JP5862299B2 - Method for producing crystalline norbornene ring-opening polymer hydride - Google Patents

Description

  The present invention relates to a method for producing a crystalline norbornene-based ring-opening polymer hydride, and more specifically, crystalline norbornene excellent in heat resistance that maintains a high melting point even after undergoing a thermal history such as melt molding. The present invention relates to a method for producing a crystalline norbornene-based ring-opened polymer hydride that can provide a hydride-based ring-opened polymer.

  For example, a ring-opening polymer hydride of a norbornene monomer such as dicyclopentadiene as described in Patent Document 1 is a kind of so-called cycloolefin polymer, such as transparency, low birefringence, and moldability. Therefore, it is used as a material applicable to various uses including optical use.

  As is also the case described in Patent Document 1, the ring-opening polymer hydride of dicyclopentadiene is generally obtained as an amorphous polymer having an atactic structure. However, the amorphous dicyclopentadiene ring-opened polymer hydride having an atactic structure may have insufficient heat resistance, mechanical strength, solvent resistance and the like depending on its use. Thus, as a technique for improving these performances, it has been proposed to impart crystallinity by imparting stereoregularity to the ring-opening polymer hydride of dicyclopentadiene.

  For example, Patent Document 1 discloses that, when a ring-opening polymerization of dicyclopentadiene is performed using a polymerization catalyst mainly composed of a Group 6 transition metal compound having a specific substituent, stereoregularity is obtained. Based on this, a ring-opening polymer having crystallinity is obtained, and further, the carbon-carbon double bond in the ring-opening polymer is hydrogenated using nickel acetylacetonate or the like as a hydrogenation catalyst, thereby producing crystals. It is disclosed that a ring-opening polymer hydride having properties can be obtained. Patent Document 2 discloses that a ring-opening polymerization of dicyclopentadiene using a polymerization catalyst mainly composed of a transition metal compound of Groups 4 to 6 of the periodic table having an aromatic dioxy group as a ligand. A ring-opening polymer having regularity and crystallinity based thereon is obtained, and further, a carbon-carbon double bond in the ring-opening polymer is replaced with bis (tricyclohexylphosphine) benzylideneruthenium (IV) dichloride. It is disclosed that a hydrogenated ring-opening polymer having crystallinity can be obtained by hydrogenation using, for example, a hydrogenation catalyst.

Non-Patent Document 1 discloses that a ring-opening polymer having isotactic stereoregularity is obtained by ring-opening polymerization of endo-dicyclopentadiene using a specific ring-opening polymerization catalyst such as tungsten imidobiphenolate. A ruthenium carbene compound such as Ru (Cy ₃ P) ₂ Cl ₂ (= CHOEt) is added as a hydrogenation catalyst to the system in which the polymer is present, and a carbon-carbon double bond in the ring-opening polymer is added. It is disclosed that hydrogenation of an endo-dicyclopentadiene ring-opening polymer having crystallinity can be obtained by hydrogenating.

Japanese Patent Laid-Open No. 11-124429 International Publication No. 01/014446 Pamphlet JP 2002-249553 A

Shigetaka Hayano and four others, “Hydrogenated Ring-Opened Poly (endo-dicyclopentadiene) s Made via Stereoselective ROMP Catalyzed by Tungsten Complexes: Crystalline Tactic Polymers and Amorphous Atactic Polymer”, Macromolecules, 2006, Vol. 39, p. 4663-4670

  However, according to the examination by the present inventors, the crystalline dicyclopentadiene ring-opened polymer hydride specifically described in Patent Documents 2 and 3 and Non-Patent Document 1 has a high melting point. However, when the melting point was measured again for one that was once melted and then cooled and solidified, it became clear that the melting point was significantly reduced compared to the measurement before melting. A decrease in the melting point after a thermal history exceeding the melting point means that when the polymer is molded by melt molding, its heat resistance is decreased.

  Therefore, an object of the present invention is a crystalline norbornene having a high melting point and hardly causing a decrease in the melting point after a thermal history exceeding the melting point and exhibiting excellent heat resistance even after molding by melt molding. It is to provide a hydride based on a ring-opening polymer.

  As a result of intensive studies to achieve the above object, the present inventor, as a result of a polymerization catalyst using a periodic table Group 6 transition metal compound having an imide group having a specific structure as a substituent on the central metal, A ring-opening polymerization of a norbornene monomer such as dicyclopentadiene, and a ruthenium hydride compound having a specific structure is added as a hydrogenation catalyst to the system in which the obtained norbornene ring-opening polymer exists, and hydrogen is further added. When added, the hydrogenation of the carbon-carbon double bond present in the norbornene-based ring-opening polymer has a high melting point and crystallinity that hardly causes a decrease in the melting point after a thermal history exceeding the melting point. It has been found that a hydride of norbornene-based ring-opening polymer can be obtained. The present invention has been completed based on this finding.

  Thus, according to the present invention, the norbornene-based monomer obtained by ring-opening polymerization of the norbornene-based monomer with the polymerization catalyst using the group 6 transition metal compound of the periodic table represented by the following formula (1) is obtained. The ruthenium compound represented by the following formula (2) is added as a hydrogenation catalyst to the system in which the ring-opening polymer is present, and then hydrogen is further added to exist in the norbornene-based ring-opening polymer. Provided is a method for producing a crystalline norbornene-based ring-opening polymer hydride in which a carbon-carbon double bond is hydrogenated.

（式（１）中、Ｍは周期表第６族遷移金属原子から選択される原子を表し、Ｒ^１は炭素数１〜１２のアルキル基および置換基を有していてもよい炭素数６〜１２のアリール基から選択される基を表し、Ｒ^２〜Ｒ^９は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜１２のアルキル基および置換基を有していてもよい炭素数６〜１２のアリール基から選択される基を表し、Ｒ^２〜Ｒ^９は互いに結合して環構造を形成してもよい。また、Ｘは独立にハロゲン原子から選択される原子を表し、ｎは１または２であり、ｍは０または２である。）

(In the formula (1), M represents an atom selected from Group 6 transition metal atoms in the periodic table, and R ¹ may have an alkyl group having 1 to 12 carbon atoms and a substituent having 6 to 6 carbon atoms. Represents a group selected from 12 aryl groups, and R ^{2 to} R ⁹ each independently have a hydrogen atom, a C 1-12 alkyl group which may have a substituent, and a substituent. Represents a group selected from aryl groups having 6 to 12 carbon atoms, R ^{2 to} R ⁹ may be bonded to each other to form a ring structure, and X is independently selected from a halogen atom. Represents an atom, n is 1 or 2, and m is 0 or 2.)

