JP5864966B2 - Method for producing norbornene polymer - Google Patents

Description

  The present invention relates to a method for producing a (co) polymer of a norbornene monomer by precipitation polymerization.

  Conventionally, a cyclic olefin addition polymer typified by a norbornene polymer has been industrially used as an organic material having excellent heat resistance and transparency in the fields of optical films and the like. It has been reported variously that such a cyclic olefin addition polymer can be produced by addition polymerization of a cyclic olefin monomer using a catalyst containing a transition metal compound such as Ti, Zr, Cr, Co, Ni, and Pd. .

  However, most of them are specialized in improving the performance of catalysts, and as a polymerization method, so-called solution polymerization is the mainstream, and reports focusing on simplification of production processes and reduction of production costs have been reported. Very few.

  In general, in the solution polymerization, the polymerization reaction proceeds while the produced polymer is dissolved in a solvent. Therefore, in order to take out the polymer in a solid state after the polymerization is completed, the solvent is volatilized or the polymer solution is stored in a large amount of polymer poor solvent. In addition to the precipitation of the polymer, it is necessary to separate it from the solvent. In these methods, in addition to the increase in the number of steps, a large amount of energy and a large amount of solvent are required, and there is a problem that the manufacturing cost increases due to the cost for recycling the solvent and the energy cost.

  Furthermore, since the polymerization reaction proceeds while the produced polymer is dissolved in the solvent in the solution polymerization, the viscosity of the solution increases remarkably when the amount of polymer production increases, and stirring becomes impossible. Not only is the control difficult, but there is a disadvantage that the polymer production amount per unit volume does not increase.

  As described above, solution polymerization has problems such as complicated polymer separation process, difficulty in controlling reaction temperature, and low productivity. Therefore, even if a high-performance catalyst is used, the polymer is industrially produced. Had the problem of not being suitable.

  Precipitation polymerization is known as a method for producing a polymer that can solve these problems. In precipitation polymerization, the monomer dissolves, but the polymer that is produced can be precipitated during the polymerization by using a poor solvent as the reaction solvent, preventing an increase in the viscosity of the reaction solution. . As a result, there are advantages that both the reaction temperature control and the productivity improvement can be achieved, and the separation of the polymer is easy. However, there are very few examples of using precipitation polymerization as a method for producing a cyclic olefin polymer.

  For example, International Publication No. 08/069568 (Patent Document 1) describes a method of producing a cyclic olefin polymer by precipitation polymerization using n-hexane, cyclohexane and heptane as an antisolvent (poor solvent for polymer). Application is disclosed. However, when producing a cyclic olefin polymer or copolymer having a polar group using these solvents, the produced polymer precipitates, but the surface of the precipitated polymer becomes sticky, and the polymer is reacted in the reactor. As the polymerization progresses as it adheres to the wall, there is a problem that it eventually becomes a large lump and stirring becomes difficult.

  Thus, in the method for producing a norbornene-based addition (co) polymer having a polar group, high polymer production per unit volume can be realized by precipitating the polymer to be produced during the polymerization, and the precipitated polymer surface is sticky. However, there is no example of an excellent precipitation polymerization method in which the reaction temperature can be controlled and the polymer can be easily separated after completion of the reaction. Therefore, development of such a precipitation polymerization method has been desired.

International Publication No. 08/069568 Pamphlet

  The subject of this invention is providing the efficient manufacturing method of the high molecular weight addition (co) polymer of the norbornene-type monomer which has a polar group.

  As a result of intensive studies to solve the above problems, the present inventors have found that when an aliphatic acetate is used in place of n-hexane, which is a conventionally known precipitation polymerization solvent, the produced polymer is powdered. And the subsequent separation of the polymer from the solvent (e.g., filtration) is facilitated, which significantly improves productivity and efficiently produces a high molecular weight addition copolymer of a norbornene monomer having a polar group. The present invention has been completed by finding out what can be done.

及び一般式（３）

（式中、Ｒ¹²は炭素数１〜１０のアルキル基を表し、Ｒ¹³、Ｒ¹⁴、及びＲ¹⁵はそれぞれ独立して水素原子または炭素数１〜１０のアルキル基を表す。）
で示されるモノマーユニットを含む前項［１］に記載のノルボルネン系共重合体の製造方法。
［３］一般式（２）及び一般式（３）で示されるモノマーユニットのみからなる前項［２］に記載のノルボルネン系共重合体の製造方法。
［４］沈殿重合の溶媒に含まれる脂肪族カルボン酸エステルが６０容量％以上である前項［１］〜［３］のいずれかに記載のノルボルネン系共重合体の製造方法。
［５］前記脂肪族カルボン酸エステルが炭素数１〜５の脂肪族カルボン酸とアルコールとのエステルである前項［１］〜［４］のいずれかに記載のノルボルネン系共重合体の製造方法。
［６］前記脂肪族カルボン酸エステルが脂肪族カルボン酸と炭素数１〜５のアルコールとのエステルである前項［１］〜［４］のいずれかに記載のノルボルネン系共重合体の製造方法。
［７］前記脂肪族カルボン酸エステルが、酢酸エチル、酢酸ｎ−プロピル、酢酸イソプロピル、酢酸ｎ−ブチルの少なくとも一種である前項［１］〜［４］のいずれかに記載のノルボルネン系共重合体の製造方法。
［８］前記沈殿重合の溶媒がトルエンと６０容量％以上の酢酸エチルを含む前項［１］〜［３］のいずれかに記載のノルボルネン系共重合体の製造方法。 That is, this invention relates to the manufacturing method of the norbornene-type copolymer of the following [1]-[8].
[1] A method for producing a norbornene (co) polymer by precipitation polymerization using a liquid that dissolves a norbornene monomer and does not dissolve a polymer of the monomer as a solvent, wherein the solvent for the precipitation polymerization is an aliphatic carboxyl A process for producing a norbornene-based (co) polymer comprising an acid ester.
[2] The norbornene-based (co) polymer has the general formula (2)

And general formula (3)

(In the formula, R ¹² represents an alkyl group having 1 to 10 carbon atoms, and R ¹³ , R ¹⁴ , and R ¹⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The manufacturing method of the norbornene-type copolymer of the preceding clause [1] containing the monomer unit shown by these.
[3] The method for producing a norbornene copolymer according to [2] above, which is composed only of the monomer units represented by the general formula (2) and the general formula (3).
[4] The method for producing a norbornene copolymer according to any one of [1] to [3], wherein the aliphatic carboxylic acid ester contained in the solvent for precipitation polymerization is 60% by volume or more.
[5] The method for producing a norbornene copolymer according to any one of [1] to [4], wherein the aliphatic carboxylic acid ester is an ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms and an alcohol.
[6] The method for producing a norbornene copolymer according to any one of [1] to [4], wherein the aliphatic carboxylic acid ester is an ester of an aliphatic carboxylic acid and an alcohol having 1 to 5 carbon atoms.
[7] The norbornene copolymer according to any one of [1] to [4], wherein the aliphatic carboxylic acid ester is at least one of ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate. Manufacturing method.
[8] The process for producing a norbornene copolymer according to any one of [1] to [3] above, wherein the solvent for precipitation polymerization contains toluene and 60% by volume or more of ethyl acetate.

  According to the present invention, a high molecular weight addition copolymer of norbornene and a norbornene monomer having a polar group can be produced efficiently. The norbornene-based copolymer obtained by the present invention has excellent transparency, heat resistance, low water absorption, electrical insulation properties, etc., and has many applications such as optical use, medical use, electric material use, packaging material use, structural material use, etc. It can be used for various purposes.

  Specifically, optical molded products such as lenses and polarizing films, films, carrier tapes, film capacitors, electrical insulating materials such as flexible printed circuit boards, press-through packages, infusion bags, medical containers such as liquid vials, wraps, It can be used for food packaging molded products such as trays, casings for electrical appliances, automobile interior parts such as inner panels, and building materials such as carports and glazings.

Hereinafter, the present invention will be described in more detail.
[Catalyst for polymerization of norbornene monomer]
There is no particular limitation on the norbornene-based monomer polymerization catalyst that can be used in the present invention. Precipitation polymerization does not depend on the type of catalyst because it depends on the combination of the monomer, the polymer to be formed, and the polymerization solvent. However, it is necessary to select a catalyst and polymerization conditions that are not poisoned by the solvent for precipitation polymerization. A composition containing a complex having palladium (Pd) or nickel (Ni) as a central metal as an essential component can be used as a catalyst.

  The norbornene-based monomer polymerization catalyst that can be used in the present invention includes, for example, a transition metal complex having Pd or Ni as a central metal as an essential component, and can react with the transition metal complex to generate a cationic transition metal compound. An essential component is a catalyst containing a compound promoter (hereinafter sometimes abbreviated as “promoter”) and a phosphine-based ligand as an optional component, or a transition metal complex having Pd or Ni as a central metal. And a catalyst containing an organoaluminum compound and a tertiary or quaternary boron compound as optional components.

