JP2002249553A - Preparation process of norbornene-based ring-opening polymer hydride - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation process of crystalline norbornene-based ring-opening polymer and its hydride and to provide a catalyst compound for the process and its preparation process. SOLUTION: (1) Using a polymerization catalyst comprising a reaction product between a halogenide or oxyhalogenide of a specific transition metal and an aromatic mono-ol or an aromatic mono-oxide, and an organic metal reducing agent, a norbornene-based monomer is polymerized by a metathesis ring-opening polymerization. Then the polymer is hydrogenated. (2) Using a polymerization catalyst comprising a reaction product between a halogenide or oxyhalogenide of a specific transition metal and an aromatic di-ol or an aromatic di-oxide, and an organic metal reducing agent, a norbornene-based monomer is polymerized by a metathesis ring-opening polymerization. Then the polymer is hydrogenated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a norbornene ring-opening polymer having crystallinity or a hydrogenated ring-opening polymer.

[0002]

2. Description of the Related Art Ring-opening metathesis polymerization of norbornene-based monomers using transition metal compounds of Groups 4 to 9 of the Periodic Table has been well known, and in addition to W and Mo of Group 6 of the Periodic Table, Nb, Ta, Re, Zr, Ti, Ru, Os, Ir
Such transition metal compounds have been used as ring-opening polymerization catalysts. A method of ring-opening polymerization of dicyclopentadiene using a polymerization catalyst comprising a halide or oxyhalide of W having a phenoxy group as a ligand, triorganotin hydride and boron halide (US Pat.
T. NO. Metathesis polymerization of cyclic olefins such as dicyclopentadiene using a reaction product of an imide transition metal compound of Groups 5 to 8 of the periodic table with a biphenol and a cocatalyst (US Pat.
O. 5405924). These disclose that only ring-opening polymerization was performed. Ziegler-type polymerization catalysts using halides or oxyhalides of W or Mo and an organometallic reducing agent are widely known. For example,
Polymerization catalyst consisting of a halide such as WCl ₆ or MoCl ₅ and an organotin such as tetraphenyltin or tetra (n-butyl) tin, an oxyhalide such as WOCl ₄ or MoOCl ₄ and triethylaluminum, diethylaluminum chloride, ethylaluminum Polymerization catalysts composed of organoaluminum such as dichloride are well known ('Olefin Metathesis a).
nd Metathesis Polymerizat
ion'K. J. Ivan, J. et al. C. Mol, 199
7, ACADEMIC PRESS, TOKYO, etc.). However, the ring-opened polymer of norbornene-based monomer or its hydride polymerized with these Ziegler-type polymerization catalysts is amorphous and has no melting point. When this polymer is used for various purposes, the mechanical strength, heat resistance, solvent resistance and the like are sometimes insufficient. Therefore, in order to solve these problems, it has been desired to develop a method for producing a norbornene-based ring-opened polymer having a melting point, that is, crystallinity, or a hydride thereof, and a polymerization catalyst used for the method.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a crystalline norbornene-based ring-opening polymer, a hydride thereof, a catalyst used therefor, and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific transition metal halide, oxyhalide or dioxyhalide and an aromatic monool are used. Or, using a polymerization catalyst comprising a reaction product with an aromatic monoxide and an organic metal reducing agent, ring-opening metathesis polymerization of a norbornene-based monomer,
Subsequent hydrogenation gives a polymer hydride having crystallinity, a halide of a specific transition metal, a reaction product of an oxyhalide or a dioxyhalide with an aromatic diol or an aromatic dioxide, Using a polymerization catalyst comprising an organometallic reducing agent, a ring-opening metathesis polymerization of a norbornene-based monomer is performed, and if necessary, hydrogenation is performed, and a polymer having crystallinity and / or a hydride is obtained. Based on such findings, the present invention has been completed. Thus, according to the present invention,

(1) A halide, oxyhalide or dioxyhalide (a) of a transition metal belonging to Groups 4 to 6 of the periodic table and an aromatic monool or an aromatic monooxide (b) having a substituent Is obtained by subjecting a norbornene-based monomer to ring-opening metathesis polymerization in the presence of a polymerization catalyst comprising a reaction product (I) and an organometallic reducing agent (II), and then present in the main chain of the obtained polymer. A method for producing a crystalline norbornene-based ring-opening polymer hydride in which 50% or more of carbon-carbon double bonds are hydrogenated in the presence of a hydrogenation catalyst, (2) Periodic Tables 4 to
From a reaction product (III) of a halide, oxyhalide or dioxyhalide (a) of a Group 6 transition metal with an aromatic diol or aromatic dioxide (c) and an organometallic reducing agent (II) For producing a crystalline norbornene-based ring-opened polymer by subjecting a norbornene-based monomer to ring-opening metathesis polymerization in the presence of a polymerization catalyst of the formula (3): Periodic group 4 to group 4 having an aromatic dioxy group as a ligand Production of a crystalline norbornene-based ring-opening polymer by ring-opening metathesis polymerization of a norbornene-based monomer in the presence of a polymerization catalyst comprising a Group 6 transition metal oxy compound or halide (IV) and an organometallic reducing agent (II) Method. (4) A crystal in which at least 50% of carbon-carbon double bonds present in the main chain of the ring-opened polymer obtained by the method according to (2) or (3) are hydrogenated in the presence of a hydrogenation catalyst. (5) a method for producing a hydrogenated norbornene ring-opening polymer, (5) a polymerization catalyst containing a transition metal oxy compound or a halide from Groups 4 to 6 of the periodic table having an aromatic dioxy group as a ligand, (6) ) The polymerization described in (5) by reacting a halide, oxyhalide or dioxyhalide (a) of a transition metal belonging to Groups 4 to 6 of the periodic table with an aromatic diol or an aromatic dioxide (c). A method for making a catalyst is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention, a norbornene monomer is prepared by using a polymerization catalyst comprising a reactant (I), (III) or compound (IV) and an organometallic reducing agent (II). Is subjected to ring-opening metathesis polymerization and, if necessary, a hydrogenation reaction. The reactant (I) of the present invention comprises a halide, oxyhalide or dioxyhalide (a) of a transition metal belonging to Groups 4 to 6 of the periodic table and an aromatic monool or an aromatic monooxide having a substituent. The reactant (b) with (b) is a halide, oxyhalide or dioxyhalide (a) of a transition metal belonging to Groups 4 to 6 of the periodic table and an aromatic diol or aromatic dioxide ( The reaction product with c), compound (IV) is a transition metal oxy compound or a halide of Group 4 to Group 6 of the periodic table having an aromatic dioxy group as a ligand.