（式（２）中、Ｒ^１０〜Ｒ^１２は、それぞれ独立に、炭素数１〜１２のアルキル基および置換基を有していてもよい炭素数６〜１２のアリール基から選択される基を表し、Ｚは、独立に、ハロゲン原子、アルコキシ配位子、およびエステル配位子から選択される配位子を表し、ｐは０〜２の整数であり、ｑは０〜２の整数であり、ｒは１または２であり、ｓは１〜３の整数である。また、４≦ｐ＋ｑ＋ｒ+ｓ≦６である。）

(In Formula (2), R < ¹⁰ > -R < ¹² > respectively independently is group selected from the C1-C12 alkyl group and C6-C12 aryl group which may have a substituent. Z represents a ligand independently selected from a halogen atom, an alkoxy ligand, and an ester ligand, p is an integer of 0 to 2, and q is an integer of 0 to 2. , R is 1 or 2, and s is an integer of 1 to 3. Also, 4 ≦ p + q + r + s ≦ 6.

  In the above method for producing a crystalline norbornene-based ring-opening polymer hydride, the polymerization catalyst further uses an organometallic compound other than the Group 6 transition metal compound of the periodic table represented by the formula (1) as a cocatalyst. It is preferable that

  According to the method for producing a crystalline norbornene-based ring-opening polymer hydride of the present invention, the melting point is high, and the molding is performed by melt molding that hardly causes a decrease in the melting point after a thermal history exceeding the melting point. A crystalline norbornene-based ring-opening polymer hydride that exhibits excellent heat resistance can be provided later.

  The method for producing a crystalline norbornene-based ring-opening polymer hydride according to the present invention comprises a ring-opening polymerization of a norbornene-based monomer using a polymerization catalyst comprising a Group 6 transition metal compound of the periodic table represented by the formula (1). Then, a ruthenium compound represented by the following formula (2) is added as a hydrogenation catalyst to the system in which the obtained norbornene-based ring-opening polymer exists, and then further hydrogen is added to thereby remove the norbornene-based polymer. A crystalline norbornene-based ring-opening polymer hydride that hydrogenates a carbon-carbon double bond present in a ring polymer is produced.

  The norbornene monomer, which is a monomer used in the present invention, is a compound having a norbornene ring structure, and can give crystallinity to the finally obtained norbornene ring-opening polymer hydride. As long as it is not particularly limited, for example, norbornenes and norbornene derivatives having a ring structure other than the norbornene ring condensed to the norbornene ring can be mentioned.

  Specific examples of norbornenes that can be used as the norbornene-based monomer in the present invention 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 Norbornenes having a polar group containing an oxygen atom such as 5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate; 5-cyanonorbornene; And norbornenes having a polar group containing a nitrogen atom such as norbornene-5,6-dicarboxylic imide.

In the present invention, specific examples of the norbornene derivative having a ring structure other than the norbornene ring condensed to the norbornene ring that can be used as a norbornene-based monomer include dicyclopentadiene; tricyclo [4.3.1 ^2,5. . 0] dec-3-ene; tricyclo [4.4.1 ^2,5 . 0] und-3-ene, tetracyclo ^{[6.5.1 2,5.} 0 ^1,6 . 0 ^8,13] trideca -3,8,10,12- tetraene (1,4-methano -1,4,4a, also referred 9a- tetrahydrofluorene); tetracyclo ^{[6.6.1 2,5.} 0 ^1,6 . 0 ^8,13] tetradeca -3,8,10,12- tetraene (1,4-methano -1,4,4a, also referred to as 5,10,10a- hexa hydro anthracene); tetracyclododecene, 8-methyl Tetracyclododecenes having an unsubstituted or alkyl group, such as tetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene; 8-methylidenetetracyclod Double outside the ring such as decene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene, etc. Tetracyclododecenes having a bond; 8-phenyltetracyclod Tetracyclododecenes having an aromatic ring such as cene; tetracyclododecenes having a substituent containing an oxygen atom such as 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, etc. A tetracyclododecene having a substituent containing a nitrogen atom such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imide; a halogen atom such as 8-chlorotetracyclododecene; Tetracyclododecenes having a substituent; tetracyclododecenes having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene; hexacycloheptadecene, 12-methylhexacycloheptadecene, 12 -Ethylhexacycloheptadecene, 12-cyclohexylhexa Hexacycloheptadecenes having an unsubstituted or alkyl group such as cycloheptadecene, 12-cyclopentylhexacycloheptadecene; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene , 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12-cyclopentenylhexacycloheptadecene, etc., hexacycloheptadecenes having a double bond outside the ring; 12-phenylhexacycloheptadecene, etc. Substituents containing an oxygen atom such as 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, etc. Hexacycloheptadecenes having a substituent containing a nitrogen atom such as 12-cyanohexacycloheptadecene and hexacycloheptadecene 12,13-dicarboxylic imide; 12-chlorohexacycloheptadecene and the like And hexacycloheptadecenes having a substituent containing a silicon atom such as 12-trimethoxysilylhexacycloheptadecene, and the like. One of these norbornene monomers may be used alone, or two or more thereof may be used in combination.

  In the method for producing a crystalline norbornene-based ring-opening polymer hydride of the present invention, the heat resistance of the norbornene-based ring-opening polymer hydride is particularly favorable, and from the viewpoint of increasing the crystallization rate, As the norbornene monomer, those containing dicyclopentadiene are preferably used. The ratio of dicyclopentadiene in the norbornene-based monomer is not particularly limited, but is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more. preferable.

  Moreover, in the manufacturing method of the crystalline norbornene-type ring-opening polymer hydride of the present invention, a norbornene-type monomer can be used in combination with another monomer. Examples of other monomers that can be used in combination with the norbornene-based monomer include monocyclic cycloalkenes. Specific examples of the monocyclic cycloalkene include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1,4-cyclooctadiene, cyclodecene, and the like. However, in the method for producing a crystalline norbornene-based ring-opening polymer hydride according to the present invention, the heat resistance of the norbornene-based ring-opening polymer hydride is particularly good, and the crystallization speed is high. Therefore, the amount of the monomer other than the norbornene-based monomer is preferably 20% by weight or less, more preferably 10% by weight or less, and more preferably 5% by weight or less based on the whole monomer. It is particularly preferred that

  In the method for producing a crystalline norbornene ring-opening polymer hydride according to the present invention, a norbornene monomer as described above is used as a group 6 transition metal compound of the periodic table represented by the following formula (1). Ring-opening polymerization with the polymerization catalyst.