A specific example of a transition metal complex in a catalyst containing a transition metal complex having Pd or Ni as a central metal that can be used in the present invention as an essential component and a cocatalyst and a phosphine ligand as optional components is bis (acetylacetate). Nato) palladium, (π-allyl) palladium chloride dimer, cyclopentadienyl (π-allyl) palladium, methylcyclopentadienyl (π-allyl) palladium, pentamethylcyclopentadienyl (π-allyl) palladium, indenyl (Π-allyl) palladium, fluorenyl (π-allyl) palladium, di (π-allyl) bis [μ- (N, N′-diphenylbenzamidinato) -N: N ′] dipalladium, di (π- Allyl) bis {μ- [N, N′-bis (2-methylphenyl) benzamidinate] -N: N ′} dipalladium Di (π-allyl) bis {μ- [N, N′-bis (2-isopropylphenyl) benzamidinate] -N: N ′} dipalladium, di (π-allyl) bis {μ- [N, N′-bis (2,6-diisopropylphenyl) benzamidinate] -N: N ′} dipalladium, di (π-allyl) bis {μ- [N, N′-dicyclohexylbenzamidinate] -N : N ′} dipalladium, di (π-allyl) bis {μ- [N, N′-diisopropylbenzamidinate] -N: N ′} dipalladium, di (π-allyl) bis [μ- (N , N′-diphenylacetamidinate) -N: N ′] dipalladium, (π-allyl) {4- (2,6-diisopropylphenylimino) -2-pentene-2-olato-κ ² N, O } Palladium, (π-allyl) {4- (1-naphthylimino)- - penten-2 Orato-kappa ² N, O} palladium, cyclopentadienyl (methyl) (triphenylphosphine) nickel, methylcyclopentadienyl (methyl) (triphenylphosphine) nickel, pentamethylcyclopentadienyl (Methyl) (triphenylphosphine) nickel, indenyl (methyl) (triphenylphosphine) nickel, fluorenyl (methyl) (triphenylphosphine) nickel, cyclopentadienyl (methyl) (tricyclohexylphosphine) nickel, pentamethylcyclo Pentadienyl (methyl) (tricyclohexylphosphine) nickel, indenyl (methyl) (tricyclohexylphosphine) nickel, fluorenyl (methyl) (tricyclohexylphosphine) nickel, bisui Denirunikkeru, bis (acetylacetonato) and nickel.

  Specific examples of the cocatalyst and phosphine ligand to be combined with this transition metal complex include those similar to the cocatalyst (B) and phosphine ligand (C) in the detailed description of the catalyst described later. Can do.

  Specific examples of the transition metal complex in a catalyst containing a transition metal complex having Pd or Ni as a central metal that can be used in the present invention as an essential component and an organoaluminum compound and a tertiary or quaternary boron compound as optional components include cyclohexane Pentadienyl (methyl) (triphenylphosphine) nickel, methylcyclopentadienyl (methyl) (triphenylphosphine) nickel, pentamethylcyclopentadienyl (methyl) (triphenylphosphine) nickel, indenyl (methyl) (tri Phenylphosphine) nickel, fluorenyl (methyl) (triphenylphosphine) nickel, cyclopentadienyl (methyl) (tricyclohexylphosphine) nickel, pentamethylcyclopentadienyl (methyl) (tricyclohexylphosphine) Icel, indenyl (methyl) (tricyclohexylphosphine) nickel, fluorenyl (methyl) (tricyclohexylphosphine) nickel, bisindenyl nickel, bis (acetylacetonato) nickel, cyclopentadienyl (π-allyl) palladium, methyl Cyclopentadienyl (π-allyl) palladium, pentamethylcyclopentadienyl (π-allyl) palladium, indenyl (π-allyl) palladium, fluorenyl (π-allyl) palladium, (π-allyl) palladium chloride dimer, bis (Acetyl acetonato) palladium etc. are mentioned. Among these, bisindenyl nickel and bis (acetylacetonato) nickel are preferable.

  Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexyl. Aluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohydride hydride Xyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum di Idoraido, include iso-heptyl aluminum dihydride and the like, among these, trimethylaluminum, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated di-iso-heptyl aluminum preferred. These organoaluminum compounds can be used singly or in combination of two or more.

  Specific examples of the tertiary or quaternary boron compound include tris (pentafluorophenyl) boron, trityltetrakis (pentafluorophenyl) borate, N, N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate and the like. it can.

  In the method for producing a norbornene (co) polymer by precipitation polymerization of the present invention, it is preferable to use the following polymerization catalyst. In the following description, this catalyst will be described as an example, but the polymerization method of the present invention can be applied to other catalyst systems as described above.

  The norbornene-based monomer polymerization catalyst preferably used in the method of the present invention is an ionic compound having a transition metal complex (A) as an essential component and capable of producing a cationic transition metal compound by reacting with the transition metal complex (A). It contains a certain promoter (B) (hereinafter sometimes abbreviated as “promoter (B)”) and a phosphine-based ligand (C) as optional components.

Transition metal complex (A):
The transition metal complex (A) as an essential component is a 1991 periodic table Group 8 element, Group 9 element, and Group 10 transition metal having a π-allyl ligand, and salicyl which is a bidentate ligand. It consists of aldimine.

で示される。 The transition metal complex (A) has the general formula (1)

Indicated by

  M in the general formula (1) represents one transition metal selected from Group 8 elements, Group 9 elements, and Group 10 elements of the 1991 periodic table. Specific examples include iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), and the like. Of these, cobalt, nickel, palladium and platinum are preferable elements from the viewpoint of the stability of the complex and the ease of synthesis, and nickel or palladium is more preferable.

R ¹ , R ² , R ³ and R ⁴ in the general formula (1) are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a halogen atom or an alkoxy group. An aryloxy group, a silyl group having a hydrocarbon group having 1 to 20 carbon atoms, a siloxy group having a hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a cyano group, an amide having a hydrocarbon group having 1 to 10 carbon atoms Or a dialkylamino group having an alkyl group having 1 to 10 carbon atoms, R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a ring structure.

  Specific examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an isobutyl group. , An octyl group, a 2-ethylhexyl group, a 2-methoxyethyl group or the like, an alkyl group having a linear or branched chain having 1 to 20 carbon atoms; a cyclopentyl group, a cyclohexyl group, a 3-methoxycyclohexyl group, a 4-methylcyclohexyl group Cycloalkyl group having 3 to 20 carbon atoms such as adamantyl group; aryl group having 6 to 20 carbon atoms such as phenyl group, naphthyl group, anthracenyl group, tolyl group, xylyl group, benzyl group and 4-fluorophenyl group, alkyl An aryl group or an aralkyl group is mentioned. Examples of the halogen atom include a chlorine atom and a fluorine atom. As an alkoxy group, a C1-C20 alkoxy group is preferable, and a methoxy group, an ethoxy group, an isopropoxy group, a sec-butoxy group etc. are mentioned specifically ,. Examples of the aryloxy group include a phenoxy group and a benzyloxy group. Examples of the silyl group having a hydrocarbon group having 1 to 20 carbon atoms include a trioxysilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group and the like having a hydrocarbon group having 1 to 20 carbon atoms. Examples of the group include a trimethylsiloxy group and a triethylsiloxy group. In addition, a nitro group, a cyano group, an amide group having a hydrocarbon group having 1 to 10 carbon atoms, a dialkylamino group having an alkyl group having 1 to 10 carbon atoms, and the like can be given. Among these, from the viewpoint of ease of synthesis of the complex, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a halogen atom are preferable, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferable.

R ⁵ in the general formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples include a hydrogen atom; a C1-C20 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, octyl group, 2-ethylhexyl group, etc. Alkyl groups having a straight chain or branched chain; cycloalkyl groups having 3 to 20 carbon atoms such as cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group; carbon numbers 6 such as phenyl group, tolyl group, xylyl group, benzyl group ˜20 aryl groups, alkylaryl groups, aralkyl groups, etc., among these, from the viewpoint of ease of synthesis of the complex, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferred, and a hydrogen atom is more preferred. preferable.

R ⁶ in the general formula (1) represents a hydrocarbon group having 1 to 20 carbon atoms. Specific examples include straight chain having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, octyl group and 2-ethylhexyl group. Alkyl group having a branched chain; cycloalkyl group having 3 to 20 carbon atoms such as cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group; phenyl group, tolyl group, xylyl group, 2,6-diisopropylphenyl group, benzyl group Aryl groups having 6 to 20 carbon atoms, such as aryl groups, alkylaryl groups, or aralkyl groups. Among these, aryls having 6 to 20 carbon atoms from the viewpoint of ease of synthesis of the complex and stability of the complex. Group and an alkylaryl group are preferable, and a phenyl group and a 2,6-diisopropylphenyl group are particularly preferable.

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in the general formula (1) each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring structure. Specific examples include a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, and an octyl group. An alkyl group having a linear or branched chain having 1 to 20 carbon atoms such as 2-ethylhexyl group; an alkenyl group having a linear or branched chain having 1 to 20 carbon atoms such as ethenyl group or 2-propenyl group; Examples thereof include aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, and xylyl group, alkylaryl groups, and aralkyl groups. Among these, from the viewpoint of ease of synthesis of the complex, a hydrogen atom and a carbon number An alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms are preferable, and a hydrogen atom or a methyl group is particularly preferable.