[0007] Group 4 to 6 of the periodic table constituting transition metal halides, oxyhalides or dioxyhalides (a) (hereinafter, referred to as "compound (a)") of the transition metals of Groups 4 to 6. Group transition metals include Ti, Zr,
V, Nb, Ta, Mo, W, and the like.
Among them, Mo and W are preferable because of their high polymerization activity. TiCl ₄ , ZrCl as the halide of the transition metal
₄ , VCl ₅ , NbCl ₅ , TaCl ₅ , MoCl ₅ ,
WCl ₆ , TiBr ₄ , ZrBr ₄ , VBr ₅ , NbB
r ₅ , TaBr ₅ , MoBr ₅ , WBr ₆ , TiF ₄ ,
ZrF ₄ , VF ₅ , NbF ₅ , TaF ₅ , MoF ₅ , W
F ₆ , TiI ₄ , ZrI ₄ , VI ₅ , NbI ₅ , TaI
₅ , MoI ₅ , WI _{6 and the} like. As oxyhalides of transition metals of Groups 4 to 6 of the periodic table, V
OCl ₃ , MoOCl ₄ , WOCl ₄ , VOBr ₃ , M
oOBr ₄ , WOBr ₄ , VOF ₃ , MoOF ₄ , WO
F ₄ , VOI ₃ , MoOI ₄ , WOI _{4 and the} like can be given. MoO ₂ Cl ₂ , WO ₂ Cl ₂ , MoO ₂ as dioxy halides of transition metals of Groups 4 to 6 of the periodic table
Br ₂ , WO ₂ Br ₂ , MoO ₂ F ₂ , WO ₂ F ₂ , MoO ₂ I
₂ , WO ₂ I _{2 and the} like.

The substituted aromatic monools or aromatic monoxides (b) used in the present invention (hereinafter referred to as "b")
It is called "compound (b)". ) Is an aromatic compound having one hydroxyl group and further having a substituent (other than a hydroxyl group) or a metal salt thereof. The substituent is not particularly limited,
Bulk substituents are preferred. Specifically, a halogen atom,
Examples thereof include an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a haloalkyl group, a haloaryl group, and a cyano group. In particular, it is preferable to have a substituent on the carbon adjacent to the carbon to which the oxide group is bonded. The substituent is preferably as bulky as possible. For example, a secondary alkyl group such as an iso-propyl group, a tertiary alkyl group such as a t-butyl group, a phenyl group or a substituted phenyl group, and a haloalkyl group such as a trifluoromethyl group. Groups are preferred. As a structural example of the compound (b), a general formula [1]

General formula [1]:

Embedded image (Wherein, R ¹ and R ⁵ are each independently a halogen atom,
It represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a haloalkyl group, a haloaryl group, or a cyano group. R ^{2 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a haloalkyl group, a haloaryl group, or a cyano group;
They may combine with each other to form a ring structure. M ¹ is a hydrogen atom or a metal atom selected from alkali metals (Li, Na, K, etc.), alkaline earth metals (Mg, Ba, etc.) and aluminum. m is determined by the valence of the element ^{M 1} integer of 0 to 2. X ¹ is a halogen atom. ).

Specific examples thereof include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6
-Di (iso-propyl) phenol, 2,6-di (t
-Butyl) phenol, 2,6-di (t-butyl) -4
-Methylphenol, 2,6-diphenylphenol,
Phenols such as 2,6-di (trifluoromethyl) phenol; sodium 2,6-di (iso-propyl) phenoxy, 2,6-di (t-butyl) phenoxylithium, 2,6-di (t- Phenoxides such as butyl) -4-methylphenoxypotassium, 2,6-diphenylphenoxylithium, and 2,6-di (trifluoromethyl) phenoxylithium; 2,6-di (iso-propyl) phenoxymagnesium bromide; 6-di (t-butyl) phenoxymagnesium chloride, 2,
Examples thereof include phenoxides such as 6-di (t-butyl) -4-methylphenoxyaluminum dichloride, 2,6-diphenylphenoxymagnesium bromide, and 2,6-di (trifluoromethyl) phenoxymagnesium bromide.

Further, naphthols or naphthoxides, anthracenols or anthracenoxides, in which an aromatic ring is further bonded to phenols or phenoxides, can also be mentioned. To give specific examples of these,
1,3-di (iso-propyl) -2-naphthol,
1,3-di (t-butyl) -2-naphthoxylithium,
2- (iso-propyl) -1-naphthol, 2-phenyl-1-naphthol, 2-phenyl-1-naphthoxylithium, 1,3-di (t-butyl) -2-naphthoxyaluminum dichloride, 2- Examples thereof include naphthols and naphthoxides such as phenyl-1-naphthoxymagnesium bromide; and anthracenols and anthracenoxides such as 9-anthracenol and 2-methyl-1-anthracenol.

The aromatic diols or aromatic dioxides (c) (hereinafter, referred to as "compound (c)") used in the present invention are aromatic compounds having two or more hydroxyl groups or metal salts thereof. . The compound (c) preferably further has a substituent. The substituent is preferably bonded to the carbon next to the carbon bonded to the oxy group. Those having a bulky substituent are particularly preferable, and examples of the bulky substituent include those similar to the compounds (b). As a structural example of the compound (c), those represented by the general formulas [2] and [3] are preferable.

