JP2015083705A - Hydrogenated crystalline cyclic olefin ring-opened polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogenated crystalline cyclic olefin ring-opened polymer suitable for an optical material, in which a ring-opened polymer and a catalyst are efficiently separated from each other.SOLUTION: The hydrogenated crystalline cyclic olefin ring-opened polymer is obtained through steps of: subjecting a polycyclic norbornene monomer containing dicyclopentadiene by 50 wt.% or more to ring-opening polymerization in a hydrocarbon solvent by using a metal compound expressed by formula (3) as a ring-opening polymerization catalyst; and hydrogenating the obtained ring-opened polymer by using a homogeneous catalyst. In the obtained polymer, a proportion of racemo dyads is 88% or more. In the formula, M represents a group 6 transition metal atom in the periodical table; Rrepresents a phenyl group which may have a substituent at 3, 4 or 5 position, or CHR; Rrepresents an alkyl group or an aryl group which may have a substituent; X represents a halogen atom, an alkyl group, an aryl group, or an alkylsilyl group; L represents an electron-donating neutral ligand; a represents 0 or 1; b represents 0, 1 or 2; and Rrepresents a hydrogen atom, or an alkyl group or an aryl group which may have a substituent.

Description

  The present invention relates to a hydrogenated crystalline cyclic olefin ring-opening polymer suitable for optical materials.

Conventionally, a method for removing a catalyst residue from a cyclic olefin ring-opened polymer hydrogenated product has been studied. For example, in Patent Document 1, in the method for producing a cyclic olefin ring-opening polymer having a polar group, the ring-opening polymerization reaction solution is selected from activated clay, activated carbon, diatomaceous earth, activated alumina, and zeolite in the presence of water and / or alcohol. A method for removing a polymerization catalyst by treating with an adsorbent has been proposed. Moreover, in patent document 2, the cyclic olefin ring-opening polymer which has a polar group and has a hetero atom in a bridgehead makes it easy to form a coordination bond with a catalyst metal, and makes removal of a metal residue difficult. For the purpose of solving the problem, an organic compound having a basic functional group and an acidic functional group is brought into contact with a cyclic olefin ring-opening polymer hydrogenated solution in which a ring-opening polymerization catalyst and a hydrogenation catalyst remain, and then a base. The method of contacting the sorbent adsorbent is described in the examples. Here, the hydrogenation catalyst is added to the reaction solution after the ring-opening polymerization reaction, and the hydrogenation reaction is continued.
Even in the case of a cyclic olefin ring-opening polymer hydrogenated product that does not have a polar group, and in the examples of Patent Document 3, the hydrogenation catalyst utilizes the ability to adsorb the catalyst used in the ring-opening polymerization reaction, and toluene. The norbornene-based monomer was subjected to ring-opening polymerization, and then hydrogenated with a nickel-based hydrogenation catalyst without filtration to obtain a cyclic olefin ring-opening polymer hydrogenated product.
In Patent Document 4, a polycyclic norbornene-based monomer is subjected to ring-opening polymerization in a hydrocarbon solvent, so that a precipitated ring-opening polymer is collected, and this is again converted into ruthenium in a hydrocarbon solvent. Hydrogenation was performed using a catalyst to obtain a hydrogenated cyclic olefin ring-opening polymer.

Japanese Patent Laid-Open No. 3-066725 International Publication WO2011 / 048784 JP-A-9-241484 JP 2002-020464 A

  An object of the present invention is to provide a hydrogenated crystalline cyclic olefin ring-opening polymer having excellent optical properties.

In industrial production of a cyclic olefin ring-opening polymer hydrogenated product obtained by using a polycyclic norbornene-based monomer, the present inventors made a polycyclic reaction in a hydrocarbon solvent according to the description in Patent Document 4. After ring-opening polymerization of the norbornene-based monomer and deactivating the ring-opening polymerization catalyst with isopropanol, many catalyst residues remain in the filtered ring-opening polymer, and the activity of the hydrogenation catalyst decreases. In order to obtain a high hydrogen conversion rate, it was confirmed that a large amount of hydrogenation catalyst had to be reacted for a long time. In fact, in Example 2 of Patent Document 4, the hydrogenation reaction is performed for as long as 10 hours using 0.62 parts of the hydrogenation catalyst with respect to 100 parts by weight of the ring-opened polymer. A large amount of the hydrogenation catalyst used causes an increase in the catalyst residue in the finally obtained hydrogenation product, and a long reaction time results in a decrease in productivity, which is not suitable for industrial production. Therefore, with reference to the description in Patent Document 1, it was studied to deactivate the ring-opening polymerization catalyst using water instead of isopropanol. However, it has been found that this method is not suitable for industrial production because the filter agent is clogged when the deposited catalyst is filtered off.
Based on this knowledge, a polycyclic norbornene-based monomer containing 50% by weight or more of dicyclopentadiene is subjected to ring-opening polymerization using a specific ring-opening polymerization catalyst in a hydrocarbon solvent. A crystalline cyclic olefin ring-opening polymer hydrogenated product obtained by hydrogenating a ring polymer using a homogeneous catalyst and having a racemo dyad ratio of 88% or more has been found to have excellent optical properties. The invention has been completed.

Thus, according to the present invention, the following (1) to (3) crystalline cyclic olefin ring-opening polymer hydrogenated products are provided.
(1) Ring opening of a polycyclic norbornene-based monomer containing 50% by weight or more of dicyclopentadiene in a hydrocarbon solvent using a metal compound represented by the following formula (3) as a ring-opening polymerization catalyst A crystalline cyclic olefin ring-opened polymer hydrogenated product obtained by polymerizing and hydrogenating the obtained ring-opened polymer using a homogeneous catalyst and having a racemo dyad ratio of 88% or more.

(In the formula, M is a metal atom selected from Group 6 transition metal atoms in the periodic table, and R ⁸ is phenyl optionally having a substituent at at least one of the 3, 4, and 5 positions. Or a group represented by CH ₂ R ¹⁰ , wherein R ⁹ is a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent, and X Is a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L is an electron-donating neutral ligand, a is 0 or 1, and b is an integer of 0-2. R ¹⁰ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.

(2) After the ring-opening polymerization, the obtained reaction solution is contacted with a polyhydric alcohol, and then contacted with an adsorbent selected from a layered inorganic compound, silica gel, and an ion exchange resin, and then filtered. The crystalline cyclic olefin ring-opening polymer hydrogenated product according to (1), which is obtained by hydrogenation.
(3) After the ring-opening polymerization, the obtained reaction solution is contacted with a polyhydric alcohol, then contacted with a layered inorganic compound, and then filtered to obtain the solution obtained by hydrogenation (1 The crystalline cyclic olefin ring-opening polymer hydrogenated product according to (4).
(4) The crystalline cyclic olefin ring-opening polymer hydrogen according to any one of (1) to (3), wherein the polycyclic norbornene-based monomer is dicyclopentadiene having an end-body ratio of 80% or more. Additive.