  Specific examples of the transition metal complex (A) represented by the general formula (1) are shown below, but are not limited thereto. In the following specific examples, “M” has the same meaning as “M” in the general formula (1). Me represents a methyl group, Et represents an ethyl group, t-Bu represents a t-butyl group, and Ph represents a phenyl group.

  Among these, (π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium, (π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] -4-fluorophenolato} palladium, (π-allyl) [2- (N-phenyliminomethyl) phenolato] palladium, (π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl]- 6-methylphenolato} palladium is preferred.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶は一般式（１）と同じ意味を示す。）の配位子交換反応により製造することができる。具体的な製造方法として、例えばＪ．Ｏｒｇａｎｏｍｅｔ．Ｃｈｅｍ．，１９７４，８１，２２７−２４６に記載の方法を挙げることができる The transition metal complex (A) of the present invention comprises a precursor (π-allyl) palladium (II) compound and a salicylaldimine compound

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as in the general formula (1)). As a specific manufacturing method, for example, J. Org. Organomet. Chem. , 1974, 81, 227-246.

  The (π-allyl) palladium (II) compound is not particularly limited as long as it is a compound having a ligand capable of ligand exchange with a salicylaldimine compound. For example, di (π-allyl) di (μ-chloro) dipalladium and (π-allyl) (acetylacetonato) palladium are preferable.

  Although the specific example of the salicylaldimine compound used when manufacturing a transition metal complex (A) is shown below, it is not limited to these.

  As such a salicylaldimine compound, a commercially available one can be used as it is. Organometallics, 1998, 17, p. 3149-3151 or Organometallics, 1998, 17, p. What was manufactured by the method of 3460-3465 can also be used.

  In the ligand exchange reaction, a (π-allyl) palladium (II) compound as a precursor is dissolved in a solvent, a salicylaldimine compound or, if necessary, a base added thereto, is added at a predetermined temperature. Can be carried out by stirring for a predetermined time.

  The solvent used in the ligand exchange reaction is not particularly limited as long as it does not react with each substrate. For example, aliphatic hydrocarbons such as pentane, hexane and heptane; alicyclic carbonization such as cyclohexane Hydrogen; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether, dioxane and tetrahydrofuran Can be mentioned. These solvents may be used as a mixture. The solvent used is preferably dehydrated and degassed.

  The amount of the solvent used is not particularly limited as long as the reaction is not significantly delayed, but can be appropriately determined according to the solubility of the precursor (π-allyl) palladium (II) compound. Usually, 1 to 100 g of a solvent is used per 1 g of the (π-allyl) palladium (II) compound as a precursor.

  The reaction temperature is not particularly limited, but is generally -100 to 150 ° C, preferably -50 to 120 ° C. When the temperature is lower than −100 ° C., the reaction rate is slow, and when the temperature is higher than 150 ° C., the formed complex may be decomposed. The reaction rate can be adjusted by selecting the reaction temperature within the above range.

  The reaction time is not particularly limited, and is, for example, 1 minute to 50 hours. The reaction is desirably performed in an inert gas atmosphere such as nitrogen gas or argon gas.

  After completion of the reaction, the intended transition metal complex (A) can be isolated by carrying out ordinary separation / purification operations. Specifically, the salt produced by the reaction is removed by centrifugation or filtration, and then the target transition metal complex (A) is isolated by recrystallization.

Confirmation that the product obtained by the reaction is the target transition metal complex (A) can be carried out by NMR spectrum, elemental analysis, mass spectrum, X-ray crystallography and the like.
The transition metal complex (A) obtained as described above is useful as a catalyst component for polymerization of norbornene monomers.

  The norbornene-based monomer polymerization catalyst of the present invention may be any catalyst that contains at least one transition metal complex (A), but can react with the transition metal complex (A) to produce a cationic transition metal compound. What further contains the promoter (B) which is an ionic compound, and a phosphine-type ligand (C) is preferable at the point which can express a higher catalyst activity.

Cocatalyst (B):
The cocatalyst (B), which is an ionic compound capable of reacting with the transition metal complex (A) used in the present invention to form a cationic transition metal compound, includes an ionic compound in which a non-coordinating anion and a cation are combined. Is mentioned.

  Non-coordinating anions include quaternary anions of Group 13 elements of the 1991 periodic table. Specifically, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (Tetrafluoromethylphenyl) borate, tetrakis [3,5-di (trifluoromethyl) phenyl] borate, tetra (triyl) borate, tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, [tris (pentafluoro Phenyl) phenyl] borate, tridecahydride-7,8-dicarbaoundecaborate and the like.

  Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

  Specific examples of the carbonium cation include tri-substituted carbonium cations such as a triphenyl carbonium cation and a tri-substituted phenyl carbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

  Specific examples of oxonium cations include hydroxonium cations, alkyloxonium cations such as methyloxonium cations, dialkyloxonium cations such as dimethyloxonium cations, trialkyloxonium cations such as trimethyloxonium cations and triethyloxonium cations. And cations.

  Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation, and the like, N, N-diethylanilinium cation, N N, N-dialkylanilinium cation such as N, N-2,4,6-pentamethylanilinium cation, dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation.

  Specific examples of the ferrocenium cation include dialkylferrocenium cations such as a ferrocenium cation, 1,1-dimethylferrocenium cation, and 1,1-diethylferrocenium cation.

  Preferred examples of the cocatalyst (B) include trityltetrakis (pentafluorophenyl) borate, triphenylcarbonium tetra (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, trityltetrakis [3, 5-di (trifluoromethyl) phenyl] borate, N, N-dimethylanilinium tetrakis [3,5-di (trifluoromethyl) phenyl] borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) Borate and the like.

Phosphine-based ligand (C):
The phosphine-based ligand (C) used in the present invention is a trivalent phosphorus compound in which three substituents independently selected from a hydrogen atom, an alkyl group or an aryl group are bonded. Specifically, trialkylphosphines such as trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-t-butylphosphine, tricycloalkylphosphines such as tricyclopentylphosphine and tricyclohexylphosphine, and triaryl such as triphenylphosphine. Mention may be made of phosphines. Of these, tricyclohexylphosphine, tri-t-butylphosphine, and triisopropylphosphine are preferable from the viewpoint of improving catalytic activity.

In the present invention, since a norbornene-based polymer can be produced with high activity, in the general formula (1), R ¹ , R ² , R ³ and R ⁴ are methyl groups or halogens as the transition metal complex (A). Using a complex in which R ⁵ is a hydrogen atom, R ⁶ is an alkyl-substituted phenyl group, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are all hydrogen atoms, B) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate {[Ph (Me) ₂ NH] [B (C ₆ F ₅ ) ₄ ]} or trityltetrakis (pentafluorophenyl) borate {[Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]} and a catalyst using triisopropylphosphine or tri-t-butylphosphine as the phosphine-based ligand (C) is preferable.

Further, as a transition metal complex (A), in the general formula ^{(1), R 1, R} 3 is a methyl group or a fluorine atom, R ^2, R ^4, and R ⁵ is a hydrogen atom, R ⁶ is phenyl Or a 2,6-diisopropylphenyl group, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are all hydrogen atoms, and N, N-dimethyl is used as a promoter (B). A catalyst using anilinium tetrakis (pentafluorophenyl) borate {[Ph (Me) ₂ NH] [B (C ₆ F ₅ ) ₄ ]} and further using triisopropylphosphine as a phosphine-based ligand (C) More preferred.

  The ratio of the transition metal complex (A) and the cocatalyst (B) used in the catalyst used in the present invention is not uniquely determined because it varies depending on various conditions, but is usually (A) / (B) ( The molar ratio is 1 / 0.1 to 1/100, preferably 1 / 0.5 to 1/50, and more preferably 1/1 to 1/10.

  The ratio of use of the transition metal complex (A) and the phosphine-based ligand (C) is also not uniquely determined because it varies depending on various conditions, but is usually (A) / (C) (molar ratio). It is 1 / 0.1 to 1/2, preferably 1 / 0.5 to 1 / 1.8, more preferably 1/1 to 1 / 1.5.

  The temperature at which each catalyst component is brought into contact is not particularly limited, but is generally -100 to 150 ° C, preferably -50 to 120 ° C. When the temperature is lower than −100 ° C., the reaction between the components is delayed, and when the temperature is higher than 150 ° C., the decomposition of each component is caused and the activity of the catalyst is lowered. By selecting the contact temperature within the above range, the polymerization rate, the molecular weight of the produced polymer, and the like can be adjusted when used for polymerization.

  Each catalyst component may be mixed in the presence of a solvent. The solvent that can be used is not particularly limited, but a solvent that has no reactivity with each catalyst component, is manufactured on an industrial scale, and is easily available is preferable. Specifically, aliphatic hydrocarbons such as pentane, hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene; Nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether, dioxane and tetrahydrofuran can be used. Among these, aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons are preferable. These solvents may be used as a mixture.