（式（１）中、Ｍは周期表第６族遷移金属原子から選択される原子を表し、Ｒ^１は炭素数１〜１２のアルキル基および置換基を有していてもよい炭素数６〜１２のアリール基から選択される基を表し、Ｒ^２〜Ｒ^９は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜１２のアルキル基および置換基を有していてもよい炭素数６〜１２のアリール基から選択される基を表し、Ｒ^２〜Ｒ^９は互いに結合して環構造を形成してもよい。また、Ｘは独立にハロゲン原子から選択される原子を表し、ｎは１または２であり、ｍは０または２である。）

(In the formula (1), M represents an atom selected from Group 6 transition metal atoms in the periodic table, and R ¹ may have an alkyl group having 1 to 12 carbon atoms and a substituent having 6 to 6 carbon atoms. Represents a group selected from 12 aryl groups, and R ^{2 to} R ⁹ each independently have a hydrogen atom, a C 1-12 alkyl group which may have a substituent, and a substituent. Represents a group selected from aryl groups having 6 to 12 carbon atoms, R ^{2 to} R ⁹ may be bonded to each other to form a ring structure, and X is independently selected from a halogen atom. Represents an atom, n is 1 or 2, and m is 0 or 2.)

  That is, in the method for producing a crystalline norbornene ring-opening polymer hydride of the present invention, a specific imide group represented by the formula (1) and a component of a polymerization catalyst for ring-opening polymerization of a norbornene monomer, and A periodic table group 6 transition metal compound having a ligand having a specific biphenolate structure is used. In the present invention, the central metal (M in the formula (1)) of the group 6 transition metal compound of the periodic table used as a component of the polymerization catalyst may be an atom selected from group 6 transition metal atoms of the periodic table. From the viewpoint of increasing the activity of the polymerization catalyst, W atom or Mo atom is preferably used.

The sixth transition metal compound of the Periodic Table for use in the present invention are those having an imide group on the central metal atom, (R ¹ of formula ⁽¹⁾⁾ a substituent having a nitrogen atom in the imide group, It is a group selected from an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have a substituent. The alkyl group having 1 to 12 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t -C1-C20 linear or branched alkyl groups, such as a butyl group and a pentyl group; C3-C20 cycloalkyl groups, such as a cyclohexyl group and an adamantyl group, can be mentioned. In addition, as the aryl group having 6 to 12 carbon atoms which may have a substituent, a phenyl group or a 1 to 5 substituted phenyl having a substituent in at least one of the 2, 3, 4, 5, 6 positions More specific examples include aryl groups having 6 to 24 carbon atoms such as phenyl group, 2,6-dimethylphenyl group and 2,6-diisopropylphenyl. The substituent that the aryl group may have is not particularly limited, but specific examples thereof include an alkyl group, an aryl group, a halogen group, an alkoxy group, an amino group, and an imino group.

Moreover, the periodic table group 6 transition metal compound used in the present invention further has a ligand having one or two biphenolate structures. The ligand having a biphenolate structure may be an unsubstituted biphenolate ligand or may have a substituent on the biphenyl ring. The substituent on the biphenyl ring of this ligand (R ^{2 to} R ^{9 in} formula (1)) is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms and a substituent. These are groups selected from aryl groups having 6 to 12 carbon atoms which may be present, and these may be the same as or different from each other. A plurality of substituents on these biphenyl rings may be bonded to form a ring structure. In addition, as a specific example of the substituent which the C1-C12 alkyl group which may have this substituent, and the C6-C12 aryl group which may have a substituent may have, The same thing as what was mentioned as a specific example of the substituent which the nitrogen atom in an imide group has can be mentioned. Further, when this Group 6 transition metal compound has one ligand having a biphenolate structure, the metal compound has two halogen atoms as substituents on the central metal atom. It is necessary to have. The halogen atom may be any halogen atom, but is preferably a chlorine atom. Further, the two halogen atoms may be the same or different.

In the method for producing a crystalline norbornene-based ring-opening polymer hydride of the present invention, the heat resistance of the norbornene-based ring-opening polymer hydride is particularly favorable, and from the viewpoint of increasing the crystallization rate, In the ligand having a biphenolate structure of the Group 6 transition metal compound of the periodic table, the substituents at the 3 and 3 ′ positions, that is, R ² and R ^{9 in} the formula (1) are bulky substituents. Specifically, it is a group selected from an alkyl group having 1 to 12 carbon atoms which may have a substituent and an aryl group having 6 to 12 carbon atoms which may have a substituent. Preferably, it may have a C3-C12 branched alkyl group which may have a substituent, a C3-C12 cyclic alkyl group which may have a substituent, and a substituent. Select from good aryl groups with 6 to 12 carbon atoms More preferred are isopropyl, t-butyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, (1-phenyl) -1-methyl) ethyl group, 1,1-diphenylethyl group, triphenylmethyl group, (1,1-dimethyl-2,2-dimethyl) propyl group, and particularly a group selected from adamantyl group preferable.

  Specific examples of Group 6 transition metal compounds used in the present invention include bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-. Biphenoxy} (phenylimido) molybdenum (VI), bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} (2,6- Diisopropylphenylimido) molybdenum (VI), bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} (cyclohexylimide) molybdenum (VI ), {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} (phenylimido) molybdenum (VI) dichloride, bis {3,3 '-Diphenyl-1,1'-binaphthyl-2, '-Dioxy} (phenylimido) molybdenum (VI), bis {3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy} (2,6-diisopropylphenylimide) molybdenum (VI), Bis {3,3′-diphenyl-1,1′-binaphthyl-2,2′-dioxy} (adamantylimide) molybdenum (VI), {3,3′-diphenyl-1,1′-binaphthyl-2,2 '-Dioxy} (phenylimido) molybdenum (VI) dichloride, bis {3,3'-di (t-butyl) -5,5', 6,6'-tetramethyl-2,2'-biphenoxy} (phenyl Imido) tungsten (VI), bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} (2,6-diisopropylphenyl Mid) tungsten (VI), bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} (cyclohexylimido) tungsten (VI), Bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} (ethylimido) tungsten (VI), {3,3′-di ( t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} (phenylimido) tungsten (VI) dichloride, bis {3,3′-diphenyl-1,1′-binaphthyl -2,2'-dioxy} (phenylimido) tungsten (VI), bis {3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy} (2,6-diisopropylphenylimide) tungsten (VI), bis {3,3′-diphenyl-1,1′-binaphthyl-2,2′-dioxy} (adamantylimide) tungsten (VI), {3,3′-diphenyl-1,1′-binaphthyl -2,2'-dioxy} (phenylimido) tungsten (VI) dichloride.

