%.

[0297] [Chemical formula 13]

[0298]

[0299] <Example 1: Production and Evaluation of Norbornene-Based Polymer>

[0300] (1-1) Production of Ring-Opening Polymer

[0301] In a glass reaction vessel substituted with nitrogen, 96 g of dehydrated toluene, 2 mol% of 1-hexene, and 1.2 mol% of diethyl ethoxide aluminum (Et2Al(OEt)) were added and mixed at room temperature, and then, while maintaining 50°C, the entire amount of 0.4 mol% of 2.0 wt% toluene solution of tungsten tetrachloride benzimide (tetrahydrofuran) (complex 1) was added, and then, a mixed monomer of exo-2-naphthyl norbornene and tetracyclododecene (TCD) (molar ratio = 56:44, total 0.03 mol) was added continuously over 2 hours to carry out ring-opening polymerization. Next, 48 mol% of isopropanol was added to the polymerization solution to deactivate the polymerization catalyst and terminate the polymerization reaction. The total amount of the reaction solution was 121 g. The weight average molecular weight Mw of the obtained ring-opening polymer was 2.5×10 4 In addition, the conversion rate of the monomer to the polymer is 100%. Herein, "mol %" means a % value based on the molar number of the mixed monomers.

[0302] (1-2) Production of norbornene-based polymers by hydrogenation

[0303] Next, 155 g of cyclohexane was added to 95 g of the reaction solution containing the ring-opening polymer obtained in the above step (1-1), and 0.05 wt % of carbonyl chlorohydrogen tris(triphenylphosphine)ruthenium as a hydrogenation catalyst was further added. The mixture was pressurized to 4.5 MPa by hydrogen and stirred while heating to a temperature of 160°C. The mixture was then reacted for 8 hours to obtain a reaction solution containing the hydrogenated product of exo-2-naphthyl norbornene / TCD ring-opening copolymer. The obtained solution was injected into a large amount of isopropanol to precipitate the norbornene polymer as a hydrogenated product of the ring-opening polymer. After filtering the precipitated norbornene polymer, it was dried in a vacuum dryer (200°C, 1 Torr) for 10 hours to obtain 5 g of norbornene polymer. The weight average molecular weight of the norbornene polymer is 3.04×10 4 .

[0304] (1-3) Evaluation of norbornene-based polymers

[0305] The glass transition temperature (Tg) and stress birefringence (C R ), refractive index (n d ), and the Abbe number (ν d The results are shown in Table 1.

[0306] <Examples 2 to 7 and Comparative Example 1: Production and Evaluation of Norbornene-Based Polymers>

[0307] The same procedure as in Example 1 was carried out except that the types and composition ratios of the monomer compounds in the mixed monomers used were as shown in Table 1, or the monomer compounds shown in Table 1 were used instead of the mixed monomers. The evaluation results are shown in Table 1.

[0308] [Table 1]

[0309] Table 1. Monomer composition and physical properties of norbornene-based polymers

[0310]

[0311] The abbreviations of the compound names in Table 1 are as follows.

[0312] exo-2-NaphNB: exo-2-naphthyl norbornene

[0313] exo-1-NaphNB: exo-1-naphthyl norbornene

[0314] TCD: Tetracyclododecene

[0315] MTCD: 8-methoxycarbonyl-8-methyltetracyclo[4.4.0.12,5.17,10]-3-dodecene

[0316] MTF: 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene

[0317] Industrial Applicability

[0318] According to the present invention, a cyclic olefin polymer having a high refractive index, a low Abbe number, and a low birefringence can be provided.

[0319] Furthermore, according to the present invention, a composition that can be advantageously used as a material for an optical element or the like, and a molded product that can be advantageously used as an optical element or the like can be provided.

Claims

1. A cyclic olefin polymer, which is a ring-opening polymer containing a structural unit derived from a naphthyl-containing alicyclic compound (A) represented by the following formula (1) or a hydrogenated product thereof, In formula (1), R 2a ~R 5a Any one of them is naphthyl, and the remaining groups and R 1a Each independently is: (i) Hydrogen atoms; (ii) a halogen atom; or (iii) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, the hydrocarbon group excluding a hydrocarbon group containing an aromatic ring, The ratio of the structural unit derived from the compound (A) in all the structural units is 20 mol% or more and 100 mol% or less.