[Method for producing norbornene polymer]
The method for producing a norbornene polymer of the present invention is characterized in that a norbornene monomer is subjected to addition polymerization in the presence of a polymerization catalyst.

  The production method of the present invention includes (i) a method of obtaining a single addition polymer of a norbornene monomer by addition polymerization of only one kind of norbornene monomer, and (ii) an addition copolymerization of two or more types of norbornene monomers. To obtain an addition copolymer of a norbornene-based monomer, and (iii) addition-copolymerizing one or more norbornene-based monomers with one or more other vinyl monomers copolymerizable with the norbornene-based monomers. It is one of methods for obtaining an addition copolymer of monomers.

Norbornene monomer:
The norbornene monomer used in the present invention is not particularly limited as long as it is a compound having a norbornene ring structure (hereinafter sometimes simply referred to as “norbornenes”). It may have a polar or non-polar substituent and may have a ring structure other than the norbornene ring.
As norbornene, what is shown by General formula (4) is preferable.

In the formula, R ^{16 to} R ¹⁹ each independently have a hydrogen atom; a halogen atom; a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom or a silicon atom; a halogen atom or the functional group. The C1-C20 hydrocarbon group which may be sufficient. R ^{16 to} R ¹⁹ may be bonded to each other to form a ring. n is 0 or 1.

The norbornenes represented by the general formula (4) include bicyclo [2.2.1] hept-2-enes in which n is 0 and tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-enes. Any of the production methods of the present invention can be used.

Specific examples of R ^{16 to} R ¹⁹ in the general formula (4) include a hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom, and a fluorine atom; a hydroxyl group, an alkoxy group, an aryloxy group, a carbonyl group, and a hydroxycarbonyl group. , Functional groups containing oxygen atoms such as alkoxycarbonyl groups and aryloxycarbonyl groups; nitrogen such as amino groups, alkylamino groups, arylamino groups, aminocarbonyl groups, alkylaminocarbonyl groups, arylaminocarbonyl groups, and cyano groups Functional groups containing atoms; functional groups containing sulfur atoms such as mercapto groups, alkoxythio groups, and aryloxythio groups; silicon such as silyl groups, alkylsilyl groups, arylsilyl groups, alkoxysilyl groups, and aryloxysilyl groups Mention may be made of functional groups containing atoms. Moreover, hydrocarbon groups, such as a C1-C20 alkyl group, alkenyl group, and aryl group which may have these functional groups, are also mentioned. Furthermore, R ^{16 to} R ¹⁹ may be bonded to each other to form a ring, and examples of such examples include an acid anhydride structure, a carbonate structure, and a dithiocarbonate structure.

Specific examples of norbornenes used in the present invention include 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-n-butyl-2-norbornene, and 5-n-hexyl-2. -Norbornene, 5-n-decyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2 - norbornene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclo [9.2.1.0 ^2,10. 0 ^3,8] tetradec -3,5,7,12- tetraene, tetracyclo [10.2.1.0 ^2,11. 0 ^4,9 ] bicyclo [2.2.1] hept-2-enes having an unsubstituted or hydrocarbon group such as pentadeca-4,6,8,13-tetraene;

Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] tetracyclo an unsubstituted or a hydrocarbon group such as dodeca-4-ene [6.2.1.1 ^{3, 6.} 0 ^2,7 ] dodec-4-enes;

Methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, n-butyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 2-methyl- Ethyl 5-norbornene-2-carboxylate, n-butyl 2-methyl-5-norbornene-2-carboxylate, methyl 5-norbornene-2,3-dicarboxylate, ethyl 5-norbornene-2,3-dicarboxylate, etc. Bicyclo [2.2.1] hept-2-enes having the following alkoxycarbonyl group; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylate, tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an alkoxycarbonyl group such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylate. 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1] hept-2-enes having a hydroxycarbonyl group such as 5-norbornene-2-carboxylic acid and 5-norbornene-2,3-dicarboxylic acid; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a hydroxycarbonyl group such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid. 0 ^2,7 ] dodeca-9-enes;

Has hydroxyl groups such as 2-hydroxy-5-norbornene, 2-hydroxymethyl-5-norbornene, 2,2-di (hydroxymethyl) -5-norbornene, 2,3-di (hydroxymethyl) -5-norbornene Bicyclo [2.2.1] hept-2-enes; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-en-4-ol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-methanol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4,5-dimethanol and the like tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-enes;

Has an acetoxyl group such as 2-acetoxy-5-norbornene, 2-acetoxymethyl-5-norbornene, 2,2-di (acetoxymethyl) -5-norbornene, 2,3-di (acetoxymethyl) -5-norbornene Bicyclo [2.2.1] hept-2-enes; 4-acetoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-acetoxymethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4,5-di (acetoxymethyl) tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an acetoxyl group such as 0 ^2,7 ] dodec-9-ene. 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1] hept-2-enes having a functional group containing a nitrogen atom such as 5-norbornene-2-carbonitrile and 5-norbornene-2-carboxamide; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carbonitrile, tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a functional group containing a nitrogen atom such as 0 ^2,7 ] dodec-9-ene-4-carboxamide. 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1] hept-2-enes having a halogen atom such as 2-chloro-5-norbornene and 2-fluoro-5-norbornene; 4-chlorotetracyclo [6.2.1.1 ^{3 , 6} . 0 ^2,7 ] dodec-9-ene, 4-fluorotetracyclo [6.2.1.1 ^3,6 . ^02,7 ] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1 having functional groups containing silicon atoms such as 2-trimethylsiloxy-5-norbornene, 2-trimethoxysilyl-5-norbornene, 2-tris (trimethoxysilyloxy) silyl-5-norbornene ] Hept-2-enes; 4-trimethylsiloxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-tris (trimethoxysilyloxy) silyltetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a functional group containing a silicon atom such as 0 ^2,7 ] dodec-9-ene. 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2] having an acid anhydride structure such as 5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-carbonate, 5-norbornene-2,3-dithiocarbonate, carbonate structure, dithiocarbonate structure 2.2.1] hept-2-enes; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4,5-carbonate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] tetracyclo [6.2.1.1 ^3,6 . Having acid anhydride structure, carbonate structure, dithiocarbonate structure such as dodeca-9-ene-4,5-dithiocarbonate. 0 ^2,7 ] dodeca-9-enes and the like.
These norbornenes can be used alone or in combination of two or more.

及び一般式（３）

（式中、Ｒ¹²は炭素数１〜１０のアルキル基を表し、Ｒ¹³、Ｒ¹⁴、及びＲ¹⁵はそれぞれ独立して水素原子または炭素数１〜１０のアルキル基を表す。）
で示されるモノマーユニットに相当するノルボルネン類を用いることが好ましい。 In the production method of the present invention, among these norbornenes, the following general formula (2)

And general formula (3)

(In the formula, R ¹² represents an alkyl group having 1 to 10 carbon atoms, and R ¹³ , R ¹⁴ , and R ¹⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
It is preferable to use norbornenes corresponding to the monomer units represented by

Alkyl group having 1 to 10 carbon atoms represented by R ¹² in the general formula (2) may be a linear or branched chain.

Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl and the like. It is done.
Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, neopentyl group, isohexyl group, isooctyl group, and isodecyl group.

Among these, as R < ¹² >, a C1-C3 linear alkyl group is preferable in terms of economy. From the viewpoint of monomer production cost, a methyl group is particularly preferable.

R ¹³ in the general formula (2) and R ¹⁴ and R ¹⁵ in the formula (3) each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 3 to 10 carbon atoms is branched. It may be. Examples of these alkyl groups include the same alkyl groups as those described above for R ¹² . Among these, as R ¹³ , R ¹⁴ and R ¹⁵ , a hydrogen atom is preferable from the viewpoint of monomer production cost.

When R ¹³ is a hydrogen atom, the norbornenes that are the basis of the monomer unit represented by the general formula (2) are 2-acetoxymethyl-5-norbornene when R ¹² is a C 1 alkyl group, When R ¹² is an alkyl group having 2 carbon atoms, 2-[(ethylcarbonyloxy) methyl] -5-norbornene, and when R ¹² is a linear alkyl group having 3 carbon atoms, 2-[(propylcarbonyloxy ) Methyl] -5-norbornene.
When R ¹⁴ and R ¹⁵ are hydrogen atoms, the norbornenes that form the basis of the monomer unit represented by the formula (3) are norbornene.

  In the production method of the present invention, the polymerization of the norbornene monomer using the transition metal complex (A), the cocatalyst (B) and the phosphine ligand (C) is carried out by precipitation polymerization.

  Precipitation polymerization is a kind of solution polymerization, and a solvent that dissolves a monomer but does not dissolve a polymer is used. In the precipitation polymerization, a polymer is precipitated together with the polymerization, so that a poor solvent (such as methanol) used in a large amount for reprecipitation purification is unnecessary, which is advantageous in terms of production cost. In the (co) polymer of the present invention, a mixed solvent of toluene and ethyl acetate is suitable for precipitation polymerization.