Hereinafter, the present invention will be described in detail.
The crystalline cyclic olefin ring-opened polymer hydrogenated product of the present invention is a polycyclic norbornene monomer containing 50% by weight or more of dicyclopentadiene represented by the following formula (3) in a hydrocarbon solvent. Ring-opening polymerization using a metal compound (hereinafter sometimes referred to as “metal compound (3)”) as a ring-opening polymerization catalyst, and the resulting ring-opening polymer is hydrogenated using a homogeneous catalyst. The obtained ratio of racemo dyad is 88% or more. The ratio of racemo dyad can be determined by the method described in the examples.

<Polycyclic norbornene monomer>
In the present invention, first, a polycyclic norbornene monomer is subjected to ring-opening polymerization in a hydrocarbon solvent using the metal compound (3) as a ring-opening polymerization catalyst.
The polycyclic norbornene monomer used may be a norbornene compound having a norbornene skeleton and one or more ring structures condensed to the norbornene skeleton in the molecule. At least a part of the polycyclic norbornene monomer is preferably a polycyclic norbornene monomer having three or more rings. From the viewpoint of particularly improving the heat resistance of the molded article made of the resin composition, a compound represented by the following formula (1) or (2) is particularly preferable as the polycyclic norbornene-based monomer.

In formulas (1) and (2), R ¹ , R ² and R ^{4 to} R ⁷ are each independently 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. R ¹ and R ² , R ⁴ and R ⁶ may be bonded to each other to form a ring. R ³ is a C 1-20 divalent hydrocarbon group which may have a substituent. m is 1 or 2.

Examples of the halogen atom for R ¹ , R ² , R ^{4 to} R ⁷ include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- Alkyl groups such as butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group; Alkenyl groups such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, cyclohexenyl group; ethynyl group, 1-propynyl group, 2-propynyl (propargyl) group , 3-butynyl group, pentynyl group, hexynyl group and other alkynyl groups; phenyl group, tolyl group Aralkyl groups such as benzyl groups and phenethyl groups; xylyl group, a biphenylyl group, a 1-naphthyl group, 2-naphthyl group, anthryl group, an aryl group or a phenanthryl group and the like.

  Examples of these substituents include halogen atoms such as fluorine atom and chlorine atom; alkoxy groups such as methoxy group and ethoxy group;

The divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent of R ³ includes an alkylene group such as a methylene group and an ethylene group; an alkenylene such as a vinylene group; Groups; alkynylene groups such as ethynylene groups; arylene groups such as phenylene groups; combinations thereof; and the like. Examples of the substituent include those exemplified as the substituents for the hydrocarbon groups of R ¹ , R ² , and R ^{4 to} R ⁷ .

Specific examples of the polycyclic norbornene monomer represented by the formula (1) include dicyclopentadiene, methyldicyclopentadiene, 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 referred to as 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 (1,4-methano -1,4,4a, 9, 9a, also referred to as 10-hexa hydro anthracene) can be mentioned.

  Moreover, as a polycyclic norbornene-type monomer represented by Formula (2), the tetracyclododecene when m of Formula (2) is 1, and m of Formula (2) are 2. And hexacycloheptadecenes in the case.

  Specific examples of tetracyclododecenes include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene. Tetracyclododecenes having a substituted or alkyl group; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetra Tetracyclododecenes having a double bond outside the ring such as cyclododecene and 8-cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxy Carbonyltetracyclododecene, 8-methyl-8- Toxicarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride, etc. Tetracyclododecenes having substituents containing oxygen atoms; tetracyclododecenes having substituents containing nitrogen atoms such as 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic imide A tetracyclododecene having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; a tetracyclododecene having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene; Can be mentioned.

  Specific examples of hexacycloheptadecenes include hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. Hexacycloheptadecenes having a substituted or alkyl group; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexa Hexacycloheptadecenes having a double bond outside the ring such as cycloheptadecene, 12-cyclopentenylhexacycloheptadecene, etc .; Heterocyclic rings such as 12-phenylhexacycloheptadecene Sacycloheptadecenes; 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12 , 13-dicarboxylic acid, hexacycloheptadecene 12,13-dicarboxylic anhydride, etc., hexacycloheptadecenes having a substituent containing an oxygen atom; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13- Hexacycloheptadecenes having a substituent containing a nitrogen atom such as dicarboxylic acid imide; Hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; Hexa cycloheptanone decene compound having a substituent containing a Le hexa cycloheptanone de silicon atoms, such as Sen; and the like.

These polycyclic norbornene monomers can be used singly or in combination of two or more.
In the present invention, from the viewpoint of improving the crystallinity and particularly improving the heat resistance of the resulting molded article, the one containing 50% by weight or more of dicyclopentadiene with respect to the entire polycyclic norbornene-based monomer Is used. In particular, it is preferable to use dicyclopentadiene alone.

  In addition, polycyclic norbornene monomers include endo isomers and exo isomers, both of which can be used as monomers, and one isomer can be used alone. Alternatively, an isomer mixture in which endo and exo isomers are present in an arbitrary ratio can be used. However, from the viewpoint of improving the crystallinity and particularly improving the heat resistance of the resulting resin composition, it is preferable to increase the ratio of one stereoisomer, for example, the ratio of the endo isomer or exo isomer, It is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. In addition, it is preferable that the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic | combination ease.

  In the present invention, a monomer other than the polycyclic norbornene monomer may be copolymerized with the polycyclic norbornene monomer. Monomers that can be copolymerized with polycyclic norbornene monomers include bicyclic norbornene compounds, monocyclic olefins, cyclic dienes, and derivatives thereof that do not have a ring structure condensed to a norbornene skeleton. .

  Specific examples of a bicyclic norbornene compound having no ring structure condensed to a norbornene skeleton include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5 -Norbornenes having an unsubstituted or alkyl group such as cyclohexyl norbornene and 5-cyclopentyl norbornene; alkenyl groups such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene and 5-cyclopentenyl norbornene Norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methyl Xoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5, Norbornenes having a polar group containing an oxygen atom, such as 5-di (hydroxymethyl) norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene; 5 -Norbornenes having a polar group containing a nitrogen atom such as cyanonorbornene.

Specific examples of the monocyclic olefin include cyclohexene, cycloheptene, and cyclooctene.
Specific examples of the cyclic diene include cyclohexadiene and cycloheptadiene.

  From the viewpoint of improving the crystallinity and particularly improving the heat resistance of the resulting molded article, the monomer used may contain 80% by weight or more of the polycyclic norbornene-based monomer. It is particularly preferable that it is substantially composed of only a polycyclic norbornene monomer.