General formula [2]:

Embedded image

General formula [3]:

Embedded image

General formula [4]:

Embedded image

General formula [5]:

Embedded image

General formula [6]

Embedded image (Wherein, R ^{6 to} R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group,
An alkoxy group, an aryloxy group, a haloalkyl group or a haloaryl group, or a cyano group, which may be bonded to each other to form a ring structure. Z is selected from general formula [3], general formula [4], general formula [5], general formula [6], an oxygen atom and a sulfur atom. Here, R ¹⁴ and R ¹⁵ represent a hydrogen atom or a hydrocarbon having 1 to 6 carbon atoms. q is 0 or 1. M ¹ and M ² are each independently a hydrogen atom or an alkali metal (Li, Na, K, etc.) or an alkaline earth metal (M
g, Ca, Ba, etc.) and aluminum. X is a halogen atom, m and n are integers of 0 to 2 and are determined by the valences of the elements M ¹ and M ² . )

General formula [7]:

Embedded image (Wherein, R ^{16 to} R ²¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a haloalkyl group, a haloaryl group, or a cyano group. M ¹ and M ² may be each independently a hydrogen atom or an alkali metal (eg, Li, Na, K);
Metal atoms selected from alkaline earth metals (Mg, Ca, Ba, etc.) and aluminum. X is a halogen atom, m and n are integers of 0 to 2 and are determined by the valences of the elements M ¹ and M ² . Furthermore, q in the general formula [2] is 0, that is, biphenol or biphenoxy is most preferred.

Specific examples of the compound in which q in the general formula [2] is 0 include 2,2'-biphenol, 3,3'-dimethyl-2,2'-biphenol, and 3,3'-diethyl-. 2,2′-biphenol, 3,3′-di (iso-propyl) -2,2′-biphenol, 3,3′-di (t
-Butyl) -2,2'-biphenol, 3,3'-di (t-butyl) -5,5 ', 6,6'-tetramethyl-
2,2'-biphenol, 3,3'-diadamantyl-
Biphenols such as 5,5 ', 6,6'-tetramethyl-2,2'-biphenol;2,2'-biphenoxylithium,3,3'-dimethyl-2,2'-biphenoxysodium, , 3'-Diethyl-2,2'-biphenoxypotassium, 3,3'-di (iso-propyl)-
2,2'-biphenoxylithium, 3,3 ', 5,5'
Sodium tetra (t-butyl) -2,2′-biphenoxy, 3,3′-di (t-butyl) -5,5 ′, 6,
6'-tetramethyl-2,2'-biphenoxylithium, 3,3'-diadamantyl-5,5 ', 6,6'-
Potassium tetramethyl-2,2'-biphenoxy, 2,
2'-biphenoxy magnesium bromide, 3,3'-
Diethyl-2,2'-biphenoxymagnesium chloride, 3,3'-di (iso-propyl) -2,2'-biphenoxyaluminum dichloride, 3,3'-di (t
-Butyl) -2,2′-biphenoxymagnesium chloride, 3,3′-di (t-butyl) -5,5 ′, 6,
6'-tetramethyl-2,2'-biphenoxyaluminum dibromide, 3,3'-diadamantyl-5,
Biphenoxides such as 5 ′, 6,6′-tetramethyl-2,2′-biphenoxymagnesium bromide can be mentioned.

Further, there may also be mentioned, for example, binaphthols or binaphthoxides in which an aromatic ring is further bonded to biphenols or biphenoxides. Specific examples of these include 1,1′-binaphthyl-2,2′-diol, 3,3′-dimethyl-1,1′-binaphthyl-2,
2'-dioxylithium, 3,3'-diethyl-1,
1'-binaphthyl-2,2'-dioxypotassium, 3,
3′-di (iso-propyl) -1,1′-binaphthyl-2,2′-dioxymagnesium bromide, 3,3 ′
-Di (t-butyl) -1,1'-binaphthyl-2,2 '
-Diol, 3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxylithium, 3,3'-diadamantyl-1,1'-binaphthyl-2,2'-dioxyaluminum dichloride And the like.

Specific examples of the compound in which q in the general formula [2] is 1 include 2,2'-methylenebis (4-chlorophenol) and 2,2'-methylenebis (6-t-butyl-4-). Methylphenol), 2,2′-methylenebis (6-t-butyl-4-ethylphenol), 2,2 ′
-Methylenebis (3,4,6-trichlorophenol), 3,3'-di (t-butyl) -2,2'-dihydroxy-1,1'-diphenylether, 3,3'-di (t-butyl) -2,2'-dihydroxy-1,1'-
Examples thereof include diphenylthioether, 1,8-dihydroxyanthraquinone, and metal salts thereof.

Specific examples of naphthodiols represented by the general formula [7] include 1,8-naphthodiol, 2,7
-Diphenyl-1,8-naphthodiol, 2,7-dimethyl-1,8-naphthodiol, and 2,7-di (t-butyl) -1,8-naphthodiol.

The reactant (I) used in the present invention can be obtained by mixing the compound (a) with the compound (b). Reactant (III) is obtained by mixing compound (a) and compound (c). Compound (a),
The compound (b) or the compound (c) is usually mixed after being dissolved or dispersed in an organic solvent. The organic solvent used is not particularly limited as long as it dissolves or disperses the compound (a), the compound (b) or the compound (c) and does not affect the reaction.

Specific examples of such an organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; halogen-based aliphatic hydrocarbon solvents such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene; Halogenated aromatic hydrocarbon solvents such as dichlorobenzene; nitromethane, nitrobenzene,
Nitrogen-containing hydrocarbon solvents such as acetonitrile; ether solvents such as diethyl ether and tetrahydrofuran; aromatic ether solvents such as anisole and phenetole; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; cyclohexane; Alicyclic hydrocarbon solvents such as methylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, and cyclooctane can be used. Among these solvents, aromatic hydrocarbon-based solvents, halogen-based aromatic hydrocarbon-based solvents, ether-based solvents or aromatic ether-based solvents,
The compound (a), the compound (b) or the compound (c) is preferable because it has excellent solubility and little influence on the subsequent polymerization reaction or hydrogenation reaction. The concentration of compound (a), compound (b) or compound (c) in the solution containing compound (a), compound (b) or compound (c) can be arbitrarily selected.

The mixing is carried out in an atmosphere of a rare gas such as argon or a nitrogen gas, and the solution containing the compound (b) or (c) may be added to the solution containing the compound (a), or vice versa. Alternatively, both may be simultaneously added to another container and mixed. The molar ratio of the compound (b) or the compound (c) to the compound (a) is preferably 1 to 10 times, more preferably 1 to 8 times, and particularly preferably 1 to 5 times. When the ratio of the compound (b) or the compound (c) to the compound (a) is too small, unreacted compound (a) remains, which may inhibit polymerization. If it is too large, unreacted compound (b) or compound (c) affects the polymerization,
May cause side reactions. The reaction temperature is not particularly limited, but is generally between -100 ° C and 100 ° C.
If the temperature is too low, the progress of the reaction is too slow, and if it is too high, a side reaction may occur or the product may be decomposed.
A preferred range of the reaction temperature is -80C to 80C, and a more preferred range is -70C to 70C. It is preferable that the mixing is performed at a low temperature of 0 ° C. or less, and then the reaction is performed while gradually increasing the temperature to around room temperature. The reaction time is 1
There is no particular limitation as long as it is between minutes and one week.