  The method for synthesizing the Group 6 transition metal compound of the periodic table used in the present invention is not particularly limited as long as it is obtained, but the Group 6 transition metal imide halide and the biphenol metal salt of the periodic table are used. It is preferable to synthesize by reacting. As the Group 6 transition metal imide halide of the periodic table, a compound having a metal atom and an imide group to be included in the Group 6 transition metal compound used as a polymerization catalyst may be used. Although it does not specifically limit and should just select from arbitrary halogen atoms, it is preferable that it is a chlorine atom from a reactive or versatility viewpoint. Specific examples of Group 6 transition metal imide halides that can be used include phenylimidomolybdenum tetrachloride, 2,6-diisopropylphenylimidemolybdenum tetrachloride, cyclohexylimidemolybdenum tetrachloride, adamantylimidomolybdenum tetrachloride. , Phenylimide tungsten tetrachloride, 2,6-diisopropylphenylimide tungsten tetrachloride, cyclohexylimide tungsten tetrachloride, ethylimide tungsten tetrachloride, adamantylimide tungsten tetrachloride. In addition, these periodic table group 6 transition metal imide halides may be coordinated with one equivalent of an electron-donating base. Examples of the electron donating base include diethyl ether, dibutyl ether, tetrahydrofuran, pyridine, 2,6-lutidine, and triethylamine.

  Moreover, as a biphenol metal salt, the thing of the structure corresponding to the ligand which has a biphenolate structure made to have to the periodic table group 6 transition metal compound used as a polymerization catalyst should just be used, and as a metal atom which comprises a metal salt Is preferably an alkali metal atom. Specific examples of the biphenol metal salt that can be used include 3,3′-di (isopropyl) -2,2′-biphenoxylithium, 3,3 ′, 5,5′-tetra (t-butyl) -2, 2′-biphenoxy sodium, 3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxylithium, 3,3′-diphenyl-2, 2′-biphenoxy lithium, 3,3′-ditrityl-2,2′-biphenoxy lithium, 3,3′-diadamantyl-5,5 ′, 6,6′-tetramethyl-2,2′-bi Phenoxy potassium, 3,3′-di (isopropyl) -1,1′-binaphthyl-2,2′-dioxylithium, 3,3′-di (t-butyl) -1,1′-binaphthyl-2, 2'-dioxylithium, 3,3'-di (t-butyl)- , 1′-binaphthyl-2,2′-dioxysodium, 3,3′-diphenyl-1,1′-binaphthyl-2,2′-dioxylithium, 3,3′-diadamantyl-1,1 ′ -Binaphthyl-2,2'-dioxylithium can be mentioned.

  In the reaction of the Group 6 transition metal imide halide with the biphenol metal salt, the method of mixing these is not particularly limited, but the Group 6 transition metal imide halide dissolved in or dispersed in an organic solvent and the organic A method of mixing a biphenol metal salt dissolved or dispersed in a solvent is preferably used. The organic solvent used in this method is not particularly limited as long as it can dissolve or disperse Group 6 transition metal imide halides and biphenol metal salts of the periodic table and does not adversely affect these reactions. Instead, a commonly used organic solvent can be used.

  Specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene. Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; ether solvents such as diethyl ether and tetrahydrofuran; aromatic ether solvents such as anisole and phenetole; aromatic amine solvents such as pyridine and lutidine; Aliphatic hydrocarbons such as pentane, hexane and heptane; and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, and cyclooctane. Among these organic solvents, from the viewpoint of excellent solubility of Group 6 transition metal imide halides and biphenol metal salts in the periodic table, and reducing the influence on subsequent reactions, aromatic hydrocarbon solvents or ether solvents Is preferably used. Moreover, the density | concentration of the periodic table 6 group transition metal imide halide and biphenol metal salt in the solution containing a periodic table group 6 transition metal imide halide and the solution containing a biphenol metal salt can be selected arbitrarily.

  The mixing for reacting the Group 6 transition metal imide halide with the biphenol metal salt is preferably performed in an inert gas atmosphere. This mixing may be performed by adding a solution containing a biphenol metal salt to a solution containing a Group 6 transition metal imide halide of the periodic table, or vice versa. Moreover, you may add both to another container simultaneously, and may mix them. The molar ratio of the biphenol metal salt to the Group 6 transition metal imide halide of the periodic table is preferably 1 to 10 times, more preferably 1 to 8 times, and particularly preferably 1 to 3 times. If the molar ratio of the biphenol metal salt to the Group 6 transition metal imide halide of the periodic table is less than 1 time, unreacted Group 6 transition metal imide halide of the unreacted periodic table remains, which is not preferable because it affects the polymerization. If the molar ratio is too large, the unreacted biphenol metal salt may affect the polymerization or cause side reactions, which is not preferable. Although reaction temperature is not specifically limited, Generally, it carries out between -100 degreeC-100 degreeC. If the temperature is too low, the progress of the reaction is too slow, and if it is too high, side reactions occur and the product is decomposed, which is not preferable. The preferable range of the reaction temperature is -80 ° C to 80 ° C, more preferably -70 ° C to 70 ° C. Mixing is preferably performed at a low temperature of 0 ° C. or lower, and then the reaction is preferably performed while gradually raising the temperature to room temperature. The reaction time is not particularly limited as long as it is between 1 minute and 1 week.

  For example, in recovering the Group 6 transition metal compound of the periodic table used in the present invention from the reaction solution obtained as described above, an organic solvent in which the target Group 6 transition metal compound is insoluble, such as pentane, is used. It is also possible to add a reactant to the saturated hydrocarbon to precipitate the target compound, or to distill off the solvent used in the reaction to recover the target compound. Further, the reaction solution can be used as it is as a polymerization catalyst.

  In the method for producing a crystalline norbornene ring-opening polymer hydride of the present invention, for example, the norbornene monomer is opened by a polymerization catalyst using the Group 6 transition metal compound of the periodic table obtained as described above. Although ring polymerization is performed, this polymerization catalyst may be a combination of other components other than the Group 6 transition metal compound of the periodic table. In particular, the activity of the polymerization catalyst is increased when the polymerization catalyst is an organic metal compound other than the group 6 transition metal compound of the periodic table represented by the formula (1) as a cocatalyst. preferable. As the organometallic compound used as the cocatalyst, an organometallic compound of any one of Groups 1, 2, 12, 13 and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms is preferably used. Of these, organolithium compounds, organomagnesium compounds, organozinc compounds, organoaluminum compounds, and organotin compounds are preferably used, and among these, organolithium compounds and organoaluminum compounds are preferably used. Specific examples of the organic lithium compound include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, and neophyllithium. Specific examples of the organomagnesium compound include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride, and neophyllmagnesium chloride. Examples of the organic zinc compound include dimethyl zinc, diethyl zinc, and diphenyl zinc. Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum dichloride, and ethylaluminum diethoxide. Examples of the organic tin compound include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin. The addition amount of the organometallic compound used as the cocatalyst is preferably 0.1 to 100 mol times, preferably 0.2 to 50 mol times the central metal of the Group 6 transition metal compound of the periodic table. More preferably, it is used in an amount of 0.5 to 20 mole times. If the amount added is too small, the polymerization activity may not be sufficiently improved, and if it is too large, side reactions may easily occur.