The reaction is carried out in a hydrocarbon solvent.
The hydrocarbon solvent to be used is not particularly limited, but specific examples thereof include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, And alicyclic hydrocarbons such as decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindene, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, and xylene; and mixed solvents thereof. Among these, cyclic hydrocarbons such as aromatic hydrocarbons and alicyclic hydrocarbons are preferably used.

<Metal compound (3)>
In the present invention, the metal compound (3) is used as a ring-opening polymerization catalyst.

In the formula, M is a metal atom selected from Group 6 transition metal atoms in the periodic table, and R ⁸ is a phenyl group optionally having a substituent at at least one of the 3, 4, and 5 positions. , Or a group represented by CH ₂ R ¹⁰ , wherein R ⁹ is a group selected from an optionally substituted alkyl group and an optionally substituted aryl group, and X is A group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L is an electron-donating neutral ligand, a is 0 or 1, and b is an integer of 0-2. is there. R ¹⁰ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.

The metal atom (M) constituting the metal compound (3) is selected from group 6 transition metal atoms (chromium, molybdenum, tungsten) in the periodic table. Among these, molybdenum or tungsten is preferably used, and tungsten is particularly preferably used.
The metal compound (3) comprises a metal imide bond. R ⁸ is a substituent on the nitrogen atom constituting the metal imide bond.
Examples of the substituent that the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions may include an alkyl group such as a methyl group or an ethyl group; a fluorine atom, a chlorine atom, or a bromine atom A halogen atom such as methoxy group, ethoxy group, isopropoxy group or the like; and further, substituents present in at least two positions of 3,4,5 are bonded to each other. Also good.
Specific examples of the phenyl group which may have a substituent at at least one of the 3, 4, and 5 positions include a phenyl group; a 4-methylphenyl group, a 4-chlorophenyl group, a 3-methoxyphenyl group, 4 A monosubstituted phenyl group such as a cyclohexylphenyl group or a 4-methoxyphenyl group; a 2-substituted group such as a 3,5-dimethylphenyl group, a 3,5-dichlorophenyl group, a 3,4-dimethylphenyl group, or a 3,5-dimethoxyphenyl group; Substituted phenyl group; trisubstituted phenyl group such as 3,4,5-trimethylphenyl group and 3,4,5-trichlorophenyl group; 2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2- 2-naphthyl group which may have a substituent such as a naphthyl group.
The metal compound (3) has a substituent of R ^{10 in} the group represented by —CH ₂ R ^10, which can be used as a substituent on the nitrogen atom (R ⁸ in formula (3)). The number of carbon atoms of the good alkyl group is not particularly limited, but is usually 1 to 20, preferably 1 to 10. The alkyl group may be linear or branched. Although the substituent which this alkyl group may have is not specifically limited, For example, the phenyl group which may have substituents, such as a phenyl group and 4-methylphenyl group; Alkoxyl groups, such as a methoxy group and an ethoxy group; Is mentioned.
Examples of the aryl group that may have a substituent of R ¹⁰ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The substituent of the aryl group is not particularly limited, and examples thereof include a phenyl group which may have a substituent such as a phenyl group and a 4-methylphenyl group; an alkoxyl group such as a methoxy group and an ethoxy group; Can be mentioned.
R ¹⁰ is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, or a decyl group. Is preferred.
The metal compound (3) has 3 or 4 groups selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. That is, in the formula (3), X represents a group selected from a halogen atom, an alkyl group, an aryl group, and an alkylsilyl group. In addition, when there are two or more groups represented by X in the metal compound (3), these groups may be bonded to each other.

  Examples of the halogen atom that can be a group represented by X include a chlorine atom, a bromine atom, and an iodine atom. 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 t-butyl group, a pentyl group, a neopentyl group, a benzyl group, and a neophyll group. 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. Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a t-butyldimethylsilyl group.

The metal compound (3) may have one metal alkoxide bond or one metal aryloxide bond. The substituent on the oxygen atom constituting this metal alkoxide bond or metal aryloxide bond (R ⁹ in formula (3)) may have an alkyl group which may have a substituent and a substituent. It is a group selected from good aryl groups. The alkyl group which may have a substituent and the aryl group which may have a substituent which can be the group represented by R ⁹ are the same as those in the group represented by R ¹⁰ described above. Can be used.
The metal compound (3) may have one or two electron-donating neutral ligands. As this electron-donating neutral ligand (L in Formula (3)), for example, an electron-donating compound containing an atom of Group 14 or Group 15 of the Periodic Table can be mentioned. Specific examples thereof include phosphines such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine; ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and tetrahydrofuran; trimethylamine, triethylamine, pyridine, And amines such as lutidine. Among these, ethers are particularly preferably used.

The metal compound (3) particularly preferably used as a ring-opening polymerization catalyst for obtaining a cyclic olefin ring-opening polymer having syndiotactic stereoregularity is a tungsten compound having a phenylimide group (in the formula (3)) , M is a tungsten atom, and R ⁸ is a phenyl group), among which tetrachlorotungstenphenylimide (tetrahydrofuran) is particularly preferable.

  The metal compound (3) is an oxyhalide of a Group 6 transition metal and phenyl isocyanates which may have a substituent at at least one of the 3, 4, and 5 positions, or a monosubstituted methyl isocyanate And an electron-donating neutral ligand (L) and, if necessary, an alcohol, a metal alkoxide, a metal aryloxide, etc. (for example, a method described in JP-A-5-345817) ) Can be synthesized. The synthesized metal compound (3) may be purified and isolated by crystallization or the like, or the catalyst synthesis solution can be used as it is as a ring-opening polymerization catalyst without purification.

  The amount of the metal compound (3) used as the ring-opening polymerization catalyst is usually 1: 100 to 1: 2,000,000 in a molar ratio of (metal compound (3): polycyclic norbornene-based monomer). The amount is preferably 1: 500 to 1: 1,000,000, more preferably 1: 1,000 to 1: 500,000. If the amount of catalyst is too large, it may be difficult to remove the catalyst. If the amount is too small, sufficient polymerization activity may not be obtained.

In using the metal compound (3) as a ring-opening polymerization catalyst, the metal compound (3) can be used alone, but an organic metal reducing agent is used in combination with the metal compound (3) from the viewpoint of increasing the polymerization activity. It is preferable to do.
Examples of the organometallic reducing agent used include Groups 1, 2, 12, 13, and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Among these, organolithium, organomagnesium, organozinc, organoaluminum, or organotin are preferably used, and organoaluminum or organotin are particularly preferably used.
Examples of the organic lithium include n-butyl lithium, methyl lithium, phenyl lithium and the like. Examples of the organic magnesium include butyl ethyl magnesium, butyl octyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, allyl magnesium bromide and the like. Examples of the organic zinc include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum ethoxide, diisobutylaluminum isobutoxide, ethylaluminum diethoxide, isobutylaluminum diisobutoxide, etc. Is mentioned. Examples of the organic tin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.

