JP5007464B2 - Ring-opening metathesis polymerization catalyst and method for producing ring-opening metathesis polymer - Google Patents

Description

  The present invention relates to a novel ring-opening metathesis polymerization catalyst and a method for producing a ring-opening metathesis polymer in which cyclic olefins are subjected to ring-opening polymerization using the polymerization catalyst.

  Catalysts for ring-opening metathesis polymerization of cyclic olefins include transition metal compounds of Group 4 to 8 of the periodic table such as tungsten chloride, tungsten oxide chloride, molybdenum chloride, titanium chloride, or vanadium chloride, and organic aluminum and organic tin. A catalyst system comprising a combination with a promoter (or cocatalyst) such as a Lewis acid is known (see Non-Patent Document 1). However, in these catalyst systems, the structure of the catalytically active species is unclear, so that it is difficult to control the polymerization reaction. In addition, problems such as gelation of the polymer may occur.

On the other hand, unlike these conventional ring-opening metathesis polymerization catalysts, tungsten or molybdenum alkylidene complexes have been reported in which cyclic olefins are subjected to ring-opening metathesis polymerization without the need for the above-mentioned cocatalyst (Non-Patent Documents). 2). In these complex catalysts, since the structure of the catalytically active species is clear, the polymerization reaction can be controlled. However, these complex catalysts have problems such as difficulty in synthesis.
In recent years, unlike conventional ring-opening metathesis polymerization catalysts, a vanadium complex has been reported that undergoes ring-opening metathesis polymerization of cyclic olefins without the need for the above-mentioned promoter (see Patent Document 1). This complex catalyst is easy to synthesize and can be manufactured at a low cost, but has a problem in industrial implementation because of its extremely low catalytic activity.
Ivin, K .; J. et al. Olefin Metathesis; Academic Press: New York, 1983. Schrock, Richard R. , "Living Ring-Opening Metabolism Polymerization by Well-Characterized Transition-Metal Alkylidene Complexes"; Acc. Chem. Res. 158-165, 23, 1990 JP 2002-53647 A

  Therefore, a polymerization catalyst that can control ring-opening metathesis polymerization, has a sufficiently high catalytic activity, and can be produced industrially at low cost has not yet been found. An object of the present invention is to provide a ring-opening metathesis polymerization catalyst which can control ring-opening metathesis polymerization, has a sufficiently high catalytic activity and can be produced industrially at a low cost, and further a ring-opening metathesis polymer using the polymerization catalyst It is in providing the manufacturing method of.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a periodic group 5 transition metal complex having a specific structure is an extremely excellent ring-opening metathesis polymerization catalyst, and completes the present invention. It came to. That is, the present invention
[1] (A1) A ring-opening metathesis polymerization catalyst comprising a transition metal alkylidene complex represented by the following general formula (1).

(In the formula, M represents a transition metal of Group 5 of the periodic table. R ¹ represents an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and R ² represents an alkyl having 1 to 20 carbon atoms. , Aryl or an arylalkyl group, R ³ and R ⁴ each independently represents hydrogen, an alkyl, aryl, arylalkyl or alkylsilyl group having 1 to 20 carbon atoms, and R ³ , R ⁴ may be bonded to each other, and E represents a ligand composed of an electron-donating compound containing an amine, pyridine, phosphine, ether, or thioether.
[2] The ring-opening metathesis polymerization catalyst according to [1], wherein the transition metal M in the general formula (1) is vanadium.
[3] The ring-opening metathesis polymerization catalyst according to [2], wherein E in the general formula (1) is a ligand composed of an electron donating compound containing phosphine.
[4] (A2) a transition metal alkyl complex represented by the following general formula (2) and (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers It is a ring-opening metathesis polymerization catalyst characterized by including.

(In the formula, M represents a transition metal of Group 5 of the periodic table. R ⁵ represents an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and R ⁶ represents an alkyl having 1 to 20 carbon atoms. Represents an aryl or arylalkyl group, R ⁷ and R ⁸ each independently represents an alkyl having 1 to 20 carbon atoms or an arylalkyl group, and R ⁷ and R ⁸ are bonded to each other. May be.)
[5] (A3) a transition metal halogen complex represented by the following general formula (3), and (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers; (C) A ring-opening metathesis polymerization catalyst comprising an alkyl metal compound.

(In the formula, M represents a transition metal of Group 5 of the periodic table. R ⁹ represents an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and R ¹⁰ represents an alkyl having 1 to 20 carbon atoms. Represents an aryl group or an arylalkyl group, and X ¹ and X ² each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)
[6] A method for producing a ring-opening metathesis polymer, characterized by ring-opening polymerization of cyclic olefins using any of the ring-opening metathesis polymerization catalysts described above.

  According to the present invention, ring-opening metathesis polymerization can be controlled, and a ring-opening metathesis polymerization catalyst having a sufficiently high catalytic activity can be provided industrially at a lower cost than conventional methods. An industrially advantageous process for producing ring-opening metathesis polymers is provided.

Hereinafter, the present invention will be specifically described.

  In the transition metal alkylidene complex represented by (A1) general formula (1) of the present invention, M is a transition metal of Group 5 of the periodic table, more specifically, vanadium, niobium, or tantalum. is there. Of these periodic table Group 5 transition metals, vanadium is preferred.

R ¹ in the general formula (1) is an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and a part of these is a halogen atom, an oxygen atom, a nitrogen atom, or a silicon atom. May be substituted.