  In the method for producing a crystalline norbornene ring-opening polymer hydride according to the present invention, in order to ring-open polymerization the norbornene monomer, the norbornene monomer and the polymerization catalyst may be mixed. The amount of the polymerization catalyst used relative to the norbornene monomer is not particularly limited, but the molar ratio of (transition metal of the periodic table Group 6 transition metal compound in the polymerization catalyst: norbornene monomer) is A range of 1:10 to 1: 2,000,000 is preferred, a range of 1: 200 to 1: 1,000,000 is more preferred, and a range of 1: 500 to 1: 500,000 is particularly preferred. . If the amount of the polymerization catalyst used is too large, it may be difficult to remove the polymerization catalyst, and if it is too small, sufficient polymerization activity may not be obtained.

  The polymerization reaction can be carried out in a solvent-free system, but is preferably carried out in an organic solvent from the viewpoint of controlling the reaction well. The organic solvent used in this case is not particularly limited as long as it can dissolve or disperse the produced ring-opening polymer and does not adversely affect the polymerization reaction. Specific examples of organic solvents that can be used include aliphatic hydrocarbons such as pentane, hexane, heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, Alicyclic hydrocarbons such as tricyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene , Halogenated aromatic hydrocarbons such as dichlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether, tetrahydrofuran D like - ether; anisole, and aromatic ethers such as phenetole. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, or aromatic ethers are particularly preferably used.

  When the polymerization reaction is performed in an organic solvent, the concentration of the monomer in the reaction system is not particularly limited, but is preferably 1 to 50% by weight, and preferably 2 to 45% by weight. More preferred is 3 to 40% by weight. If the concentration of the monomer is too low, the productivity may be deteriorated. If it is too high, the viscosity of the reaction solution after the polymerization reaction becomes too high, and the subsequent hydrogenation reaction may be difficult.

  The polymerization temperature is not particularly limited, but is usually −30 ° C. to 200 ° C., preferably 0 ° C. to 180 ° C. The polymerization time is not particularly limited, but is usually selected in the range of 1 minute to 100 hours.

  In carrying out the polymerization reaction, a vinyl compound or a diene compound may be added to the polymerization reaction system for the purpose of adjusting the molecular weight of the resulting ring-opening polymer. The vinyl compound used for the purpose of adjusting the molecular weight is not particularly limited as long as it is an organic compound having a vinyl group, but α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene, vinyl Styrenes such as toluene; ethers such as ethyl vinyl ether, i-butyl vinyl ether and allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate; Examples thereof include silicon compounds such as vinyl compounds, vinyltrimethylsilane and vinyltrimethoxysilane. Further, the diene compound used for the purpose of adjusting the molecular weight is not particularly limited, but 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, Non-conjugated dienes such as 2,5-dimethyl-1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3- Examples thereof include conjugated dienes such as pentadiene and 1,3-hexadiene. The amount of the vinyl compound or diene compound to be added may be determined according to the target molecular weight, but is usually selected in the range of 0.1 to 10 mol% with respect to the monomer.

  In the present invention, the ring-opening polymerization reaction of the norbornene-based monomer is performed under the conditions as described above by using the polymerization catalyst using the group 6 transition metal compound of the periodic table represented by the formula (1) as described above. As a result, a norbornene-based ring-opening polymer having isotactic stereoregularity can be obtained. If the hydrogenation reaction is carried out as described below, the tacticity of the polymer will not be changed by the hydrogenation reaction, so that the norbornene-based ring-opening polymer having this isotactic stereoregularity is subjected to the hydrogenation reaction. Thus, a norbornene-based ring-opening polymer hydride having crystallinity based on having isotactic stereoregularity can be obtained. The norbornene-based ring-opening polymer may be recovered from the reaction solution and used for the hydrogenation reaction, but the reaction solution containing the norbornene-based ring-opening polymer may be directly used for the hydrogenation reaction.

The number average molecular weight (Mn) measured by ¹ H-NMR of the norbornene-based ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is preferably 1,000 to 1,000,000, More preferably, it is 000-800,000. By subjecting the norbornene-based ring-opening polymer having such a number average molecular weight to a hydrogenation reaction, it is possible to obtain a norbornene-based ring-opening polymer particularly excellent in the balance between molding processability and heat resistance. The number average molecular weight of the norbornene-based ring-opening polymer can be adjusted by adjusting the amount of the molecular weight modifier used during polymerization.

  The method for producing a crystalline norbornene ring-opening polymer hydride according to the present invention includes a ruthenium compound represented by the following formula (2) in a system in which the norbornene ring-opening polymer obtained as described above is present. Is added as a hydrogenation catalyst, and then hydrogen is added to hydrogenate the carbon-carbon double bond present in the norbornene-based ring-opening polymer, thereby producing a crystalline norbornene-based ring-opening polymer hydrogen. To obtain a compound.

（式（２）中、Ｒ^１０〜Ｒ^１２は、それぞれ独立に、炭素数１〜１２のアルキル基および置換基を有していてもよい炭素数６〜１２のアリール基から選択される基を表し、Ｚは、独立に、ハロゲン原子、アルコキシ配位子、およびエステル配位子から選択される配位子を表し、ｐは０〜２の整数であり、ｑは０〜２の整数であり、ｒは１または２であり、ｓは１〜３の整数である。また、４≦ｐ＋ｑ＋ｒ+ｓ≦６である。）

(In Formula (2), R < ¹⁰ > -R < ¹² > respectively independently is group selected from the C1-C12 alkyl group and C6-C12 aryl group which may have a substituent. Z represents a ligand independently selected from a halogen atom, an alkoxy ligand, and an ester ligand, p is an integer of 0 to 2, and q is an integer of 0 to 2. , R is 1 or 2, and s is an integer of 1 to 3. Also, 4 ≦ p + q + r + s ≦ 6.

  That is, the method for producing a crystalline norbornene-based ring-opening polymer hydride according to the present invention uses a formula (2) as a hydrogenation catalyst for hydrogenating a carbon-carbon double bond existing in a norbornene-based ring-opening polymer. The specific ruthenium compound (ruthenium hydride compound) represented by this is used. In the present invention, in carrying out the hydrogenation reaction, it is important to add the ruthenium compound itself represented by the formula (2) to the system in which the norbornene-based ring-opening polymer exists. In the method for producing a crystalline norbornene ring-opening polymer hydride of the present invention, the specific ruthenium compound represented by the formula (2) is added to the system in which the norbornene ring-opening polymer exists, and then Further, by adding hydrogen, it is possible to obtain a hydrated crystalline norbornene-based ring-opening polymer that has a high melting point and hardly causes a decrease in the melting point after a thermal history exceeding the melting point. It is.