  0.1-100 mol times is preferable with respect to a metal compound (3), as for the usage-amount of an organometallic reducing agent, 0.2-50 mol times is more preferable, and 0.5-20 mol times is especially preferable. If the amount used is too small, the polymerization activity may not be improved, and if it is too much, side reactions may easily occur.

<Ring-opening polymerization reaction>
The ring-opening polymerization reaction can be initiated by mixing the polycyclic norbornene-based monomer, the metal compound (3), and other additives used as necessary. The order in which these components are added is not particularly limited. When mixing each component, the total amount of each component may be added at once, or may be added in multiple portions, and added continuously over a relatively long time (for example, 1 minute or more). You can also Among these, from the viewpoint of controlling the polymerization temperature and the molecular weight of the resulting ring-opening polymer to obtain a resin composition having particularly excellent moldability, the polycyclic norbornene monomer and / or metal compound (3) Is preferably added in a plurality of times or continuously, and the polycyclic norbornene-based monomer is particularly preferably added in a plurality of times or continuously.

  The concentration of the polycyclic norbornene monomer during the polymerization reaction in the hydrocarbon solvent is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 45% by weight. ˜40% by weight is particularly preferred. If the concentration of the polycyclic norbornene monomer is too low, the productivity of the polymer may be deteriorated. If it is too high, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction becomes difficult. There is.

  An activity regulator may be added to the polymerization reaction system. The activity regulator can be used for the purpose of stabilizing the metal compound (3), adjusting the polymerization reaction rate and the molecular weight distribution of the polymer. The activity regulator is not particularly limited as long as it is an organic compound having a functional group, but is preferably an oxygen-containing, nitrogen-containing, or phosphorus-containing organic compound. Specifically, ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, furan and tetrahydrofuran; ketones such as acetone, benzophenone and cyclohexanone; esters such as ethyl acetate; nitriles such as acetonitrile benzonitrile; triethylamine , Amines such as triisopropylamine, quinuclidine, N, N-diethylaniline; pyridines such as pyridine, 2,4-lutidine, 2,6-lutidine, 2-t-butylpyridine; triphenylphosphine, tricyclohexylphosphine Phosphines such as trimethyl phosphate and triphenyl phosphate; phosphine oxides such as triphenyl phosphine oxide; and the like. These activity regulators can be used singly or in combination of two or more. The amount of the activity regulator to be added is not particularly limited, but it may be usually selected between 0.01 and 100 mol% with respect to the metal compound used as the ring-opening polymerization catalyst.

Further, a molecular weight modifier may be added to the polymerization reaction system in order to adjust the molecular weight of the ring-opening polymer. Examples of molecular weight modifiers include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, acetic acid Oxygen-containing vinyl compounds such as allyl, allyl alcohol and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1 , 6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene and other nonconjugated dienes; 1,3-butadiene, 2-methyl-1,3-butadiene, 2, 3-dimethyl-1,3-butadiene, 1,3-penta Ene, conjugated dienes such as 1,3-hexadiene; and the like.
The amount of the molecular weight modifier to be added may be determined according to the target molecular weight, but is usually selected in the range of 0.1 to 50 mol% with respect to the monomer used.

  Although there is no restriction | limiting in particular in superposition | polymerization temperature, Usually, it is the range of -78 degreeC-+200 degreeC, Preferably it is the range of -30 degreeC-+180 degreeC. The polymerization time is not particularly limited and depends on the reaction scale, but is usually in the range of 1 minute to 1000 hours.

<Polyhydric alcohol>
In the present invention, it is preferable to add a polyhydric alcohol to the reaction solution after the ring-opening polymerization of the polycyclic norbornene monomer is allowed to proceed.
Usually, the ring-opening polymerization reaction stops when the ring-opening polymerization reaction solution and the polyhydric alcohol come into contact with each other. That is, in the present invention, the polyhydric alcohol functions as a stopper for the ring-opening polymerization reaction.

Examples of the polyhydric alcohol include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -Butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 2,4-pentanediol, 1,4-pentanediol, 1,2-pentanediol, 2-methyl-2,3 -Butanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,4-pentanediol, 1,3-cyclopentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1, -Hexanediol, 1,5-hexanediol, 2,5-hexanediol, 2,5-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,3-dimethyl-2,3- Butanediol, 3,3-dimethyl-1,2-butanediol, 3-methyl-2,4-pentanediol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-dihydroxybenzene, 1,3 -Dihydroxybenzene, 1,4-dihydroxybenzene, 1,2,3-propanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, 2-ethyl 2-hydroxymethyl-1,3-propanediol, 3-methyl-1,3,5-pentanetriol, 2,2-bis Hydroxymethyl) -1-butanol, 1,3,5-cyclohexanetriol, 1,2,3-cyclohexanetriol, 1,2,3,4-butanetetraol, tetra (hydroxymethyl) methane, 1,2,3 -1,2-ethanediol, 1,3-propanediol and 1,2,3-propane, which include trihydroxybenzene, 1,3,5-hydroxybenzene and the like and have a low melting point and can be handled in a liquid state at room temperature A C2-C3 polyhydric alcohol such as triol is preferably used.
Although there is no special restriction | limiting in the quantity of the polyhydric alcohol contacted with a ring-opening polymerization reaction liquid, It is 0.01-5 weight part normally with respect to 100 weight part of ring-opening polymers, and the solution stability of a ring-opening polymer From this viewpoint, the content is preferably 0.1 to 3 parts by weight.

<Layered inorganic compound>
In the present invention, the catalyst residue is adsorbed on the adsorbent by contacting the ring-opening polymerization reaction solution in contact with the polyhydric alcohol with the layered inorganic compound functioning as the adsorbent, and then the ring-opening polymer is isolated. It is preferable to do this.
The layered inorganic compound is not particularly limited as long as it functions as an adsorbent, and examples thereof include hydrotalcite-like compounds such as hydrotalcite, alunite, calcite, and magnesite, dickite, nacrite, kaolinite, anoxite. , Kaolins such as metahalloysite and halloysite, smectites such as kuito, beidellite, nontronite, saponite, hectorite and stevensite, vermiculites such as vermiculite, mica, illite, sericite, micas such as sea chlorite Attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group. Moreover, these may form the mixed layer.
There is no particular limitation on the amount of the adsorbent to be brought into contact with the ring-opening polymerization reaction solution, but it is usually 0.05 to 10 parts by weight with respect to 100 parts by weight of the ring-opening polymer. From the viewpoint of suppressing a decrease in filtration rate in the separating filtration step, the content is preferably 0.5 to 5 parts by weight.