  In the method of the present invention in which the copolymer containing the monomer units represented by the general formula (2) and the general formula (3) is produced by precipitation polymerization, the monomer is dissolved but the produced polymer is not dissolved. Those containing a group carboxylic acid ester are used. The solvent for precipitation polymerization is not particularly limited as long as it contains an aliphatic carboxylic acid ester, and may be a mixed solvent composed of two or more aliphatic carboxylic acid esters. Moreover, you may contain the good solvent (toluene etc.) and poor solvent of the said polymer in the range which the produced | generated polymer does not melt | dissolve. A good solvent may be used to dissolve the catalyst. Furthermore, a solvent other than the aliphatic carboxylic acid ester may be used in combination with a solvent that dissolves the monomer but does not dissolve the produced polymer, such as n-hexane. However, when the ratio of the aliphatic carboxylic acid ester is reduced, the handling may be deteriorated such that the produced polymer does not completely precipitate or does not precipitate in powder form.

  The aliphatic carboxylic acid ester is preferably an ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms, and an aliphatic carboxylic acid alkyl ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms and an alcohol having 1 to 5 carbon atoms. More preferred are ethyl acetate, n-propyl acetate, isopropyl acetate and n-butyl acetate.

The mixed solvent composed of two or more aliphatic carboxylic acid esters is preferably two mixed solvents arbitrarily selected from ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate. Ethyl acetate and n-acetate A mixed solvent of propyl is more preferable. The mixed solvent of the aliphatic carboxylic acid ester and the other solvent is preferably a mixed solvent of an alkyl ester having 1 to 5 carbon atoms of an aliphatic carboxylic acid having 1 to 5 carbon atoms and an aromatic hydrocarbon, and acetic acid. A mixed solvent of ethyl and toluene or n-propyl acetate and toluene is more preferable.

  In the method for producing a (co) polymer of the present invention, when a mixed solvent composed of two or more aliphatic carboxylic acid esters is used in carrying out precipitation polymerization, there is no particular limitation on the mixing ratio, and how What mixed in a small ratio can also be used.

  Moreover, when using the mixed solvent of aliphatic carboxylic acid ester and another solvent, it is preferable that the ratio of aliphatic carboxylic acid ester is 60 volume% or more, and 80 volume% or more is more preferable. When the proportion of the aliphatic carboxylic acid ester is less than 60% by volume, the produced (co) polymer is difficult to precipitate and the polymer recovery rate may be lowered. In addition, the ratio of aliphatic carboxylic acid ester means the ratio in the total amount of all solvent components, such as the solvent used for melt | dissolution of a catalyst.

  When carrying out precipitation polymerization in the method for producing a (co) polymer of the present invention, if an aliphatic hydrocarbon often used in general precipitation polymerization, such as hexane, heptane, or cyclohexane, is used as a solvent, the polymer is formed. Although it precipitates at the same time, the produced polymer adheres to the reactor wall, and eventually agglomerates, and finally a lump is formed and stirring cannot be continued, so it cannot be used as a solvent for precipitation polymerization. However, handling is slightly inferior to the case of using an aliphatic carboxylic acid ester.

  In addition, when carrying out precipitation polymerization in the method for producing a (co) polymer of the present invention, alcohol compounds such as methanol and ethanol, acetone, and methyl ethyl ketone (MEK) often used for precipitating a polymer by solution polymerization. When such a ketone compound is used, the activity of the polymerization catalyst is significantly reduced.

  From the above, when carrying out precipitation polymerization in the method for producing a (co) polymer of the present invention, the selection of the solvent is important, the polymer to be produced does not dissolve, the deposited polymer surface is not sticky, It can be seen that aliphatic carboxylic acid esters are suitable as non-poisoning solvents.

  The solubility of the polymer is affected by the molecular structure of the polymer, but the influence of the type of polymerization catalyst is small if the monomer composition and quantity ratio do not change much. Accordingly, not only the polymerization catalyst of the present invention, but also when a (co) polymer containing monomer units represented by the general formula (2) and the general formula (3) is produced by precipitation polymerization using another polymerization catalyst. The solvent system can be applied. Any catalyst containing a Ni compound or a Pd compound capable of polymerizing a cyclic olefin compound can be used except that it is poisoned by a carboxylic acid alkyl ester and does not exhibit activity.

  When performing the polymerization, the main catalyst (A), the cocatalyst (B) and the phosphine-based ligand (C) are mixed, and the mixing order is such that the main catalyst (A) contacts the cocatalyst (B). Others are not particularly limited as long as they are mixed with the phosphine-based ligand (C) before the operation. A main catalyst (A) component and a phosphine-based ligand (C) are mixed in advance, and a co-catalyst (B) is further mixed to obtain a reaction composition, which is added to a solution containing a monomer to be polymerized. Also good. Further, the promoter (B) may be added to the solution containing the monomer to be polymerized, the main catalyst (A) and the phosphine-based ligand (C), and the monomer to be polymerized and the promoter (B). A mixture of the main catalyst (A) and the phosphine-based ligand (C) may be added to the mixed solution.

  In the present invention, the main catalyst (A) and the phosphine-based ligand (C) are mixed in advance and contacted for 1 minute or more, preferably about 30 minutes to 1 hour, and then mixed with the promoter (B). Preferably, it is added to the reaction system, or a mixture of the main catalyst (A) and the phosphine-based ligand (C) is added to the reaction system containing the promoter (B). By performing such an operation, it becomes possible to express higher polymerization activity.

  The polymerization temperature is not particularly limited, but is generally -100 to 150 ° C, preferably -50 to 120 ° C. When the temperature is lower than −100 ° C., the polymerization rate is slow, and when the temperature is higher than 150 ° C., the activity of the catalyst may be lowered. By selecting the polymerization temperature within the above range, the polymerization rate, molecular weight and the like can be adjusted.

  The polymerization time is not particularly limited, and is, for example, 1 minute to 100 hours. The reaction is desirably performed in an inert gas atmosphere such as nitrogen gas.

  After completion of the polymerization reaction, the product norbornene-based polymer is isolated by performing post-treatment by known operations and treatment methods (for example, reprecipitation) as necessary, filtering and then drying. .

  In the norbornene copolymer composed of the monomer units represented by the general formula (2) and the general formula (3) produced by the production method of the present invention, the content of the monomer unit represented by the general formula (2) is: It is preferable that it is 10-70 mol%. When the monomer unit represented by the general formula (2) is less than 10 mol%, the hydrophobicity of the copolymer increases and the solubility in an organic solvent decreases, but the water absorption tends to decrease. On the other hand, when it exceeds 70 mol%, the copolymer becomes hydrophilic and the solubility in an organic solvent is improved, but the water absorption tends to increase. Therefore, it is possible to control the solubility of the copolymer in the solvent and the water absorption by adjusting the content of the monomer unit represented by the general formula (2).

To the solvent required when the norbornene-based copolymer composed of the monomer units represented by the general formula (2) and the general formula (3) produced by the production method of the present invention is formed into a film, a sheet or the like. From the standpoint of achieving both moderate solubility and low water absorption, the content of the monomer unit represented by the general formula (2) is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and more preferably 20 to 60 mol. % Is more preferable. The content of the monomer unit represented by the general formula (2) is calculated from an integral value obtained by measuring a ¹ H-NMR by dissolving a powdery or film-like copolymer in a suitable deuterated solvent. be able to.

  The norbornene-based (co) polymer produced by the production method of the present invention is basically composed only of norbornenes. However, even in this case, it does not exclude the presence of a very small amount, for example, 1 mol% or less of the third monomer unit that hardly changes the properties of the norbornene (co) polymer of the present invention. Moreover, the norbornene-type (co) polymer manufactured with the manufacturing method of this invention may copolymerize the 3rd monomer in the range which does not impair the effect of this invention for physical property improvement.

  Although there is no restriction | limiting in particular in a 3rd monomer, The monomer which has an ethylenic carbon-carbon double bond is preferable, for example, alpha-olefins, such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene; Aromatic vinyl compounds such as styrene, α-methylstyrene and divinylbenzene; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and propyl vinyl ether; methyl acrylate, ethyl acrylate, 2- Examples thereof include acrylates such as ethylhexyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate; Of these, α-olefins such as ethylene, propylene and 1-hexene, and aromatic vinyl compounds such as styrene are particularly preferable.

  In the norbornene copolymer produced by the production method of the present invention, the copolymerization mode of each monomer unit can be random, block, or alternating depending on the polymerization conditions, but from the viewpoint of improving the physical properties of the copolymer. It is desirable to be random.

  The polystyrene-equivalent number average molecular weight (Mn) of the norbornene-based (co) polymer produced by the production method of the present invention measured by gel permeation chromatography (GPC) is 50,000 to 2,000,000. . Furthermore, 100,000 to 1,500,000 is more preferable. If the number average molecular weight in terms of polystyrene is less than 50,000, the mechanical strength is insufficient. When the number average molecular weight in terms of polystyrene exceeds 2,000,000, not only the solubility in a solvent is lowered when a cast film is formed, but also the solution viscosity is increased and the molding processability is lowered. Further, the molecular weight distribution Mw / Mn (weight average molecular weight / number average molecular weight) is preferably 1.00 to 4.00, more preferably 1.30 to 3.50, and still more preferably 1.50 to 3.30. When the molecular weight distribution is wide, the solution at the time of forming the cast film is difficult to be uniform, so that it is difficult to produce a good film.