  In the present invention, the ruthenium compound used as the hydrogenation catalyst has one or two hydrogen atoms per molecule as a substituent or a ligand bonded to the ruthenium atom as represented by the formula (2). And 1 to 3 phosphine ligands, and further, 0 to 2 carbonyl ligands and 0 to 2 as substituents or ligands bonded to a ruthenium atom optionally present Having a halogen atom, an alkoxy ligand, and a ligand selected from ester ligands. Moreover, the coordination number (value of p + q + r + s in Formula (2)) in the ruthenium compound represented by Formula (2) is an integer of 4-6.

The substituent (R ^{10 to} R ^{12 in} formula (2)) of the phosphine ligand in the ruthenium compound represented by formula (2) has an alkyl group having 1 to 12 carbon atoms and a substituent. Or a group selected from aryl groups having 6 to 12 carbon atoms, which may be the same as or different from each other. In addition, as a specific example of this C1-C12 aryl group which may have a C1-C12 alkyl group and a substituent, it mentions as a specific example of the substituent which the nitrogen atom in an imide group has. The same thing can be mentioned. Moreover, the ligand selected from the halogen atom, the alkoxy ligand, and the ester ligand that the ruthenium compound represented by the formula (2) has is not particularly limited. A chlorine atom and a bromine atom can be mentioned as examples of an alkoxy ligand, a methoxy ligand and an ethoxy ligand as examples of an ester ligand, and an acetyloxy ligand as an example of an ester ligand.

Specific examples of the ruthenium compound represented by the formula (2) used as the hydrogenation catalyst in the present invention include RuHCl (CO) (PPh ₃ ) ₃ , RuHCl (CO) [P (p-Me-Ph) _{3] 3, RuHCl (CO)} (PCy 3) 2, RuHCl (CO) [P (n-Bu) 3] 3, RuHCl (CO) [P (i-Pr) 3] 2, RuH 2 (CO) ( _{PPh 3) 3, RuH 2 (} CO) [P (p-Me-Ph) 3] 3, RuH 2 (CO) (PCy 3) 3, RuH 2 (CO) [P (n-Bu) 3] 3 RuH _{(OCOCH 3) (CO) (} PPh 3) 2, RuH (OCOPh) (CO) (PPh 3) 2, RuH (OCOPh-CH 3) (CO) (PPh 3) 2, RuH (OCOPh-OCH 3) ( CO) _{PPh 3) 2, RuH (OCOPh} ) (CO) (PCy 3) 2 and the like.

  The hydrogenation reaction is usually performed in an inert organic solvent. Examples of inert organic solvents that can be used include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decahydronaphthalene; tetrahydrofuran, ethylene And ethers such as glycol dimethyl ether.

  In the method for producing a crystalline norbornene-based ring-opening polymer hydride of the present invention, a norbornene-based ring-opening polymer is obtained by adding hydrogen to a system in which a norbornene-based ring-opening polymer and a hydrogenation catalyst are present. Hydrogenates the carbon-carbon double bonds present therein. The suitable temperature range of the hydrogenation reaction varies depending on the hydrogenation catalyst 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 hydrogenation rate may be too slow, and if it is too high, there will be restrictions 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 10 hours. After the hydrogenation reaction, the target crystalline norbornene-based ring-opening polymer hydride may be recovered according to a conventional method, and in recovering the polymer, the catalyst residue can be removed by a technique such as filtration.

  The hydrogenation rate (ratio of hydrogenated main chain double bonds) in the hydrogenation reaction of the ring-opening polymer is not particularly limited, but is preferably 98% or more, more preferably 99% or more, and particularly preferably 99.99. 5% or more. The higher the hydrogenation rate, the better the heat resistance of the finally obtained crystalline norbornene ring-opening polymer hydride.

  Further, the presence or absence of stereoregularity of the crystalline norbornene ring-opening polymer hydride is not particularly limited as long as the polymer is crystalline (that is, having a melting point). In the production method of the invention, a crystalline norbornene ring-opening polymer hydride having isotactic regularity is usually obtained. More specifically, the ratio of the racemo dyad with respect to the repeating unit of the norbornene-based monomer can be 20% or less, and can be 10% or less.

  The crystalline norbornene-based ring-opening polymer hydride obtained by the production method of the present invention as described above has a high melting point and hardly causes a decrease in the melting point after passing through a thermal history exceeding the melting point. . Therefore, it can be said that this crystalline norbornene-based ring-opening polymer hydride exhibits excellent heat resistance even after being molded by melt molding, and is particularly suitable as a material for a molded body that requires heat resistance. Can be used. The use of the molded body is not particularly limited, but examples thereof include light reflectors, insulating materials, optical films, connectors, food packaging materials, bottles, pipes, gears, fibers and nonwoven fabrics, etc. it can.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

In addition, the measurement and evaluation in each example were performed by the following methods.
(1) Number average molecular weight of norbornene-based ring-opening polymer
^{Based on the 1} H-NMR measurement, the ratio of the number of hydrogen atoms present at the polymer chain terminal to the number of hydrogen atoms present in the polymer chain other than the terminal is determined, and the norbornene-based ring-opening polymer is determined based on the ratio. The number average molecular weight of was calculated.
(2) Hydrogenation rate in hydrogenation reaction of norbornene ring-opening polymer
^It calculated | required based on < ¹ > H-NMR measurement.
(3) Melting | fusing point of crystalline norbornene-type ring-opening polymer hydride It measured by heating up at 10 degree-C / min using the differential scanning calorimeter.
(4) Ratio of racemo dyad of crystalline norbornene-based ring-opening polymer hydride A ¹³ C-NMR measurement was performed at 150 ° C. using orthodichlorobenzene-d ₄ as a solvent, and a 43.35 ppm signal derived from meso dyad And the intensity ratio of 43.43 ppm signal derived from Racemo Dyad.
(5) Solder immersion evaluation of crystalline norbornene-based ring-opening polymer hydride Sample piece prepared by hot-pressing a crystalline norbornene-based ring-opening polymer hydride as a sample into a shape of 10 mm × 100 mm × 1 mm Was immersed in 260 ° C. solder for 20 seconds, and the presence or absence of deformation was evaluated. Those that do not cause visible deformation are excellent in heat resistance.
(6) Curling value of crystalline norbornene ring-opening polymer hydride The end face of the sample piece subjected to solder immersion evaluation was placed on a horizontal plane, and the distance between the end face on the opposite side of the long axis direction of this sample piece and the horizontal plane was determined. The measured value was taken as the curl value. The smaller the curl value, the better the heat resistance.