<Hydrogenation>
The resulting ring-opening polymer can then be hydrogenated by contacting with hydrogen in the presence of a hydrogenation catalyst according to conventional methods. In the present invention, the hydrogenation catalyst is easy to disperse in the hydrogenation reaction solution, so that the addition amount may be small, and since it is active even if it is not at a high temperature and high pressure, the polymer will not be decomposed or gelled, resulting in low cost. Adopt a homogeneous catalyst with excellent quality stability and high catalyst removal efficiency.

  Examples of the homogeneous catalyst include, for example, a Wilkinson complex, that is, a catalyst comprising a combination of chlorotris (triphenylphosphine) rhodium (I); a transition metal compound and an alkyl metal compound, specifically, cobalt acetate / triethylaluminum, nickel acetyl Examples include combinations of acetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, and the like.

In particular, the hydrogenation reaction of the cyclic olefin ring-opening polymer (hydrogenation of the main chain double bond) is performed by supplying hydrogen into the reaction system in the presence of a homogeneous ruthenium catalyst as a hydrogenation catalyst. .
Homogeneous ruthenium catalysts include chlorohydridocarbonyltris (triphenylphosphine) ruthenium, bis (tricyclohexylphosphine) benzilidineruthenium (IV) dichloride, dichlorotris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium , Chlorohydridocarbonyltris (tricyclohexylphosphine) ruthenium, RuH (OCOPh) (CO) (PPh ₃ ) ₂ , RuH (OCOPh-CH ₃ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh-C ₂ H ₅ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh-C ₅ H ₁₁ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh-C ₈ H ₁₇ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh _{-OCH 3) (CO) (PPh} 3) 2, RuH (OCOPh-OC 2 H 5) (CO) (PPh 3) 2, RuH (OCOPh) (CO) (P (c-C 6 H 11) 3) _{2, RuH (OCOPh-NH 2} ) (CO) (PPh 3) 2 and the like.

The addition amount of the homogeneous catalyst is usually 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the cyclic olefin ring-opening polymer, and the viewpoint of optical properties of the molded product obtained from the ring-opening polymer hydride. From 0.005 to 0.1 part by weight is preferable.
Although there is no special restriction | limiting in the quantity of the adsorbent made to contact a ring-opening polymerization reaction liquid, It is 0.001-0.5 weight part normally with respect to 100 weight part of ring-opening polymers, and a ring-opening polymer hydride. From the viewpoint of the optical properties of the molded product obtained from the above, it is preferably 0.005 to 0.1 parts by weight.

The hydrogenation reaction is usually performed in an inert organic solvent. Examples of such inert organic solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, 1,2-ethane. And ethers such as diol dimethyl ether.
The suitable conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst system used, but the reaction temperature is usually -20 ° C to + 250 ° C, preferably -10 ° C to + 220 ° C, more preferably 0 ° C to 200 ° C. . If the hydrogenation temperature is too low, the reaction rate may be too slow, and if it is too high, side reactions may occur.
The hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogen addition rate may be too slow, and if it is too high, there is a restriction on the apparatus in that a high pressure reactor is required.
Although reaction time will not be specifically limited if it can be set as the desired hydrogenation rate, Usually, it is 0.1 to 8 hours, However, 1 to 5 hours are preferable from a viewpoint of productivity and a hydrogenation rate.
The hydrogenation rate in the hydrogenation reaction of the cyclic olefin ring-opening polymer (ratio of hydrogenated main chain double bonds) is not particularly limited, but is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more, most preferably 99% or more. The higher the hydrogenation rate, the better the heat resistance of the cyclic olefin ring-opening polymer hydrogenated product.

  The cyclic olefin ring-opening polymer hydrogenated product obtained as described above has a repeating unit derived from a polycyclic norbornene-based monomer as represented by the following formula (4) or formula (5). Is.

(In the formula, each of R ¹ and R ² independently contains a hydrogen atom; a halogen atom; an optionally substituted hydrocarbon group having 1 to 20 carbon atoms; or a silicon atom, an oxygen atom, or a nitrogen atom. R ¹ and R ² may be bonded to form a ring, and R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. .)

(In formulas (4) and (5), R ^{1 to} R ⁷ and m represent the same meaning as described above.)

In the present invention, when the cyclic olefin ring-opening polymer hydrogenated product obtained using a homogeneous catalyst has no melting point, its glass transition point is preferably 50 ° C. or higher, more preferably 70 to 250 ° C. In the case of having a melting point, the melting point is preferably 200 ° C. or higher, more preferably 230 to 350 ° C.
In particular, the crystalline cyclic olefin ring-opened polymer hydrogenated product obtained using a homogeneous ruthenium catalyst is not particularly limited as long as it has crystallinity, but has a melting point of 200 ° C. or higher. Preferably, it has a melting point of 230 to 290 ° C. By using a crystalline cyclic olefin ring-opening polymer hydrogenated product having such a melting point, a molding material having an excellent balance between moldability and heat resistance can be obtained.

  The crystalline cyclic olefin ring-opened polymer hydrogenated product of the present invention is molded by a method such as melt molding with additives added as necessary. The shape of the molded body is not particularly limited.

  Additives include: antioxidants such as phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants; light stabilizers such as hindered amine light stabilizers; petroleum waxes, Fischer-Tropsch waxes and polyalkylene waxes Waxes such as: sorbitol compounds, metal salts of organic phosphoric acid, metal salts of organic carboxylic acids, nucleating agents such as kaolin and talc; diaminostilbene derivatives, coumarin derivatives, azole derivatives (for example, benzoxazole derivatives, benzotriazole derivatives) , Benzimidazole derivatives, and benzothiazole derivatives), carbazole derivatives, pyridine derivatives, naphthalic acid derivatives, and imidazolone derivatives, etc .; benzophenone UV absorbers, salicylic acid UV absorbers, benzotriazole purple UV absorbers such as line absorbers; glass fibers; colorants; flame retardants; flame retardant aids; antistatic agents; plasticizers; near infrared absorbers; and cyclic olefin ring-opening polymers such as lubricants and soft polymers Examples thereof include polymer materials other than hydrogenated materials.