The reaction product (I) or (III) is added to the reaction solution as it is or to an organic solvent in which (I) or (III) is insoluble (for example, a saturated hydrocarbon solvent such as pentane). To precipitate (I) or (III),
Alternatively, a solvent recovered by distilling off the solvent used for the reaction can be used as a polymerization catalyst.

The main component of the reactant (I) is a compound having an aromatic monooxy group having a substituent as a ligand.
It is a Group 6 transition metal compound. In particular, a bulky substituent on the carbon next to the carbon to which the oxy group is attached, for example, is
Those having a secondary alkyl group such as an o-propyl group, a tertiary alkyl group such as a t-butyl group, a phenyl group or a substituted phenyl group, or a haloalkyl group such as a trifluoromethyl group are highly stereoregular polymerization reactions. Can be performed, and a crystalline norbornene-based ring-opening polymer hydride can be obtained, which is preferable. Also, reactant (III)
Are transition metal compounds belonging to Groups 4 to 6 of the periodic table having an aromatic dioxy group as a ligand. By using an aromatic dioxy group, which is a bidentate ligand having high steric restraint, as a ligand, stereoregularity can be further enhanced, so that a highly crystalline norbornene-based ring-opened polymer and its hydride can be obtained. be able to.

The reaction product (I) or (III) can be isolated by the above separation method. When isolated, the structure of the obtained compound can be identified by ¹ H-NMR spectrum or elemental analysis.

The transition metal oxy compounds or halides (IV) of Groups 4 to 6 of the periodic table having an aromatic dioxy group as a ligand used in the present invention are the main components of the reactant (III). For example, the general formula [8] or [9]

General formula [8]:

Embedded image (Wherein, M represents the periodic table 4-6 transition metal atom, X is a halogen ^atom, R 22 ^{to R 2 9} are each independently a hydrogen atom,
A halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a haloalkyl group or a haloaryl group, or a cyano group, which may be bonded to each other to form a ring structure. Z is a general formula [3],
It is selected from general formula [4], general formula [5], general formula [6], oxygen atom and sulfur atom. Here, R ³⁰ and R ³¹ each independently represent a hydrogen atom or a hydrocarbon having 1 to 6 carbon atoms. m is 0 or 1, n is 0 to 4, p is 1 or 2, q is 0
And n + p + q is determined by the valence of the M element. )

General formula [9]:

Embedded image (Wherein, M represents the periodic table 4-6 transition metal atom, X is a halogen ^atom, R 32 ^{to R 3 7} each independently represent a hydrogen atom,
A halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a haloalkyl group or a haloaryl group, or a cyano group, which may be bonded to each other to form a ring structure. n is 0 to 4 and p is 1
Or, 2 and q are 0 to 2, and n + p + q is determined by the valence of the M element. ).

Among them, metal oxy compounds or halides whose central metal is Mo or W are most preferred from the viewpoint of polymerization activity. Specific examples of the metal complex include bis @ 3,
3'-di (t-butyl) -5,5 ', 6,6'-tetramethyl-2,2'-biphenoxydioxymolybdenum (VI), {3,3'-di (t-butyl) -5 , 5 ',
6,6′-tetramethyl-2,2′-biphenoxy {oxymolybdenum (VI) dichloride, bis {3,3′-
Diphenyl-1,1′-binaphthyl-2,2′-dioxy} oxymolybdenum (VI), {3,3′-diphenyl-1,1′-binaphthyl-2,2′-dioxy} oxymolybdenum (VI) dichloride , Bis {3,3'-di (t-butyl) -5,5 ', 6,6'-tetramethyl-
2,2'-biphenoxydioxytungsten (V
I), {3,3′-di (t-butyl) -5,5 ′, 6,
6'-tetramethyl-2,2'-biphenoxydioxytungsten (VI) dichloride, bis {3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxydioxytungsten (VI),} 3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxydioxytungsten (VI) dichloride, bis {3,3 '
-Di (t-butyl) -5,5 ', 6,6'-tetramethyl-2,2'-biphenoxytungsten (VI) dichloride, {3,3'-di (t-butyl) -5,5 ',
6,6'-tetramethyl-2,2'-biphenoxytungsten (VI) tetrachloride, bis {3,3'-
Diphenyl-1,1'-binaphthyl-2,2'-dioxy {tungsten (VI) dichloride, {3,3'-diphenyl-1,1'-binaphthyl-2,2'-dioxy} tungsten (VI) tetrachloride And the like.

These compounds are used in the Periodic Tables 4 to 6
It is obtained by reacting a halide, oxyhalide or dioxyhalide (a) of a group transition metal with an aromatic diol or an aromatic dioxide (c) and separating them. Regarding the reaction conditions and the like, the same method as that for producing the reactant (III) can be used.

In the present invention, the above reaction product (I)
Or (III), or a transition metal oxy compound or a halide (IV) of Groups 4 to 6 of the periodic table having an aromatic dioxy group as a ligand,
Combination with I) results in a highly active polymerization catalyst.

Examples of the organometallic reducing agent include organometallic compounds belonging to Groups 1, 2, 12, 13 and 14 of the periodic table having a hydrocarbon group having 1 to 20 carbon atoms. Of these, organolithium, organomagnesium, organozinc, organoaluminum or organotin is preferred, and organolithium, organoaluminum or organotin is particularly preferred. Examples of the organic lithium include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, neofillithium, and the like. Examples of the organic magnesium include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride, and neophylmagnesium chloride. Examples of the organic zinc include dimethyl zinc, diethyl zinc, diphenyl zinc and the like. Examples of the organic aluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, and ethylaluminum dichloride. Examples of the organotin include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.