Synthesis Example (Synthesis of bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} phenylimidotungsten (VI))
To a glass reactor equipped with a stirrer, 2.90 g of tungsten phenylimide tetrachloride diethyl ether complex (W (= NPh) Cl 4 (Et ₂ O)) and 30 ml of diethyl ether were added and cooled to −78 ° C. Further, a solution prepared by dissolving 4.19 g of 3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxylithium in 30 ml of diethyl ether was added. . The mixture was gradually returned to room temperature and reacted for 18 hours. After the reaction, diethyl ether was distilled off from the reaction mixture, then dissolved in a toluene / hexane weight ratio 1/3 mixed solvent, the white precipitate was filtered off through Celite, and all the solvent was distilled off from the solution. A red solid was obtained in 96% yield. This was cooled to −30 ° C., allowed to stand, and recrystallized to obtain a solid substance of red needle crystallites. The yield of the obtained solid was 4.63 g (yield 80%). This solid was analyzed by ¹ H-NMR, ¹³ C-NMR and elemental analysis to give bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2 ′. -Biphenoxy} phenylimidotungsten (VI).

[Example 1]
In a glass reactor equipped with a stirrer, bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} phenylimide tungsten ( VI) 0.0556 g and 4 ml of toluene were added and this was cooled to -78 ° C. Further, 0.00726 g of n-butyllithium dissolved in 1 ml of hexane was added, and this was returned to room temperature and reacted for 15 minutes. Subsequently, 7.5 g of dicyclopentadiene, 27 g of cyclohexane and 0.32 g of 1-hexene were added to the obtained reaction mixture, and a polymerization reaction was performed at 80 ° C. A white precipitate immediately precipitated after the polymerization reaction started. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction solution to aggregate the precipitate, washed by filtration, and dried under reduced pressure at 40 ° C. for 24 hours. The yield of the obtained ring-opening polymer was 7.4 g, and the number average molecular weight was 17,800. Next, 3.0 g of the obtained ring-opening polymer and 47 g of cyclohexane were added to an autoclave equipped with a stirrer. Then, a solution obtained by dispersing 0.00157 g of RuHCl (CO) (PPh ₃ ) _{2 in} 10 ml of cyclohexane was further added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.0 MPa and 160 ° C. for 8 hours. This hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate a hydrogenated ring-opening polymer, which was washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured by using the ring-opened polymer hydride dried under reduced pressure as a sample as it was was 290 ° C. Then, the ring-opened polymer hydride dried under reduced pressure was heated at 300 ° C. for 10 minutes and sufficiently melted, then cooled down to 10 ° C./minute and cooled to room temperature, and sufficiently crystallized. The melting point (hereinafter sometimes referred to as the melting point after melting) measured as a sample (hereinafter also referred to as the sample after melting) was 289 ° C. Moreover, solder immersion evaluation and measurement of a curl value were performed on the sample after melting. The results are shown in Table 1.

[Example 2]
To a glass reactor equipped with a stirrer is added 0.0401 g of 3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenol, 5 ml of toluene and 5 ml of diethyl ether. This was cooled to -78 ° C. Further, a solution prepared by dissolving 0.00726 g of n-butyllithium in 1.5 ml of n-hexane was added, and the solution was gradually returned to room temperature. Next, 0.0282 g of tungsten phenylimide tetrachloride diethyl ether complex, 10 ml of toluene and 10 ml of diethyl ether were added to another glass reactor equipped with a stirrer, and this was cooled to −78 ° C. To this, the whole amount of the aforementioned solution was added, and the mixture was gradually returned to room temperature. After returning to room temperature, the mixture was further stirred at 50 ° C. for 30 minutes, then this solution was cooled to −78 ° C., and 0.00726 g of n-butyllithium dissolved in 0.75 ml of n-hexane was added to this solution. Then, the catalyst solution was prepared by gradually returning to room temperature over 30 minutes. Then, 7.5 g of dicyclopentadiene, 27 g of cyclohexane and 0.32 g of 1-hexene were added to the obtained catalyst solution, and a polymerization reaction was performed at 80 ° C. A white precipitate immediately precipitated after the polymerization reaction started. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction solution to aggregate the precipitate, washed by filtration, and dried under reduced pressure at 40 ° C. for 24 hours. The yield of the obtained ring-opening polymer was 7.4 g, and the number average molecular weight was 17,900. Next, 3.0 g of the obtained ring-opening polymer and 47 g of cyclohexane were added to an autoclave equipped with a stirrer. Then, a solution obtained by dispersing 0.00157 g of RuHCl (CO) (PPh ₃ ) _{2 in} 10 ml of cyclohexane was further added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.0 MPa and 160 ° C. for 8 hours. This hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate a hydrogenated ring-opening polymer, which was washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured using the hydride of the ring-opened polymer dried under reduced pressure as it was as a sample was 290 ° C., and the melting point after melting was 289 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

Example 3
In a glass reactor equipped with a stirrer, the bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} phenylimidotungsten obtained in the synthesis example ( VI) 0.0556 g and 4 ml of toluene were added and this was cooled to -78 ° C. Further, 0.00726 g of n-butyllithium dissolved in 1 ml of hexane was added, and this was returned to room temperature and reacted for 15 minutes. Subsequently, 7.5 g of dicyclopentadiene, 27 g of cyclohexane and 0.32 g of 1-hexene were added to the obtained reaction mixture, and a polymerization reaction was performed at 80 ° C. A white precipitate immediately precipitated after the polymerization reaction started. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction solution to aggregate the precipitate, washed by filtration, and dried under reduced pressure at 40 ° C. for 24 hours. The yield of the obtained ring-opening polymer was 7.4 g, and the number average molecular weight was 17,500. Next, 3.0 g of the obtained ring-opening polymer and 47 g of cyclohexane were added to an autoclave equipped with a stirrer. Then, a solution obtained by dispersing 0.00165 g of RuHCl (CO) (PCy ₃ ) _{2 in} 10 ml of cyclohexane was further added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.0 MPa and 160 ° C. for 8 hours. This hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate a hydrogenated ring-opening polymer, which was washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured using the hydride of the ring-opened polymer dried under reduced pressure as it was as a sample was 290 ° C., and the melting point after melting was 289 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

[Comparative Example 1]
Example 1 except that instead of RuHCl (CO) (PPh ₃ ) ₂ as a hydrogenation catalyst, a mixture of 0.0187 g of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.45 g of ethyl vinyl ether was used. In the same manner as above, a ring-opened polymer hydride was obtained. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured by using the ring-opened polymer hydride dried under reduced pressure as a sample as it was was 290 ° C., and the melting point after melting was 268 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