（式中の記号は前述と同じ意味を表す。）
で示されるモノマーユニットのみからなる重合体も好ましい。その数平均分子量（Ｍｎ）は、２００，０００〜１，０００，０００であり、数平均分子量が２００，０００未満であると耐薬品性が低下し、１，０００，０００を超えるとキャストフィルムを成形する際に溶媒への溶解度が低下するばかりでなく、溶液粘度が高くなり、成形加工性が低下することがある。 Among the norbornene (co) polymers produced by the production method of the present invention, the general formula (2)

(The symbols in the formula have the same meaning as described above.)
A polymer consisting only of monomer units represented by The number average molecular weight (Mn) is 200,000 to 1,000,000. If the number average molecular weight is less than 200,000, the chemical resistance is lowered, and if it exceeds 1,000,000, a cast film is obtained. When molding, not only the solubility in a solvent is lowered, but also the solution viscosity is increased and molding processability may be lowered.

  The saturated water absorption at 23 ° C. of the norbornene-based (co) polymer produced by the production method of the present invention is usually 0.001 to 1% by mass, preferably 0.005 to 0.7% by mass, and more preferably. It is 0.01-0.5 mass%. When the saturated water absorption is within this range, various optical properties such as transparency, retardation, uniformity of retardation, and dimensional accuracy are maintained even under conditions such as high temperature and humidity, and adhesion to other materials. In addition, since it is excellent in adhesion, peeling or the like does not occur during use, and compatibility with additives such as an antioxidant is good, so that the degree of freedom of addition is increased. In addition, the said saturated water absorption is a value calculated | required by immersing in 23 degreeC water for 24 hours, and measuring an increase mass based on JISK7209.

  The glass transition temperature (Tg) of the norbornene-based (co) polymer produced by the production method of the present invention varies depending on the type of monomer units, composition ratio, presence of additives, etc. 80-350 ° C, preferably 100-320 ° C, more preferably 120-300 ° C. When Tg is lower than the above range, the heat distortion temperature is lowered, there is a possibility that a problem occurs in heat resistance, and the change in the optical characteristics depending on the temperature of the obtained optical film may be increased. Moreover, when Tg is higher than the said range, when heating to Tg vicinity at the time of an extending | stretching process, possibility that a resin will carry out thermal degradation will become high.

  The norbornene-based (co) polymer produced by the production method of the present invention can be formed into a film by a solution casting method (solution casting method) and processed into a film. As a solvent to be used, toluene, tetrahydrofuran (THF), dichloromethane, chloroform or the like can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention does not receive any limitation by these description.

により算出した。ただし、実施例７では「パラジウムのモル数」を「ニッケルのモル数」とした。
得られたポリマーの重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、分子量分布（Ｍｗ／Ｍｎ）は、ポリスチレンを標準物質として用いたゲルパーミエイションクロマトグラフ（ＧＰＣ）により求めた。また、共重合体中のノルボルネンと５−アセトキシメチル−２−ノルボルネンの組成比は、¹Ｈ−ＮＭＲにより得られたピーク［δ：３．５−４．５ｐｐｍ，５−アセトキシメチル−２−ノルボルネン（「ＡＮＢ」と略す。）の「−ＣＯＯＣＨ₂−」ユニット］と［δ：０．５−３．０ｐｐｍ，ノルボルネン（「ＮＢ」と略す。）及び５−アセトキシメチル−２−ノルボルネンの「ＣＨ₃ＣＯＯ−」、「−ＣＨ₂−」及び「−ＣＨ＝」ユニット］の積分比から求め、ＡＮＢ含有率は以下の式

より算出した。 In each Example and Comparative Example, the catalytic activity is expressed by the following formula:

Calculated by However, in Example 7, “the number of moles of palladium” was set to “the number of moles of nickel”.
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the obtained polymer were determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. The composition ratio of norbornene and 5-acetoxymethyl-2-norbornene in the copolymer is the peak [δ: 3.5-4.5 ppm, 5-acetoxymethyl-2-norbornene obtained by ¹ H-NMR. “—COOCH ₂ —” unit ”(abbreviated as“ ANB ”) and [δ: 0.5-3.0 ppm, norbornene (abbreviated as“ NB ”) and“ CH ”of 5-acetoxymethyl-2-norbornene. ₃ COO- ”,“ —CH ₂ — ”and“ —CH = ”units]], and the ANB content is calculated by the following formula:

Calculated from

Various physical properties of the materials synthesized in Examples and Comparative Examples were measured as follows.
1. ¹ H-NMR, ¹³ C-NMR
Model used: JEOL EX-400 (400 MHz, manufactured by JEOL Ltd.)
Measurement method: Dissolved in deuterated chloroform and measured using tetramethylsilane as internal standard substance.
2. FT-IR
Model used System: Spectrum GX (Perkin Elmer),
ATR: MIRacle ™ (Pike Technologies)
Measurement method: Measured by a single reflection ATR method.

3. Gel permeation chromatography (GPC)
Model used Column: Shodex GPC KG + KF-806L × 2 (Showa Denko)
Detector: Shodex SE-61 (made by Showa Denko KK).
Measurement conditions Solvent: Tetrahydrofuran,
Measurement temperature: 40 ° C.
Flow rate: 1.0 ml / min,
Sample concentration: 1.0 mg / ml,
Injection volume: 1.0 μl,
Calibration curve: Universal Calibration curve,
Analysis program: SIC 480II (manufactured by System Instruments).

  Cyclopentadienyl (π-allyl) palladium was synthesized according to the synthesis method of Shaw et al. (Shaw. B.L., Proc. Chem. Soc., 1960, 247).

Synthesis Example 1: Synthesis of 2-acetoxymethyl-5-norbornene In a 10 L stainless steel autoclave, dicyclopentadiene (Tokyo Chemical Industry Co., Ltd., 759.80 g, 5.747 mol) and allyl acetate (Tokyo Chemical Industry Co., Ltd., 1457. 86 g, 14.561 mol) and hydroquinone (Wako Pure Chemical Industries, 2.25 g, 0.0204 mol) were added. After the system was purged with nitrogen, the autoclave was heated to 190 ° C. and stirred for 5 hours while stirring at 500 rpm. After completion of the reaction, the autoclave was cooled to room temperature, the contents were transferred to a distillation apparatus, and distilled under reduced pressure to obtain 1306.70 g of a colorless transparent liquid as a fraction of 0.07 kPa and 48 ° C.
¹ H-NMR of the obtained liquid was measured to confirm that it was the target 2-acetoxymethyl-5-norbornene. Moreover, the molar ratio of the exo isomer and endo isomer of 2-acetoxymethyl-5-norbornene obtained was exo / endo = 18/82.

Synthesis Example 2: Synthesis of 2- [N- (2,6-diisopropylphenyl) iminomethyl] phenol In a one-neck flask, salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd., 2.00 g, 16.4 mmol), 2,6-diisopropylaniline was synthesized. (Tokyo Chemical Industry Co., Ltd., 3.12 g, 17.6 mmol), ethanol (Wako Pure Chemical Industries, 20 ml) and formic acid (Wako Pure Chemical Industries, 305 mg, 6.63 mmol) were added and stirred. The reaction was carried out at room temperature for one day. The precipitate was filtered off and recrystallized from methanol to obtain 1.79 g of yellow crystals. ¹ H-NMR and ¹³ C-NMR of the obtained crystal were measured and confirmed to be 2- [N- (2,6-diisopropylphenyl) iminomethyl] phenol.