The amount of the organometallic reducing agent depends on the center of the reactant (I) or (III) or the transition metal oxy compound or halide (IV) belonging to Group 4 to 6 of the periodic table having an aromatic dioxy group as a ligand. The molar ratio is 0.1 to the metal.
It is preferably 1 to 100 times, more preferably 0.2 to 50 times, and particularly preferably 0.5 to 20 times. When the amount is 0.1 or less, the polymerization activity is not improved, and when the amount is 100 or more,
Side reactions are likely to occur.

The monomer used in the production method of the present invention is a norbornene-based monomer, and specifically, has the general formula [10]

General formula [10]:

Embedded image(Where R³⁸~ R⁴¹Is a hydrogen atom, having 1 to 20 carbon atoms
Hydrocarbon group or halogen atom, silicon atom, oxygen atom
Or a substituent containing a nitrogen atom;³⁸And R ⁴¹But
They may combine to form a ring. r is an integer of 0 to 2
You. ) Wherein r is 0, and r is 0
In R³⁸And R⁴¹Binds to a ring structure other than the norbornene ring
Norbornene derivative having the structure
Clododecenes, hexacycloheptadece wherein r is 2
Can be mentioned. Above all, Norbornene
, Norbornene having a ring structure other than the norbornene ring
The derivative or tetracyclododecene is a crystalline polymer
Preferred because it is easy to obtain a hydride, norbornenes or
Norbornene derivatives having a ring structure other than the norbornene ring
The body is particularly preferred.

The norbornenes of the general formula [10] where r is 0 can be classified as follows according to the substituents of R ^{38 to} R ⁴¹ , and any monomer can be used. Specific examples of the norbornenes include unsubstituted or alkyl groups such as norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene. Norbornenes having an alkenyl group such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene and 5-cyclopentenyl norbornene; and aromatic rings such as 5-phenyl norbornene. Norbornenes having;

5-methoxycarbonylnorbornene, 5
-Ethoxycarbonylnorbornene, 5-methyl-5
Methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-
Methyl propionate, norbornenyl-2-methyloctaneate, norbornene-5,6-dicarboxylic anhydride, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5,5-di (hydroxymethyl) Norbornenes having a polar group containing an oxygen atom, such as norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene; 5-cyanonorbornene, norbornene-5 , 6
Norbornenes having a polar group containing a nitrogen atom such as dicarboxylic acid imide;

Among them, norbornenes having no substituent or a relatively small substituent are preferred because they exhibit high crystallinity. Specifically, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, norbornene-5,6
-Dicarboxylic anhydride, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene,
5,5-di (hydroxymethyl) norbornene, 5-cyanonorbornene, norbornene-5,6-dicarboxylic imide, and the like.

In the general formula [10], when r is 0, R ³⁸ and R
Examples of the norbornene derivative having a ring structure other than the norbornene ring to which ⁴¹ is bonded include dicyclopentadienes having a 5-membered ring structure, norbornene derivatives having an aromatic ring, and the like. Specific examples of the dicyclopentadiene compound, tricyclo saturated with double bonds of 5-membered ring portion of dicyclopentadiene or dicyclopentadiene [4.3.1 ^{2, 5.} 0] dec-3-ene, tricyclo [4.4.1 ^2,5 . 0] under-3-ene and the like. Examples of the norbornene derivative having an aromatic ring include tetracyclo [6.5.1.2 ^5,5 . 0
^1,6 . 0 ^8,13] trideca -3,8,10,12-
Tetraene (also referred to as 1,4-methano-1,4,4a, 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, 5,10,10a-hexahydroanthracene), and the like. The dicyclopentadiene and the norbornene derivative having an aromatic ring shown in the above specific examples are preferably used for obtaining a crystalline ring-opened polymer or a hydrogenated product thereof because it is composed of only a ring structure.

Specific examples of the tetracyclododecenes of the general formula [10] wherein r is 1 include tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, and 8-cyclohexyltetrade. Unsubstituted or alkyl-containing tetracyclododecenes such as cyclododecene and 8-cyclopentyltetracyclododecene; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, and 8-vinyltetracyclododecene , 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene and the like having a exocyclic double bond; 8-phenyltetracyclododecene; Tetracyclododecenes having an aromatic ring; Isobornyl tetracyclododecene, 8
-Methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-
Carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-
Tetracyclododecenes having a substituent containing an oxygen atom such as 8,9-dicarboxylic anhydride;

Tetracyclododecenes having a substituent containing a nitrogen atom, such as 8-cyanotetracyclododecene and tetracyclododecene-8,9-dicarboxylic imide;
Tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; tetracyclododecenes having a substituent containing a silicon atom such as 8-trimethoxysilyltetracyclododecene; No. Among them, tetracyclododecenes which are unsubstituted or have a relatively small substituent are preferred because they exhibit high crystallinity. Tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8
-Methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-hydroxymethyltetracyclododecene, tetracyclododecene-8,9-dicarboxylic anhydride, 8-
Cyanotetracyclododecene, tetracyclododecene-
8,9-dicarboxylic imide, 8-chlorotetracyclododecene, and the like.

Specific examples of hexacycloheptadecenes of the general formula [10] wherein r is 2 include hexacycloheptadecene, 12-methylhexacycloheptadecene,
Hexacycloheptadecenes having an unsubstituted or alkyl group, such as 2-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene; 12-methylidenehexacycloheptadecene, 12-ethylidene Hexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12-cyclopentenylhexacycloheptadecene, etc. Heptadecenes; hexacycloheptadecenes having an aromatic ring such as 12-phenylhexacycloheptadecene;

12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12,13
Dicarboxylic acid, hexacycloheptadecene 12,13
Hexacycloheptadecenes having a substituent containing an oxygen atom such as dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,
Hexacycloheptadecenes having a substituent containing a nitrogen atom such as 13-dicarboxylic imide; hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; 12-trimethoxysilylhexa Hexacycloheptadecenes having a substituent containing a silicon atom, such as cycloheptadecene, and the like.

The above monomers include endo- and exo-isomers. The monomer used in the present invention may be a mixture of these isomers, but in order to further improve the crystallinity, the higher the composition ratio of any isomer component in the isomer mixture, the better. preferable. In particular,
It is preferable that any of the isomers is usually 70% or more, particularly 80% or more.