[Comparative Example 2]
A ring-opening polymer was prepared in the same manner as in Example 1 except that instead of RuHCl (CO) (PPh ₃ ) ₂ as a hydrogenation catalyst, a mixture of 0.05 g of nickel acetate and 0.20 g of triisobutylaluminum was used. A hydride was obtained. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured using the hydride of the ring-opened polymer dried under reduced pressure as it was as a sample was 270 ° C., and the melting point after melting was 269 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

[Comparative Example 3]
As a polymerization catalyst, bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} phenylimidotungsten (VI) and n-butyllithium Instead of the reactant, 2,6-diisopropylphenylimidomolybdenum (VI) neophylidene {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′- A ring-opening polymer hydride was obtained in the same manner as in Example 1 except that 0.0085 g of biphenolate was used. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured using the hydrogenated ring-opened polymer dried under reduced pressure as a sample was 290 ° C., and the melting point after melting was 280 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

[Comparative Example 4]
Comparative Example 3 except that a mixture of 0.0187 g of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.45 g of ethyl vinyl ether was used in place of RuHCl (CO) (PPh ₃ ) ₂ as the hydrogenation catalyst. In the same manner as above, a ring-opened polymer hydride was obtained. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured using the hydride of the ring-opened polymer dried under reduced pressure as it was as a sample was 272 ° C., and the melting point after melting was 270 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

[Comparative Example 5]
A ring-opening polymer was prepared in the same manner as in Comparative Example 3 except that a mixture of 0.05 g of nickel acetate and 0.20 g of triisobutylaluminum was used in place of RuHCl (CO) (PPh ₃ ) ₂ as a hydrogenation catalyst. A hydride was obtained. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured using the ring-opened polymer hydride dried under reduced pressure as it was as a sample was 290 ° C., and the melting point after melting was 273 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

[Comparative Example 6]
In a glass reactor equipped with a stirrer, 0.092 g of bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} oxymolybdenum (VI) And 4 ml of toluene were added and it was cooled to -78 ° C. And what melt | dissolved 0.0145g of n-butyllithium in 1 ml of hexane was further added, this was returned to room temperature, and it reacted for 15 minutes, and was set as the catalyst solution. And as a polymerization catalyst, bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenoxy} phenylimidotungsten (VI) and n-butyllithium A hydrogenated ring-opened polymer was obtained in the same manner as in Example 1 except that the catalyst solution obtained as described above was used in place of the reaction product. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured using the ring-opened polymer hydride dried under reduced pressure as a sample as it was was 290 ° C., and the melting point after melting was 272 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

[Comparative Example 7]
Comparative Example 6 except that instead of RuHCl (CO) (PPh ₃ ) ₂ as a hydrogenation catalyst, a mixture of 0.0187 g of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.45 g of ethyl vinyl ether was used. In the same manner as above, a ring-opened polymer hydride was obtained. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Moreover, the melting point measured using the ring-opened polymer hydride dried under reduced pressure as it was as a sample was 273 ° C., and the melting point after melting was 270 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

[Comparative Example 8]
A ring-opening polymer was prepared in the same manner as in Comparative Example 6 except that a mixture of 0.05 g of nickel acetate and 0.20 g of triisobutylaluminum was used in place of RuHCl (CO) (PPh ₃ ) ₂ as the hydrogenation catalyst. A hydride was obtained. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the ratio of racemo dyad was 5% or less. Further, the melting point measured using the hydride of the ring-opened polymer dried under reduced pressure as it was as a sample was 275 ° C., and the melting point after melting was 260 ° C. Moreover, solder immersion evaluation and measurement of the curl value were performed on the sample after melting. The results are shown in Table 1.

  As is apparent from Table 1, a polymerization catalyst using a compound corresponding to the Group 6 transition metal compound of the periodic table represented by Formula (1) and a hydrogenation catalyst which is a ruthenium compound represented by Formula (2) In combination, and a crystalline norbornene-based ring-opening polymer hydride is produced, a crystalline norbornene-based ring-opening polymer hydride having a high melting point after melting and excellent heat resistance after melting can be obtained (Example 1 to Example 1). 3). On the other hand, when at least one of the polymerization catalyst and the hydrogenation catalyst does not satisfy the above-mentioned conditions, the obtained crystalline norbornene-based ring-opening polymer hydride has a low melting point after melting and has a high heat resistance after melting. Inferior (Comparative Examples 1 to 8). Therefore, according to the method for producing a crystalline norbornene ring-opening polymer hydride of the present invention, the melting point hardly deteriorates after a thermal history exceeding the melting point, and is excellent even after molding by melt molding. It can be said that a crystalline norbornene-based ring-opening polymer hydride exhibiting heat resistance can be obtained.

Claims (2)

A system in which a norbornene-based monomer is subjected to ring-opening polymerization with a polymerization catalyst using a group 6 transition metal compound of the periodic table represented by the following formula (1), and the resulting norbornene-based ring-opening polymer is present In addition, a ruthenium compound represented by the following formula (2) is added as a hydrogenation catalyst, and then hydrogen is added to hydrogenate a carbon-carbon double bond present in the norbornene-based ring-opening polymer. A process for producing a crystalline norbornene-based ring-opening polymer hydride.

(In the formula (1), M represents an atom selected from Group 6 transition metal atoms in the periodic table, and R ¹ may have an alkyl group having 1 to 12 carbon atoms and a substituent having 6 to 6 carbon atoms. Represents a group selected from 12 aryl groups, and R ^{2 to} R ⁹ each independently have a hydrogen atom, a C 1-12 alkyl group which may have a substituent, and a substituent. Represents a group selected from aryl groups having 6 to 12 carbon atoms, R ^{2 to} R ⁹ may be bonded to each other to form a ring structure, and X is independently selected from a halogen atom. Represents an atom, n is 2 and m is 0. )

(In Formula (2), R < ¹⁰ > -R < ¹² > respectively independently is group selected from the C1-C12 alkyl group and C6-C12 aryl group which may have a substituent. Z represents a ligand independently selected from a halogen atom, an alkoxy ligand, and an ester ligand, p is an integer of 0 to 2, and q is an integer of 0 to 2. , R is 1 or 2, and s is an integer of 1 to 3. Also, 4 ≦ p + q + r + s ≦ 6.

  The crystalline norbornene-based ring-opening weight according to claim 1, wherein the polymerization catalyst further comprises an organometallic compound other than the Group 6 transition metal compound of the periodic table represented by the formula (1) as a cocatalyst. A method for producing a combined hydride.