三方コックを装備した二口フラスコを窒素置換し、これに合成例２で調製した２−［Ｎ−（２，６−ジイソプロピルフェニル）イミノメチル］フェノール（５０６ｍｇ，１．８０ｍｍｏｌ）を仕込み、脱水テトラヒドロフラン（和光純薬工業社製，２０ｍｌ）を加えて溶解した。これを、ドライアイス−エタノール浴に漬けて−７８℃に冷却した後、ｎ−ブチルリチウムの１．６ｍｏｌ／ｌヘキサン溶液（和光純薬工業社製，１．１４ｍｌ，１．８２ｍｍｏｌ）を５分かけてゆっくりと滴下し、滴下終了後、徐々に室温に戻した。
別途用意した三方コックを装備した二口フラスコを窒素置換し、これにアリルパラジウムクロリドダイマー（和光純薬工業社製，３０５ｍｇ，０．８３４ｍｍｏｌ）を仕込み、脱水ジクロロメタン（和光純薬工業社製，２０ｍｌ）を加えて溶解した。
この溶液を氷浴に漬けて０℃に冷却し、これに先に調製したテトラヒドロフラン／ヘキサン混合溶液を５分間かけてゆっくりと滴下し、０℃で２時間反応を行った。その後、減圧下に溶媒を完全に留去し、あらためて脱水トルエン（和光純薬工業社製，２０ｍｌ）を加えて撹拌した後、窒素下に遠心分離を行って、不要な塩を取り除き、上澄みのトルエン溶液を回収した。この溶液より減圧下に濃縮し、再結晶を行って、黄色結晶３５６ｍｇを得た。得られた結晶の¹Ｈ−ＮＭＲ、¹³Ｃ−ＮＭＲ及びＩＲスペクトル測定を行い、（π−アリル）｛２−［Ｎ−（２，６−ジイソプロピルフェニル）イミノメチル］フェノラト｝パラジウム［錯体Ａ−１］であることを確認した。 Synthesis Example 3: Synthesis of (π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium [complex A-1]

A two-necked flask equipped with a three-way cock was purged with nitrogen, and this was charged with 2- [N- (2,6-diisopropylphenyl) iminomethyl] phenol (506 mg, 1.80 mmol) prepared in Synthesis Example 2, and dehydrated tetrahydrofuran ( Wako Pure Chemical Industries, Ltd., 20 ml) was added and dissolved. This was immersed in a dry ice-ethanol bath and cooled to −78 ° C., and then a 1.6 mol / l hexane solution of n-butyllithium (manufactured by Wako Pure Chemical Industries, Ltd., 1.14 ml, 1.82 mmol) was added for 5 minutes. The solution was slowly added dropwise, and after completion of the addition, the temperature was gradually returned to room temperature.
A two-necked flask equipped with a three-way cock prepared separately was purged with nitrogen, and allyl palladium chloride dimer (manufactured by Wako Pure Chemical Industries, 305 mg, 0.834 mmol) was charged into this, and dehydrated dichloromethane (manufactured by Wako Pure Chemical Industries, 20 ml). ) Was added and dissolved.
This solution was immersed in an ice bath and cooled to 0 ° C., and the tetrahydrofuran / hexane mixed solution prepared previously was slowly added dropwise over 5 minutes, followed by reaction at 0 ° C. for 2 hours. Thereafter, the solvent was completely distilled off under reduced pressure, dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd., 20 ml) was again added and stirred, and then centrifuged under nitrogen to remove unnecessary salts. The toluene solution was collected. The solution was concentrated under reduced pressure and recrystallized to obtain 356 mg of yellow crystals. ¹ H-NMR, ¹³ C-NMR and IR spectra of the obtained crystals were measured, and (π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium [complex A-1 It was confirmed that

Comparative Example 1: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene (solution polymerization)
A three-necked flask equipped with a three-way cock and a mechanical stirrer was purged with nitrogen, and norbornene (4.71 g, 0.050 mol) manufactured by Tokyo Chemical Industry Co., Ltd. and 2-acetoxymethyl-5-norbornene (16. 62 g, 0.100 mol) was added and dissolved in 75 ml of toluene, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate [(C ₆ H ₅ ) (CH ₃ ) ₂ NH] [B (C ₆ F ₅ ) ₄ ] (manufactured by Strem, 8.0 mg, 0.010 mmol) was added in 1 ml of dichloromethane, and the mixture was heated to 70 ° C. (Π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium [complex A-1] (4.3 mg, prepared in Synthesis Example 3 and prepared in a separate container) 0.010 mmol) and triisopropylphosphine [P (i-C ₃ H ₇ ) ₃ ] (Strem, 1.6 mg, 0.010 mmol) dissolved in 3.5 ml of toluene were added, and the mixture was added at 70 ° C. The polymerization reaction was performed for 30 minutes. Thereafter, a solution prepared by dissolving norbornene (Tokyo Chemical Industry Co., Ltd., 4.71 g, 0.050 mol) separately prepared in 5.4 ml of toluene was added to the reaction solution, and a polymerization reaction was further performed at 70 ° C. for 30 minutes. After completion of the reaction, 8 ml of methanol to which a small amount of hydrochloric acid was added was added to the reaction solution, the reaction was stopped, diluted with toluene, poured into a large amount of methanol to precipitate a polymer, filtered and washed, and then subjected to reduced pressure. Drying at 90 ° C. for 5 hours gave 10.52 g of a white powdery polymer. The catalytic activity calculated from the polymer yield and the amount of charged catalyst was 1052 g-polymer / mmol-Pd.
The obtained polymer was easily dissolved in a general solvent such as THF and chloroform, the number average molecular weight was Mn = 916,000, and the molecular weight distribution was Mw / Mn = 2.12. The composition of 2-acetoxymethyl-5-norbornene monomer unit in the polymer calculated from the integral value of ¹ H-NMR was 20.4 mol%. A large amount of methanol was required as a poor solvent for reprecipitation to obtain a powdery polymer.

Example 1: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene A three-necked flask equipped with a three-way cock and a mechanical stirrer was purged with nitrogen, and norbornene (9.42 g, 0.100 mol) was added to 5.4 ml of toluene. The dissolved solution and 2-acetoxymethyl-5-norbornene (16.62 g, 0.100 mol) prepared in Synthesis Example 1 were added, dissolved in ethyl acetate (70 ml), and the temperature was raised to 80 ° C. (Π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium [complex A-1] (4.3 mg, prepared in Example 1 and prepared in a separate container) 0.010 mmol) and triisopropylphosphine [P (i-C ₃ H ₇ ) ₃ ] (Strem, 1.6 mg, 0.010 mmol) and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate [( A catalyst solution in which C ₆ H ₅ ) (CH ₃ ) ₂ NH] [B (C ₆ F ₅ ) ₄ ] (Strem, 8.0 mg, 0.010 mmol) was dissolved in 3.5 ml of toluene was added, and 80 The polymerization reaction was carried out at 1 ° C. for 1 hour. During the polymerization, the polymer precipitated as a white powder. After completion of the reaction, 8 ml of methanol to which a small amount of hydrochloric acid was added was added to the reaction solution to stop the reaction. The precipitated polymer was washed by filtration and then dried at 90 ° C. for 5 hours under reduced pressure to give a white powdery polymer 12. 41 g was obtained. The catalytic activity calculated from the polymer yield and the amount of charged catalyst was 1241 g-polymer / mmol-Pd.
The obtained polymer was easily dissolved in a general solvent such as THF and chloroform, the number average molecular weight was Mn = 287,000, and the molecular weight distribution was Mw / Mn = 2.18. The composition of 2-acetoxymethyl-5-norbornene monomer unit in the polymer calculated from the integral value of ¹ H-NMR was 20.1 mol%.

Example 2: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature and the polymerization time were changed as shown in Table 1.

Example 3: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene Polymerization was carried out in the same manner as in Example 1 except that the polymerization solvent was changed from ethyl acetate to n-propyl acetate.

Example 4: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene A three-necked flask equipped with a three-way cock, a dropping funnel and a mechanical stirrer was purged with nitrogen, and norbornene (6.31 g, 0.067 mol) was replaced with toluene 7 The solution dissolved in 3 ml and 2-acetoxymethyl-5-norbornene (22.11 g, 0.133 mol) prepared in Synthesis Example 1 were added, dissolved in ethyl acetate (80 ml), and the temperature was raised to 80 ° C. Separately, a solution obtained by dissolving norbornene (16.29 g, 0.173 mol) in 19.0 ml of toluene and 2-acetoxymethyl-5-norbornene (14.46 g, 0.087 mol) and acetic acid prepared in Synthesis Example 1 were added to the dropping funnel. Ethyl (80 ml) was added. Thereafter, (π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium [complex A-1] (4.) was synthesized in a flask and prepared in a separate container. 3 mg, 0.010 mmol) and triisopropylphosphine [P (i-C ₃ H ₇ ) ₃ ] (Strem, 1.6 mg, 0.010 mmol) and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate A catalyst solution in which [(C ₆ H ₅ ) (CH ₃ ) ₂ NH] [B (C ₆ F ₅ ) ₄ ] (Strem, 8.0 mg, 0.010 mmol) was dissolved in 2.5 ml of toluene was added. The polymerization was started. During the polymerization, the polymer precipitated as a white powder. The dropping of the mixed solution charged in the dropping funnel was started from 30 minutes after the start of the polymerization, and the dropping was completed over 80 minutes while performing the polymerization reaction at 80 ° C. After completion of the dropwise addition, the reaction was further carried out at 80 ° C. for 10 minutes. After 2 hours from the start of polymerization, 8 ml of methanol added with a small amount of hydrochloric acid was added to the reaction solution to stop the reaction. And dried at 90 ° C. for 5 hours to obtain 36.10 g of a white powdery polymer. The catalytic activity calculated from the polymer yield and the amount of charged catalyst was 3610 g-polymer / mmol-Pd.
The obtained polymer was easily dissolved in a general solvent such as THF and chloroform, the number average molecular weight was Mn = 420,800, and the molecular weight distribution was Mw / Mn = 2.77. The composition of 2-acetoxymethyl-5-norbornene monomer unit in the polymer calculated from the integral value of ¹ H-NMR was 39.0 mol%.