In the present invention, other copolymerizable monomers other than the norbornene-based monomer may be copolymerized with the norbornene-based monomer. Examples of other copolymerizable monomers include cyclic olefins other than norbornene-based monomers. Examples of the cyclic olefin other than the norbornene-based monomer include a C _{4 to} C ₂₀ monocyclic cyclic olefin or diolefin and a substituted or derivative thereof. Specific examples of the monocyclic olefins or diolefins include monocyclic cycloolefins such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene and cyclooctene described in JP-A-64-66216. Cyclic olefinic monomers; cyclohexadiene, methylcyclohexadiene, cyclooctadiene,
Examples thereof include cyclic diolefin monomers such as methylcyclooctadiene and phenylcyclooctadiene described in JP-A-7-258318.

In the present invention, the polymerization reaction can be carried out without a solvent. However, when a hydrogenation reaction is carried out after the polymerization, the polymerization is preferably carried out in an organic solvent. The organic solvent used in the present invention is not particularly limited as long as the polymer and the polymer hydride dissolve or disperse under predetermined conditions and do not affect polymerization and hydrogenation.

Specific examples of such an organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene , Bicycloheptane, tricyclodecane, hexahydroindenecyclohexane,
Alicyclic hydrocarbon solvents such as cyclooctane; Aromatic hydrocarbon solvents such as benzene, toluene and xylene;
Halogenated aliphatic hydrocarbon solvents such as dichloromethane, chloroform and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene; Nitrogen-containing hydrocarbon solvents such as nitromethane, nitrobenzene and acetonitrile; Ether solvents such as ter and tetrahydrofuran;
Aromatic ether solvents such as anisole and phenetole can be used. Among these solvents,
Aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents or aromatic ether solvents are preferred.

(Polymerization method) The ratio of the polymerization catalyst to the monomer in the method of the present invention is from 1: 100 to 1: 2,000,000 in a molar ratio (transition metal in the polymerization catalyst: monomer).
0, preferably 1: 200 to 1,000,000, more preferably 1: 500 to 1: 500,000. If the amount of the catalyst is too large, removal of the catalyst becomes difficult, and if the amount is too small, sufficient polymerization activity may not be obtained. When the polymerization is carried out in a solvent, the concentration of the monomer is preferably 1 to 50% by weight, more preferably 2 to 45% by weight, and particularly preferably 3 to 40% by weight. When the concentration of the monomer is 1% by weight or less, productivity is poor, and when the concentration is 50% by weight or more, the solution viscosity after polymerization is too high, and the subsequent hydrogenation reaction may be difficult.

The polymerization reaction is started by mixing a monomer and a polymerization catalyst. The polymerization temperature is not particularly limited.
Generally, -30 ° C to 200 ° C, preferably 0 ° C to 18 ° C.
0 ° C. The polymerization time can be appropriately selected so as to obtain a desired molecular weight and a polymerization conversion, and is usually 1 minute to 100 hours.

Further, a method for adjusting the molecular weight of the obtained ring-opened polymer can be carried out by adding an appropriate amount of a vinyl compound or a diene compound. The vinyl compound used for adjusting the molecular weight is not particularly limited as long as it is an organic compound having a vinyl group, and α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrene, vinyltoluene and the like Styrenes;
Ethers such as ethyl vinyl ether, i-butyl vinyl ether and allyl glycidyl ether; halogen-containing vinyl compounds such as allyl chloride; allyl acetate;
Examples thereof include oxygen-containing vinyl compounds such as allyl alcohol and glycidyl methacrylate, and nitrogen-containing vinyl compounds such as acrylamide. Diene compounds are
1,4-pentadiene, 1,4-hexadiene, 1,5
-Hexadiene, 1,6-heptadiene, 2-methyl-
Non-conjugated dienes such as 1,4-pentadiene and 2,5-dimethyl-1,5-hexadiene, or 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3- Butadiene, 1,3-pentadiene, 1,
Conjugated dienes such as 3-hexadiene can be mentioned. The amount of the vinyl compound or diene compound to be added is 0.1 to 10% by mol based on the desired molecular weight, based on the monomer.
Can be selected arbitrarily.

(Hydrogenation reaction) The hydrogenation reaction is carried out by supplying hydrogen into the reaction system in the presence of a hydrogenation catalyst. The hydrogenation catalyst can be used as long as it is generally used in hydrogenating an olefin compound, and is not particularly limited. Examples thereof include the following.

As the homogeneous catalyst, a catalyst system comprising a combination of a transition metal compound and an alkali metal compound, for example, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum,
Examples include combinations of titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, and the like. Further, noble metal complex catalysts such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium and chlorotris (triphenylphosphine) rhodium can be mentioned.

Examples of the heterogeneous catalyst include metals such as nickel, palladium, platinum, rhodium and ruthenium, or those metals such as carbon, silica, diatomaceous earth, alumina,
Solid catalyst supported on a carrier such as titanium oxide, for example,
Nickel / silica, nickel / diatomaceous earth, nickel /
Examples include catalyst systems such as alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina.

The hydrogenation reaction is usually performed in an inert organic solvent. Such inert organic solvents include benzene,
Aromatic hydrocarbon solvents such as toluene; n-pentane;
aliphatic hydrocarbon solvents such as n-hexane; alicyclic hydrocarbon solvents such as cyclohexane and decalin; ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether. The inert organic solvent is
It may be the same as the polymerization reaction solvent. In that case, a hydrogenation catalyst is added to the polymerization reaction solution as it is to cause a reaction.

The hydrogenation reaction depends on the hydrogenation catalyst system used.
Although the suitable condition range is different, the hydrogenation temperature is usually −
20 to 250 ° C, preferably -10 to 220 ° C, more preferably
Preferably, it is 0-200 ° C., and the hydrogen pressure is usually 0.1
~ 50kgf / cm², Preferably 0.5 to 40 kgf
/ Cm², More preferably 1.0 to 30 kgf / cm ²
It is. If the hydrogenation temperature is too low, the reaction rate will be slow and high.
When it breaks, a side reaction occurs. If the hydrogen pressure is too low,
If the oxidation rate is too slow, a high pressure reactor is required
Becomes

The hydrogenation ratio is usually at least 50%, preferably at least 70%, more preferably at least 80%, particularly preferably at least 90%. Rate can be achieved.