  The crystalline cyclic olefin ring-opened polymer hydrogenated product of the present invention has a very low residual metal content and is excellent in thermal properties and optical properties, and therefore can be suitably used particularly for optical materials. Examples of a method for obtaining an optical material such as an optical film include injection molding, extrusion molding, press molding, blow molding, and calendar molding.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the part and% in each example are a basis of weight unless there is particular notice.
Moreover, the measurement and evaluation in each example were performed by the following methods.
(1) Molecular weight (weight average molecular weight and number average molecular weight) of cyclic olefin ring-opening polymer
Using a gel permeation chromatography (GPC) system HLC-8320 (manufactured by Tosoh Corporation), an H-type column (manufactured by Tosoh Corporation) was used and measured at 40 ° C. using tetrahydrofuran as a solvent, and was determined as a polystyrene equivalent value.
(2) Filtration amount of the cyclic olefin ring-opening polymer solution A Whatman manufactured syringe filter having a filtration area of 1.96 × 10 ⁻² m ² and a pore diameter of 0.45 μm was attached to the dispenser, a sample was placed, and nitrogen of 0.10 MPa The solution was filtered at a constant pressure, and the filtration amount for 3 minutes was measured.
(3) Hydrogenation rate in cyclic olefin ring-opening polymer hydrogenated product It was determined by ¹ H-NMR measurement at 145 ° C. as an orthodichlorobenzene-d ⁴ solvent.
(4) Glass transition temperature and melting point of hydrogenated dicyclopentadiene ring-opening polymer A sample heated to 300 ° C. in a nitrogen atmosphere was rapidly cooled with liquid nitrogen, and 10 ° C./degree using a differential operation calorimeter (DSC). The temperature was raised in minutes, and the glass transition temperature and melting point were determined.
(5) Ratio of racemo dyad of dicyclopentadiene ring-opening polymer hydrogenated product Using ortho-dichlorobenzene-d4 as a solvent, an inverse-gated decoupling method was applied at 150 ° C., and ¹³ C-NMR measurement was performed. Using the 127.5 ppm peak of chlorobenzene-d4 as a reference shift, the ratio of racemo dyad is determined based on the intensity ratio of the 43.35 ppm signal derived from meso dyad and the 43.43 ppm signal derived from racemo dyad. It was.
(6) Total light transmittance of the film The light transmittance measurement was performed by cutting a film obtained by hot melt extrusion molding into a 120 mm × 120 mm square thin film sample and then a visible spectrophotometer (Japan) The light transmittance at a wavelength of 450 nm in the thickness direction of the film was measured by V-570 manufactured by Bunko Co., Ltd.
(7) HAZE Measurement of Film HAZE measurement was performed by cutting a film obtained by hot melt extrusion molding into a 120 mm × 120 mm square thin film sample at an arbitrary site, and then using a HAZE meter (product name “NDH5000”, NEC Using a color industry).

[Synthesis Example 1] Synthesis of dicyclopentadiene ring-opening polymer solution After fully dried, in a metal pressure-resistant reaction vessel purged with nitrogen, 154.5 parts of cyclohexane and dicyclopentadiene (endo content rate of 99% or more) were added. 42.8 parts of a 70% cyclohexane solution (30 parts as the amount of dicyclopentadiene) and 1.9 parts of 1-hexene were added and heated to 53 ° C. Meanwhile, 0.061 part of 19% diethylaluminum ethoxide / n-hexane solution was added to a solution obtained by dissolving 0.014 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 0.70 part of toluene and stirred for 10 minutes. Then, a catalyst solution was prepared. This catalyst solution was added to the reactor to initiate a ring-opening polymerization reaction. Then, it was made to react for 4 hours, keeping 53 degreeC, and the dicyclopentadiene ring-opening polymer solution was obtained. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained dicyclopentadiene ring-opened polymer are 8,750 and 28,100, respectively, and the molecular weight distribution (Mw / Mn) determined from these is 3.21.

[Example 1]
To 200 parts of the dicyclopentadiene ring-opening polymer solution obtained in Synthesis Example 1, 0.037 part of 1,2-ethanediol was added as a terminator, heated to 60 ° C., and stirred for 1 hour to carry out the polymerization reaction. Stopped. Thereafter, 1 part of a hydrotalcite-like compound (product name “KYOWARD (registered trademark) 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 60 ° C., and stirred for 1 hour. A portion of the resulting dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured to find 26.5 g / 3 minutes. 0.4 parts of Radiolite (registered trademark) # 1500 (manufactured by Showa Chemical Industry Co., Ltd.) as a filter aid was added to the remaining dicyclopentadiene ring-opening polymer solution, and a PP pleated cartridge filter (product name “TCP-HX”, The adsorbent and the solution were separated by filtration using ADVANTEC Toyo). 100 parts of cyclohexane is added to 200 parts of dicyclopentadiene ring-opening polymer solution (30 parts of polymer) after filtration, and abbreviated as chlorohydridocarbonyltris (triphenylphosphine) ruthenium (hereinafter referred to as “ruthenium catalyst”). ) 0.0043 part was added, and a hydrogenation reaction was performed at 6 MPa and 180 ° C. for 4 hours. The obtained hydrogenation reaction liquid is a slurry solution in which a polymer is precipitated. The polymer hydrogenation product and the solution are separated using a centrifuge and dried under reduced pressure at 60 ° C. for 24 hours to obtain crystals. 28.5 parts of a hydrogenated dicyclopentadiene ring-opening polymer having a property was obtained. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 262 ° C., and the ratio of racemo dyad was 89%. Antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, product) was added to 100 parts of the resulting hydrogenated dicyclopentadiene ring-opened polymer. After mixing 1.1 parts of the name “Irganox (registered trademark) 1010” (manufactured by BASF Japan), twin screw extruder (product name “TEM-37B”, Toshiba Machine Co., Ltd.) with four die holes with an inner diameter of 3 mmΦ Made into a strand-shaped formed body by hot melt extrusion molding, and then chopped by a strand cutter to obtain a pellet-shaped hot melt extruded body. The operating conditions of the twin screw extruder are listed below.
-Barrel set temperature: 270-280 ° C
・ Die setting temperature: 210 ℃
・ Screw speed: 145rpm
・ Feeder rotation speed: 50 rpm
Subsequently, the obtained pellets were formed into a film having a thickness of 100 μm and a width of 120 mm using a hot melt extrusion film forming machine (product name “Measuring Extruder Type Me-20 / 2800 V3”, manufactured by Optical Control Systems) equipped with a T-die. A film molded body was obtained by a method of winding on a roll at a speed of 2 m / min. The operating conditions of the film forming machine are listed in the following list.
・ Barrel temperature setting: 280 ℃ ～ 290 ℃
-Die temperature: 240 ° C
-Screw rotation speed: 30rpm
When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.2 and the light transmittance was 90.7%, respectively.

[Example 2]
In the same manner as in Example 1, except that the adsorbent was changed to 1 part of activated clay (product name “Galleon Earth (registered trademark)”, manufactured by Mizusawa Chemical Co., Ltd.) instead of the hydrotalcite-like compound. A pentadiene ring-opening polymer solution was obtained. A part of the obtained dicyclopentadiene ring-opening polymer solution was sampled and the amount of filtration was measured to find 17.3 g. Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 28.2 parts of a dicyclopentadiene ring-opening polymer hydrogenated product. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 260 ° C., and the ratio of racemo dyad was 89%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.3 and the light transmittance was 90.3%.