2. The cyclic olefin polymer according to claim 1, wherein The ratio of the structural unit derived from the compound (A) in all the structural units is 20 mol% or more and 90 mol% or less.

3. The cyclic olefin polymer according to claim 1 or 2, wherein R 2a ~R 5a The remaining groups except the naphthyl group and R 1a A hydrogen atom.

4. The cyclic olefin polymer according to claim 1 or 2, which is a ring-opening polymer comprising a structural unit derived from the compound (A) and one or more structural units derived from a norbornene-based monomer (B) different from the compound (A), or a hydrogenated product thereof.

5. The cyclic olefin polymer according to claim 4, wherein The norbornene-based monomer (B) is: (i) norbornenes which are unsubstituted or have an alkyl group, an alkenyl group, an aromatic ring group, a polar group containing an oxygen atom or a polar group containing a nitrogen atom as a substituent; (ii) A monomer represented by the following formula (3): In formula (3), R 1b and R 2b Each independently represents: a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; or an organic group containing a silicon atom, an oxygen atom or a nitrogen atom, R 1b and R 2b Bonded to each other to form a ring or not bonded, R 3b is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; or (iii) A monomer represented by the following formula (4): In formula (4), R 4b ~R 7b Each independently represents: a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; or an organic group containing a silicon atom, an oxygen atom or a nitrogen atom, R 4b and R 6b Bonded to each other to form a ring or not bonded, m is 1 or 2. The cyclic olefin polymer according to claim 1 or 2, which has a weight average molecular weight of 20,000 to 40,000. 7 . The cyclic olefin polymer according to claim 1 , which has a refractive index of 1.545 or more.

8. A method for producing a cyclic olefin polymer, comprising subjecting a naphthyl group-containing alicyclic compound (A) represented by the following formula (1) or a ring-opening polymer containing a structural unit derived from the compound (A) to ring-opening polymerization, In formula (1), R 2a ~R 5a One of them is naphthyl, R 2a ~R 5a The groups other than the naphthyl group and R1 in each independently represent (i) Hydrogen atoms; (ii) a halogen atom; or (iii) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, the hydrocarbon group excluding a hydrocarbon group containing an aromatic ring, The ratio of the total molar number of the compound (A) and the structural unit derived from the compound (A) to the total molar number of all monomers and structural units in the polymerization raw material is 20 mol% or more and 100 mol% or less.

9. The method according to claim 8, comprising subjecting the raw material for polymerization to ring-opening polymerization, The polymerization raw material comprises: the compound (A) or a ring-opening polymer comprising a structural unit derived from the compound (A); and one or more norbornene-based monomers (B) different from the naphthyl-containing alicyclic compound (A) or a ring-opening polymer comprising a structural unit derived from the norbornene-based monomer (B), or, The polymerization raw material includes a ring-opening polymer including a structural unit derived from the compound (A) and a structural unit derived from the norbornene-based monomer (B).

10. The method according to claim 8 or 9, wherein: The ring-opening polymerization is carried out in the presence of a metathesis polymerization catalyst. The metathesis polymerization catalyst is a transition metal imide complex represented by formula (1), M(NR a )X 4-p (OR b ) p ·L q (1) In formula (1), M is a metal atom selected from transition metal atoms of Group 6 of the Periodic Table of Elements, R a is a phenyl group or -CH2R which may have a substituent at at least one of the 3-position, 4-position and 5-position c The group represented by c is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, R b is an alkyl group which may have a substituent or an aryl group which may have a substituent, X is a halogen atom, an alkyl group, an aryl group, an aralkyl group or an alkylsilyl group, L is an electron-donating neutral ligand, p is 0 or 1, q is an integer from 0 to 2, When there are multiple Xs, the multiple Xs can be the same or different. When there are a plurality of L, the plurality of L may be the same or different.

11. The method according to claim 8 or 9, further comprising hydrogenating the ring-opening polymer obtained by the ring-opening polymerization. 12 . An optical element comprising the cyclic olefin polymer according to claim 1 .

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