(Crystalline norbornene-based ring-opening polymer and crystalline norbornene-based ring-opened polymer hydride) By the production method of the present invention, a crystalline norbornene-based ring-opened polymer and a hydrogenated ring-opened polymer thereof are obtained. The crystalline norbornene ring-opening polymer and the hydrogenated ring-opening polymer have a melting point. The melting point is usually in the range from 100 to 400C.

[0061]

The present invention will be described more specifically below with reference to examples and comparative examples. (1) The molecular weight of the ring-opened (co) polymer was measured in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent. (2) The hydrogenation rate was measured by an infrared absorption spectrum. (3) Melting point (Tm) and glass transition temperature (Tg) were measured with a differential scanning calorimeter at a rate of 10 ° C./min.

Example 1 In a glass reactor equipped with a stirrer,
1.5 parts of molybdenum oxytetrachloride (MoOCl ₄ ) and 30 parts of diethyl ether were added and the mixture was cooled to -78 ° C. Further, 3,3′-di (t-butyl) -5,5 ′,
A solution in which 4.19 parts of 6,6′-tetramethyl-2,2′-biphenoxylithium was dissolved in 30 parts of diethyl ether was added. The mixture is gradually brought to room temperature and
A time reaction was performed. After the reaction, the precipitate was separated by filtration through Celite, and the solution portion was dried under reduced pressure. This was cooled to −30 ° C. and allowed to stand to obtain a solid A. The yield of the resulting solid was 2.56 parts. ¹ of this solid A H-
The NMR spectrum was as follows. _{^{1 H-NMR (benzene-d}} 6) d 7.24
(S, 1, H _aryl ), 7.19 (s, 1, H
_{aryl), 2.13 (s, 3} , CH 3), 2.03
_{(S, 3, CH 3)} , 1.68 (s, 3, CH 3),
_{1.67 (s, 3, CH 3} ), 1.52 (s, 9, t-
Bu), 1.45 (s, 9, t-Bu). The results of elemental analysis of this solid A were as follows. Molybdenum 10.9 (wt%), carbon 70.6
(Wt%), hydrogen 8.6 (wt%), chlorine <0.1
(Wt%), others 9.9 (wt%). The other 9.9 (wt%) is considered to be the contribution of oxygen that could not be measured. The composition of these elements is bis {3,3′-di (t-butyl) -5,5 ′, 6,6′-
Elemental composition of tetramethyl-2,2'-biphenoxydioxymolybdenum (VI) (molybdenum 11.7 (wt.
%), Carbon 70.6 (wt%), hydrogen 7.9 (wt)
%) And oxygen 9.8 (wt%). The reason for the difference between the theoretical value and the measured value is considered to be the contribution of the remaining diethyl ether. From the above results, the structure of the solid A was determined to be bis {3,3′-di (t-butyl)-
It is estimated to be 5,5 ', 6,6'-tetramethyl-2,2'-biphenoxydioxymolybdenum (VI) (general formula [11]).

General formula [11]:

Embedded image

Example 2 In a glass reactor equipped with a stirrer,
0.092 parts of solid A synthesized in Example 1 and toluene 4
After the addition of parts, it was cooled to -78 ° C. And n
A solution prepared by dissolving 0.0145 parts of -butyllithium in 1 part of hexane was added, and the mixture was returned to room temperature and reacted for 1 hour. To the obtained mixture, 7.5 parts of dicyclopentadiene (DCPD), 27 parts of toluene, and 0.1 part of 1-hexene were added, and a polymerization reaction was performed at 80 ° C. After the initiation of the polymerization reaction, a white precipitate was immediately deposited. After the reaction for 2 hours, a large amount of methanol was poured into the polymerization reaction solution to coagulate the precipitate, which was separated by filtration, washed, and dried under reduced pressure at 40 ° C for 24 hours. The yield of the obtained ring-opened polymer was 7.4 parts, and the molecular weight (in terms of polystyrene) was such that the number average molecular weight (Mn) was 8,000 and the weight average molecular weight (Mw) was 1
It was 5,000. The melting point (Tm) was 245 ° C.

(Example 3) Into an autoclave equipped with a stirrer, 3.0 parts of the ring-opening polymer obtained in Example 2 and 47 parts of cyclohexane were added. Next, a solution prepared by dissolving 0.0187 part of bis (tricyclohexylphosphine) benzylidine ruthenium (IV) dichloride and 0.45 part of ethyl vinyl ether in 10 parts of cyclohexane was added to the autoclave, and a hydrogen pressure of 8 kgf / cm ² , 17
The hydrogenation reaction was performed at 5 ° C. for 8 hours. After the hydrogenation reaction, the reaction solution was poured into a large amount of isopropanol to completely precipitate the product, washed by filtration, and dried under reduced pressure at 40 ° C. for 24 hours. The hydrogenation rate of the obtained ring-opened polymer hydride is as follows:
The result of the infrared absorption spectrum was 99% or more.
In addition, Tm was 275 ° C.

Example 4 In a glass reactor equipped with a stirrer,
3,3′-di (t-butyl) -5,5 ′, 6,6′-tetramethyl-2,2′-biphenol (BMBP)
425 parts, toluene 5 parts and tetrahydrofuran (TH
F) 5 parts were added and this was cooled to -78 ° C. Further, a solution obtained by dissolving 0.231 part of n-butyllithium in 1.5 parts of n-hexane was added, and the temperature was gradually returned to room temperature to obtain a reaction solution A. In a glass reactor with a stirrer different from the above, 0.1 g of molybdenum oxytetrachloride (MoOCl ₄ ) was added.
52 parts, 10 parts of toluene and 10 parts of tetrahydrofuran were added, and this was cooled to -78 ° C. The whole amount of the reaction solution A was added to this solution, 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. The solution was cooled to −78 ° C., and a solution prepared by dissolving 0.151 part of n-butyllithium in 0.75 part of n-hexane was added to the solution, and the temperature was gradually returned to room temperature to obtain a catalyst solution B. 24 parts of dicyclopentadiene, 96 parts of toluene, 1
-Catalyst solution B was added to a glass reactor equipped with a stirrer to which 0.3 part of hexene was added, and a polymerization reaction was performed at 80 ° C for 2 hours. After the initiation of the polymerization reaction, a white precipitate was immediately deposited. A large amount of methanol was poured into the obtained polymerization reaction solution to coagulate the precipitate. The reaction solution containing the precipitate was separated by filtration, washed, and dried under reduced pressure at 40 ° C. for 24 hours. The yield of the obtained ring-opened polymer was 23.5 parts, and Tm was 245 ° C.