Example 3
A dicyclopentadiene ring-opening polymer solution was obtained in the same manner as in Example 1 except that the terminator was changed from 0.037 part of 1,2-ethanediol to 0.045 part of 1,3-propanediol. A part of the resulting dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured to find 15.8 g. Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain a hydrogenated product of dicyclopentadiene ring-opening polymer 28.3. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 262 ° C., and the ratio of racemo dyad was 90%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.3 and the light transmittance was 90.2%, respectively.

Example 4
A dicyclopentadiene ring-opening polymer solution was obtained in the same manner as in Example 1 except that the terminator was changed from 0.037 part of 1,2-ethanediol to 0.054 part of glycerol. A portion of the resulting dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured to find 24.8 g. Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 27.8 parts of a hydrogenated dicyclopentadiene ring-opening polymer. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 261 ° C., and the ratio of racemo dyad was 88%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and light transmittance of the obtained film were measured, the HAZE was 0.2 and the light transmittance was 90.9%, respectively.

Example 5
In the same manner as in Example 1, except that the adsorbent was changed to adding 1 part of smectite (product name “Lucentite (registered trademark) SWN”, manufactured by Corp Chemical Co.) instead of the hydrotalcite-like compound. A cyclopentadiene ring-opening polymer solution was obtained. A part of the resulting dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured to find 25.9 g. Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 28.0 parts of a dicyclopentadiene ring-opening polymer hydrogenated product. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 262 ° C., and the ratio of racemo dyad was 89%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.3 and the light transmittance was 90.2%, respectively.

Example 6
Dicyclopentadiene ring opening in the same manner as in Synthesis Example 1 and Example 1 except that the solvent of 100% cyclohexane as the solvent used in the polymerization reaction of Synthesis Example 1 was changed to a mixed solvent of cyclohexane / toluene = 60/40. A polymer solution was obtained. A portion of the resulting dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured to find 25.0 g. Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 28.1 parts of a dicyclopentadiene ring-opening polymer hydrogenated product. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 261 ° C., and the ratio of racemo dyad was 89%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.2 and the light transmittance was 90.6%, respectively.

Example 7
A dicyclopentadiene ring-opening polymer solution was obtained in the same manner as in Example 1 except that the terminator was changed from 0.037 parts of 1,2-ethanediol to 0.038 parts of methanol. A part of the obtained dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured. As a result, it was 7.7 g, and filtration clogging occurred during the measurement. Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 27.2 parts of a hydrogenated dicyclopentadiene ring-opening polymer. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 262 ° C., and the ratio of racemo dyad was 89%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.3 and the light transmittance was 90.3%.

Example 8
A dicyclopentadiene ring-opening polymer solution was obtained in the same manner as in Example 1 except that the terminator was changed from 0.037 parts of 1,2-ethanediol to 0.071 parts of isopropanol.
A part of the resulting dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured to find 13.9 g. Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 27.5 parts of a dicyclopentadiene ring-opening polymer hydrogenated product. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 262 ° C., and the ratio of racemo dyad was 90%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and light transmittance of the obtained film were measured, the HAZE was 0.4 and the light transmittance was 88.9%, respectively.

Example 9
Except that the adsorbent was changed to 3 parts of silica gel (product name “Caract ™ (registered trademark) Q10”, manufactured by Fuji Silysia Chemical Ltd.) instead of 1 part of the hydrotalcite-like compound, the same procedure as in Example 1 was performed. A dicyclopentadiene ring-opening polymer solution was obtained. A portion of the resulting dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured to find 18.7 g.
Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 28.1 parts of a dicyclopentadiene ring-opening polymer hydrogenated product. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 262 ° C., and the ratio of racemo dyad was 89%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.6 and the light transmittance was 87.3%, respectively.

Example 10
Instead of adding 1 part of the hydrotalcite-like compound as the adsorbent, Example 1 and Example 1 were changed except that 3 parts of ion exchange resin (product name “Diaion (registered trademark) CR11”, manufactured by Mitsubishi Chemical Corporation) was added. Similarly, a dicyclopentadiene ring-opening polymer solution was obtained. A part of the resulting dicyclopentadiene ring-opening polymer solution was collected and the amount of filtration was measured to find 27.6 g. Using the remaining dicyclopentadiene ring-opening polymer solution, a hydrogenation reaction was performed in the same manner as in Example 1 to obtain 28.5 parts of a hydrogenated dicyclopentadiene ring-opening polymer. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, the melting point was 260 ° C., and the ratio of racemo dyad was 89%. Using the obtained dicyclopentadiene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Example 1. When the HAZE and light transmittance of the obtained film were measured, the HAZE was 0.8 and the light transmittance was 86.9%, respectively.

[Synthesis Example 2] Synthesis of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution After drying sufficiently, a metal pressure-resistant reaction vessel purged with nitrogen was charged with cyclohexane / toluene = 60 / 40 mixed solvent 118.5 parts, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene 33 parts, 1-hexene 0.15 part was added and heated to 45 ° C., and further as a polymerization catalyst Ring opening polymerization by adding 0.875 part of 15% toluene solution of triisobutylaluminum, 0.0075 part of isobutyl alcohol, 0.01 part of diisopropyl ether and 10.5 part of 0.6% cyclohexane solution of tungsten hexachloride to the reactor. The reaction was started.
Then, it was made to react for 4 hours, keeping 45 degreeC, and the 1, 4- methano- 1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution was obtained. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resulting 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer are 17,300 and 28,500, respectively. The molecular weight distribution (Mw / Mn) determined from these was 1.65.