Example 5: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene 2-acetoxy prepared in Synthesis Example 1 with a solution obtained by dissolving norbornene (27.12 g, 0.288 mol) in 31.0 ml of toluene in a dropping funnel Methyl-5-norbornene (23.94 g, 0.144 mol) and ethyl acetate (135 ml) were added, it was added dropwise over 140 minutes, and after completion of the addition, the reaction was further carried out at 80 ° C. for 10 minutes. Polymerization was carried out in the same manner as in Example 4 except that the time was 3 hours to obtain 54.00 g of a white powdery polymer. The catalytic activity calculated from the polymer yield and the amount of charged catalyst was 5400 g-polymer / mmol-Pd.
The obtained polymer was easily dissolved in a general solvent such as THF and chloroform, the number average molecular weight was Mn = 402,800, and the molecular weight distribution was Mw / Mn = 3.22. The composition of 2-acetoxymethyl-5-norbornene monomer unit in the polymer calculated from the integral value of ¹ H-NMR was 34.1 mol%.

Example 6: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene 2-acetoxy prepared in Synthesis Example 1 with a solution of norbornene (38.04 g, 0.404 mol) dissolved in 44.0 ml of toluene in a dropping funnel Methyl-5-norbornene (33.58 g, 0.202 mol) and ethyl acetate (190 ml) were added, it was added dropwise over 200 minutes, and after completion of the addition, the reaction was further carried out at 80 ° C. for 10 minutes. Polymerization was carried out in the same manner as in Example 4 except that the time was 4 hours to obtain 68.10 g of a white powdery polymer. The catalytic activity calculated from the polymer yield and the amount of charged catalyst was 6810 g-polymer / mmol-Pd.
The obtained polymer was easily dissolved in a general solvent such as THF and chloroform, the number average molecular weight was Mn = 332,300, and the molecular weight distribution was Mw / Mn = 3.33. The composition of 2-acetoxymethyl-5-norbornene monomer unit in the polymer calculated from the integral value of ¹ H-NMR was 38.9 mol%.

Comparative Example 2: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene (polymerization with n-hexane solvent)
A three-necked flask equipped with a three-way cock and a mechanical stirrer was purged with nitrogen, and norbornene (4.71 g, 0.050 mol) manufactured by Tokyo Chemical Industry Co., Ltd. and 2-acetoxymethyl-5-norbornene (16. 62 g, 0.100 mol) was added and dissolved in 100 ml of n-hexane, and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate [(C ₆ H ₅ ) (CH ₃ ) ₂ NH] [B (C ₆ F ₅ ) ₄ ] (manufactured by Strem, 8.0 mg, 0.010 mmol) was added in 1 ml of dichloromethane, and the mixture was heated to 90 ° C. (Π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium [complex A-1] (4.3 mg, prepared in Example 1 and prepared in a separate container) 0.010 mmol) and triisopropylphosphine [P (i-C ₃ H ₇ ) ₃ ] (Strem, 1.6 mg, 0.010 mmol) dissolved in 3.5 ml of toluene were added, and the mixture was added at 90 ° C. The polymerization reaction was performed for 30 minutes. The polymer precipitated as a white solid immediately after the start of the polymerization, but adhered to the flask wall due to the solid surface stickiness. Then, the solution which melt | dissolved norbornene (Tokyo Chemical Industry Co., Ltd. make, 4.71 g, 0.050 mol) separately prepared in the reaction solution with 5.4 ml of toluene was added to the reaction solution, and also the polymerization reaction was performed at 90 degreeC for 30 minutes. At this point, the polymer became sticky lump and entangled with the stirring blade. After completion of the reaction, 8 ml of methanol to which a small amount of hydrochloric acid was added was added to the reaction solution, the reaction was stopped, toluene was added to dissolve the polymer, and the solution was poured into a large amount of methanol to precipitate the polymer, followed by filtration. After washing, it was dried at 90 ° C. under reduced pressure for 5 hours to obtain 12.10 g of a white powdery polymer. The catalytic activity calculated from the polymer yield and the amount of charged catalyst was 1210 g-polymer / mmol-Pd.
The obtained polymer was easily dissolved in a general solvent such as THF and chloroform, the number average molecular weight was Mn = 24,000, and the molecular weight distribution was Mw / Mn = 2.46. The composition of 2-acetoxymethyl-5-norbornene monomer unit in the polymer calculated from the integral value of ¹ H-NMR was 24.3 mol%.

Example 7: Addition copolymerization of norbornene and 2-acetoxymethyl-5-norbornene using Ni catalyst A 300 ml three-necked flask equipped with a three-way cock and a mechanical stirrer was purged with nitrogen, and then norbornene (Tokyo Chemical Industry Co., Ltd.) Product, 9.6 g, 0.102 mol) dissolved in 11.1 ml of toluene and 2-acetoxymethyl-5-norbornene (17.1 g, 0.103 mol) and 60 ml of ethyl acetate (manufactured by Showa Denko KK) were added. . On the other hand, in a 20 mL glass ampoule under nitrogen, bis (acetylacetonato) nickel (10.3 mg, 40 μmol), tris (pentafluorophenyl) boron [B (C ₆ F ₅ ) ₃ ] (61.0 mg, 120 μmol) And trimethylaluminum (manufactured by Aldrich, 2.0 M toluene solution, 0.10 ml, 200 μmol) were dissolved in 4 ml of dehydrated toluene, and the whole amount was immediately added to a three-necked flask to initiate polymerization. During the polymerization, the polymer precipitated as a white powder. The polymerization was carried out at room temperature for 30 minutes, and 8 ml of methanol added with a small amount of hydrochloric acid was added to the reaction solution to stop the reaction. The precipitated polymer was washed by filtration and then dried at 90 ° C. under reduced pressure for 5 hours to obtain 8.9 g of a white powdery polymer.
The obtained polymer is easily dissolved in common organic solvents such as THF and chloroform, the number average molecular weight is Mn = 687,000, and the molecular weight distribution between the weight average molecular weight Mw and the number average molecular weight Mn is Mw / Mn = 1. .99. The composition of 2-acetoxymethyl-5-norbornene monomer unit in the polymer calculated from the integral value of 1H-NMR was 26.0 mol%.

For Examples 1 to 7 and Comparative Examples 1 and 2, the catalyst type, polymerization conditions, etc. are shown in Table 1, and the polymerization results are shown in Table 2. The meaning of each symbol in Table 1 is as follows.
Metal complex (A):
A-1: (π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium,
S-1: Bis (acetylacetonato) nickel promoter (B):
B-1: N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
B-2: Tris (pentafluorophenyl) boron,
B-3: Trimethylaluminum.
Phosphine-based ligand (C):
C-1: triisopropylphosphine,
monomer:
NB: Norbornene,
ANB: 2-acetoxymethyl-5-norbornene.
In addition, all the polymers obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were easily dissolved in a general solvent such as THF and chloroform.

In the polymerization of Comparative Example 1, although a norbornene copolymer having a large molecular weight can be obtained, a large amount (usually 5 to 10 times) of methanol is required for the polymerization solvent to recover the polymer.
In Comparative Example 2 using n-hexane, which is a precipitation polymerization solvent described in the prior art document (International Publication No. 08/069568 pamphlet), the produced polymer adheres to the stirring blade, and the handling property of the polymer recovery is not good. It was.
In Examples 1 to 7 in which acetate was used as the polymerization solvent, the produced polymer precipitated in a powder form and could be easily recovered regardless of the catalyst type.

  According to the production method of the present invention, it is possible to efficiently produce a norbornene-based (co) polymer having excellent transparency, heat resistance, low water absorption, electrical insulation characteristics, and the like, and the production cost can be reduced. Become.

Claims (7)

A method for producing a norbornene (co) polymer by precipitation polymerization using a liquid that dissolves a norbornene monomer and does not dissolve a polymer of the monomer as a solvent, wherein the precipitation polymerization solvent is an aliphatic carboxylic acid ester. see containing the norbornene-based (co) polymer has the general formula (2)

And general formula (3)

(In the formula, R ¹² represents an alkyl group having 1 to 10 carbon atoms, and R ¹³ , R ¹⁴ , and R ¹⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
The manufacturing method of the norbornene-type (co) polymer characterized by including the monomer unit shown by these . The manufacturing method of the norbornene-type copolymer of Claim 1 which consists only of a monomer unit shown by General formula (2) and General formula (3). The method for producing a norbornene copolymer according to claim 1 or 2 , wherein the aliphatic carboxylic acid ester contained in the solvent for precipitation polymerization is 60% by volume or more. The method for producing a norbornene copolymer according to any one of claims 1 to 3 , wherein the aliphatic carboxylic acid ester is an ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms and an alcohol. The method for producing a norbornene copolymer according to any one of claims 1 to 3 , wherein the aliphatic carboxylic acid ester is an ester of an aliphatic carboxylic acid and an alcohol having 1 to 5 carbon atoms. The method for producing a norbornene copolymer according to any one of claims 1 to 5 , wherein the aliphatic carboxylic acid ester is at least one of ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate. The method for producing a norbornene copolymer according to any one of claims 1 to 6 , wherein the solvent for precipitation polymerization contains toluene and 60% by volume or more of ethyl acetate.