Example 5 A catalyst was prepared and a polymerization reaction was carried out in the same manner as in Example 4 except that tungsten hexachloride was used instead of molybdenum oxytetrachloride. The yield of the obtained ring-opened polymer was 23.5 parts, and Tm was 245 ° C.

Example 6 A catalyst was prepared and a polymerization reaction was carried out in the same manner as in Example 4 except that dioxydichloromolybdenum was used instead of molybdenum oxytetrachloride. The yield of the obtained ring-opened polymer was 15.6 parts, and Tm was 245 ° C.

Example 7 A catalyst was prepared and a polymerization reaction was carried out in the same manner as in Example 7 except that norbornene (NBE) was used instead of dicyclopentadiene. The yield of the obtained ring-opened polymer was 23.5 parts, and Tm was 105 ° C.

Example 8 To an autoclave equipped with a stirrer, 3 parts of the ring-opened polymer obtained in Example 4 and 47 parts of cyclohexane were added. Next, a hydrogenation catalyst solution in which 0.04 part of nickel acetate and 0.18 part of triisobutylaluminum were dissolved in 10 parts of cyclohexane was added, and a hydrogen pressure of 1% was added.
The hydrogenation reaction was performed at 0 kgf / cm ² and 160 ° C. for 8 hours. The hydrogenation reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, and the polymer was separated by filtration and washed.
It dried under reduced pressure for 4 hours. The hydrogenation rate of the obtained hydrogenated ring-opened polymer was 99% or more based on the result of infrared absorption spectrum. Further, Tm was 275 ° C.

(Examples 9 to 11) Using the polymers obtained in Examples 5 to 8, a hydrogenation reaction was carried out in the same manner as in Example 8. Table 1 shows the results.

Example 12 3'-Di (t-butyl)-
Catalyst in the same manner as in Example 4 except that 2,6-di (t-butyl) -4-methylphenol (BHT) was used instead of 5,5 ', 6,6'-tetramethyl-22'-biphenol Preparation and polymerization were carried out, and hydrogenation was carried out as in Example 8. Table 1 shows the results.

Comparative Example 1 3,3′-di (t-butyl)
Example 1 except that phenol was used instead of -5,5 ', 6,6'-tetramethyl-2,2'-biphenol.
Preparation of a catalyst and polymerization reaction were carried out in the same manner as described above. After the completion of the polymerization reaction, the reaction solution remained uniform. A glass transition temperature (Tg) was observed around 125 ° C., but Tm was not observed.

Comparative Example 2 Using the polymer obtained in Comparative Example 1, a hydrogenation reaction was carried out in the same manner as in Example 8. After the completion of the hydrogenation reaction, the reaction solution remained homogeneous. 95 ° C
Tg was observed in the vicinity, but Tm was not observed.

[0075]

[Table 1]

As described above, according to Examples and Comparative Examples, the reactant (III) or the compound (IV) and the organometallic reducing agent (I
The ring-opening polymerization of the norbornene-based monomer using the polymerization catalyst comprising I), and hydrogenation as necessary,
The reaction product (I) and the organometallic reducing agent (I) are obtained in a high yield of a polymer or hydride having a melting point, that is, having crystallinity.
It can be seen that a polymer or hydride having a melting point, that is, having crystallinity, can be obtained in a high yield by ring-opening polymerization and hydrogenating a norbornene-based monomer using the polymerization catalyst comprising I). .

[0077]

According to the present invention, a polymerization catalyst for providing a crystalline norbornene-based ring-opening polymer and a hydrogenated crystalline norbornene-based ring-opening polymer, a crystalline norbornene-based ring-opening polymer using the polymerization catalyst, A method for producing the hydrogenated ring-opened polymer is provided.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4H006 AB40 AB49 FC52 FE13 FE19 4J032 CA23 CA24 CA27 CA28 CA34 CA35 CA36 CA62 CA63 CA68 CB01 CB03 CC03 CD02 CD03 CD04 CD05 CD09 CE03 CE05 CE22 CE24 CF03

Claims (6)

[Claims] 1. A method of converting a halide, oxyhalide or dioxyhalide (a) of a transition metal belonging to Groups 4 to 6 of the periodic table with an aromatic monool or an aromatic monooxide (b) having a substituent. After ring-opening metathesis polymerization of a norbornene-based monomer in the presence of a polymerization catalyst comprising a reactant (I) and an organometallic reducing agent (II), the carbon present in the main chain of the obtained polymer is obtained. -A method for producing a hydrogenated crystalline norbornene-based ring-opening polymer in which 50% or more of carbon double bonds are hydrogenated in the presence of a hydrogenation catalyst. 2. A reaction product (III) of a halide, oxyhalide or dioxyhalide (a) of a transition metal belonging to Groups 4 to 6 of the periodic table with an aromatic diol or an aromatic dioxide (c). , An organometallic reducing agent (I
A method for producing a crystalline norbornene-based ring-opened polymer, comprising subjecting a norbornene-based monomer to ring-opening metathesis polymerization in the presence of a polymerization catalyst comprising I). 3. Norbornene in the presence of a polymerization catalyst comprising an oxy- or halide (IV) of a transition metal belonging to Groups 4 to 6 of the periodic table having an aromatic dioxy group as a ligand and an organometallic reducing agent (II). A method for producing a crystalline norbornene-based ring-opening polymer, comprising subjecting a monomer-based monomer to ring-opening metathesis polymerization. 4. The method according to claim 2, wherein at least 50% of carbon-carbon double bonds present in the main chain of the crystalline norbornene-based ring-opened polymer obtained by the method according to claim 2 are hydrogenated in the presence of a hydrogenation catalyst. A method for producing a crystalline norbornene-based ring-opening polymer hydride. 5. A polymerization catalyst containing a transition metal oxy compound or a halide (IV) of Groups 4 to 6 of the periodic table having an aromatic dioxy group as a ligand. 6. The reaction of a halide, oxyhalide or dioxyhalide (a) of a transition metal belonging to Groups 4 to 6 of the periodic table with an aromatic diol or an aromatic dioxide (c). A method for producing a polymerization catalyst containing the oxy compound or the halide (IV) described above.