[Comparative Example 1]
To 200 parts of the 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution obtained in Synthesis Example 2, 0.069 part of 1,2-ethanediol was added as a stopper, The mixture was heated to 0 ° C. and stirred for 1 hour to stop the polymerization reaction. Thereafter, 2 parts of a hydrotalcite-like compound (product name “KYOWARD (registered trademark) 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 50 ° C., and stirred for 1 hour. A part of the resulting 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution was sampled and the amount of filtration was measured to find 17.6 g. 0.8 parts of Radiolite (registered trademark) # 1500 (manufactured by Showa Chemical Industry Co., Ltd.) as a filter aid was added to the remaining 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution, The adsorbent and the solution were separated by filtration using a PP pleated cartridge filter (product name “TCP-HX”, manufactured by ADVANTEC Toyo). To 200 parts of the 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution after filtration, 120 parts of a mixed solvent of cyclohexane / toluene = 60/40 was added, and chlorohydridocarbonyl tris (tri Phenylphosphine) ruthenium (0.0057 parts) was added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and 160 ° C. for 2 hours. The hydrogenation rate of the hydrogenated product of the obtained 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer was 99% or more. The resulting 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated solution was added with an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t -Butyl-4'-hydroxyphenyl) propionate] methane, 0.61 part of product name "Irganox (registered trademark) 1010", manufactured by BASF Japan Ltd.) was mixed, and then a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.) was used. Strands of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated from the extruder in a molten state while removing cyclohexane and other volatile components at 270 ° C. and 1 kPa or less And then cooled to pellets to produce 38.4 parts of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated pellets. . The operating conditions of the extruder are listed below.
・ Die setting temperature: 200 ℃
・ Screw speed: 145rpm
・ Feeder rotation speed: 50 rpm
Subsequently, the obtained pellets were formed into a film having a thickness of 100 μm and a width of 120 mm using a hot melt extrusion film forming machine (product name “Measuring Extruder Type Me-20 / 2800 V3”, manufactured by Optical Control Systems) equipped with a T-die. A film molded body was obtained by a method of winding on a roll at a speed of 2 m / min. The operating conditions of the film forming machine are listed in the following list.
・ Barrel temperature setting: 230 ℃ ~ 240 ℃
-Die temperature: 190 ° C
-Screw rotation speed: 30rpm
When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.2 and the light transmittance was 89.0%, respectively.

[Comparative Example 2]
1,4-methano-1,4,4a, 9a-tetrahydrofluorene was opened in the same manner as in Comparative Example 1 except that the terminator was changed from 0.55 parts of 1,2-ethanediol to 0.50 parts of methanol. A ring polymer solution was obtained. A portion of the resulting 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution was collected and the amount of filtration was measured to find 4.3 g, which was clogged during measurement. Occurred. Using the remaining 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution, a hydrogenation reaction was performed in the same manner as in Comparative Example 1, and 1,4-methano-1,4,4 37.8 parts of 4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated pellets were obtained. The hydrogenation rate of the 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated product was 99% or more. Using the obtained 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Comparative Example 1. When the HAZE and light transmittance of the obtained film were measured, the HAZE was 0.2 and the light transmittance was 88.8%, respectively.

[Comparative Example 3]
1,4-methano-1,4,4a, 9a-tetrahydrofluorene was opened in the same manner as in Comparative Example 1 except that the terminator was changed from 0.55 parts of 1,2-ethanediol to 1.05 parts of isopropanol. A ring polymer solution was obtained. A part of the resulting 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution was sampled and the amount of filtration was measured to find 12.8 g. Using the remaining 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer solution, a hydrogenation reaction was performed in the same manner as in Comparative Example 1, and 1,4-methano-1,4,4 37.8 parts of 4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated pellets were obtained. The hydrogenation rate of the 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated product was 99% or more. Using the obtained 1,4-methano-1,4,4a, 9a-tetrahydrofluorene ring-opening polymer hydrogenated product, a film molded product was obtained in the same manner as in Comparative Example 1. When the HAZE and the light transmittance of the obtained film were measured, the HAZE was 0.5 and the light transmittance was 85.5%, respectively.

[Comparative Example 4]
The hydrogenation reaction was carried out in the same manner as in Example 1 except that the hydrogenation catalyst was changed to adding 0.6 parts of nickel-alumina catalyst (manufactured by JGC Catalysts) instead of adding 0.0043 parts of ruthenium catalyst. And a hydrogenation reaction solution was obtained. In the obtained hydrogenation reaction liquid, it was difficult to separate the precipitated polymer and the hydrogenation catalyst of the solid catalyst by centrifugation. The obtained hydrogenation reaction solution is poured into a large amount of isopropyl alcohol to completely precipitate the polymer, separated by filtration and recovered, and then added with o-dichlorobenzene and heated to 200 ° C. to dissolve only the polymer. The polymer solution of o-dichlorobenzene and the solid catalyst were separated by filtration. When the polymer dissolved in o-dichlorobenzene was cooled and deposited, it was further washed by filtration and dried under reduced pressure at 60 ° C. for 24 hours under vacuum to obtain 23.2 parts of a hydrogenated dicyclopentadiene ring-opening polymer. . The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydrogenated product was 99% or more, but the melting point was 243 ° C. and the ratio of racemo dyad was 83%. In the hydrogenation reaction using the nickel-alumina catalyst, not only separation from the crystalline polymer became difficult, but also the stereoregularity decreased due to side reactions.
The results of the above examples and comparative examples are summarized in Table 1 below.

From this result, the following can be understood.
When a nickel-alumina catalyst, which is a heterogeneous catalyst, was used as the hydrogenation catalyst, it was difficult to separate the polymer deposited after the hydrogenation reaction from the catalyst (Comparative Example 4). It can also be seen that the ratio of racemo dyad is lowered during the hydrogenation reaction, and the melting point is lowered.

Claims (4)

Ring-opening polymerization of a polycyclic norbornene-based monomer containing 50% by weight or more of dicyclopentadiene in a hydrocarbon solvent using a metal compound represented by the following formula (3) as a ring-opening polymerization catalyst; A crystalline cyclic olefin ring-opened polymer hydrogenated product obtained by hydrogenating the obtained ring-opened polymer using a homogeneous catalyst and having a racemo dyad ratio of 88% or more.

(In the formula, M is a metal atom selected from Group 6 transition metal atoms in the periodic table, and R ⁸ is phenyl optionally having a substituent at at least one of the 3, 4, and 5 positions. Or a group represented by CH ₂ R ¹⁰ , wherein R ⁹ is a group selected from an alkyl group which may have a substituent and an aryl group which may have a substituent, and X Is a group selected from a halogen atom, an alkyl group, an aryl group and an alkylsilyl group, L is an electron-donating neutral ligand, a is 0 or 1, and b is an integer of 0-2. R ¹⁰ is a group selected from a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent.   After the ring-opening polymerization, the obtained reaction solution is contacted with a polyhydric alcohol, and then contacted with an adsorbent selected from a layered inorganic compound, silica gel, and an ion exchange resin, and then filtered, The crystalline cyclic olefin ring-opening polymer hydrogenated product according to claim 1, which is obtained by addition.   2. The solution obtained by bringing the reaction solution obtained after the ring-opening polymerization into contact with a polyhydric alcohol and then brought into contact with a layered inorganic compound and then filtered, is obtained by hydrogenation. The crystalline cyclic olefin ring-opening polymer hydrogenated product described.   The crystalline cyclic olefin ring-opening polymer hydrogenated product according to any one of claims 1 to 3, wherein the polycyclic norbornene-based monomer is dicyclopentadiene having an endo-form ratio of 80% or more.