  Specific examples of alkyl include linear or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, and n-hexyl, and alicyclic alkyl such as cyclohexyl and adamantyl. Alkyl substituted with a halogen atom such as trifluoromethyl, trichloromethyl, tris (trifluoromethyl) methyl, 2,2,2-trichloroethyl, alkyl having a substituent containing an oxygen atom such as methoxymethyl, methoxyethyl, Examples include alkyl having a substituent containing a nitrogen atom such as dimethylaminomethyl and diethylaminomethyl, and alkyl having a substituent containing a silicon atom such as trimethylsilylmethyl and triethylsilylmethyl.

  Specific examples of aryl include phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-diphenylphenyl and other alkyl groups or aryl-substituted aryl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6- Aryl substituted with a halogen atom such as bis (trifluoromethyl) phenyl, Aryl having a substituent containing an oxygen atom such as 2,6-dimethoxyphenyl, Aryl having a substituent containing a nitrogen atom such as 4-dimethylaminophenyl And alkyl having a substituent containing a silicon atom such as 2,6-bis (trimethylsilyl) phenyl. That.

  Arylalkyl is alkyl in which part of the alkyl hydrogen atoms is substituted with aryl, and specific examples include phenylmethyl, diphenylmethyl, triphenylmethyl, and the like.

R ¹ is preferably aryl among these alkyls, aryls, or arylalkyls. Among the aryls, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6-bis (trifluoromethyl) phenyl, , 6-dimethoxyphenyl and 2,6-bis (trimethylsilyl) phenyl are more preferred.

Further, R ² in the general formula (1) is an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and a part of them is a halogen atom, an oxygen atom, a nitrogen atom, or a silicon atom. May be substituted. Specific examples of these groups include the same groups as those exemplified as specific examples of R ^{1 in} the general formula (1). R ² is preferably alkyl or aryl among these alkyl, aryl, or arylalkyl, and among them, t-butyl, cyclohexyl, tris (trifluoromethyl) methyl, 2,6-dimethylphenyl, 2,6 -Diisopropylphenyl, 2,6-di-t-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-bis (trifluoromethyl) phenyl 2,6-dimethoxyphenyl and 2,6-bis (trimethylsilyl) phenyl are more preferred.

R ³ and R ⁴ in the general formula (1) are each independently hydrogen, alkyl having 1 to 20 carbon atoms, aryl, arylalkyl, or alkylsilyl group, and some of these are It may be substituted with a halogen atom, an oxygen atom, a nitrogen atom, or a silicon atom. R ³ and R ⁴ may be bonded to each other. Specific examples of alkyl, aryl, and arylalkyl include the same groups as those exemplified as specific examples of R ^{1 in} the general formula (1).

  Specific examples of alkylsilyl include trimethylsilyl, triethylsilyl, tri-t-butylsilyl and the like.

Specific examples of the group in which R ³ and R ⁴ are bonded to each other include ethylene, butylene, hexylene, methylene-1,2-phenylene-methylene, and the like.
R ³ and R ⁴ are preferably hydrogen, alkyl having 1 to 20 carbon atoms, or alkylsilyl group among these hydrogen, alkyl having 1 to 20 carbon atoms, aryl, arylalkyl, or alkylsilyl groups. .

  Further, E is a ligand composed of an electron donating compound containing amine, pyridine, phosphine, ether, or thioether. These are coordinating compounds having a lone electron pair, and the catalyst is stabilized by coordinating to the transition metal M. Furthermore, it was found that the catalyst of the present invention in which E is coordinated has significantly higher catalytic activity than a catalyst that does not coordinate, and the living polymerization system can be controlled.

  Specific examples of the ligand comprising an electron-donating compound containing an amine include alkylamines such as trimethylamine, triethylamine, tri-n-butylamine and diisopropylethylamine, N, N-dimethylaniline, N, N Alkylarylamines such as 1,2,4,6-pentamethylaniline, arylamines such as triphenylamine, cyclic amines such as 1-methylpiperidine, N, N, N ′, N′-tetramethylethylenediamine, Examples include polyvalent amines such as 1,4-dimethylpiperazine.

  Specific examples of ligands composed of electron-donating compounds including pyridine include pyridine and, for example, 2,6-dimethylpyridine, 2,4-dimethylpyridine, 2,6-di-t-butyl. Examples thereof include substituted pyridines such as pyridine and 4- (dimethylamino) pyridine, and polyvalent pyridines such as bipyridine.

  Specific examples of the ligand composed of an electron-donating compound containing phosphine include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, -Substitution or absence of alkyl or alicyclic alkyl phosphines such as n-hexylphosphine and tricyclohexylphosphine, triphenylphosphine, tris (4-methoxyphenyl) phosphine, tris [4- (trifluoromethyl) phenyl] phosphine Examples thereof include substituted aryl phosphines and polyvalent phosphines such as 1,2-bis (diphenylphosphino) ethane.

  Specific examples of the ligand comprising an electron-donating compound containing ether include dialkyl ethers such as dimethyl ether and diethyl ether, alkylaryl ethers such as methylphenyl ether, diaryl ethers such as diphenyl ether, tetrahydrofuran, and the like. And cyclic ethers such as 1,4-dioxane, and polyvalent ethers such as 1,2-dimethoxyethane.

  Specific examples of ligands composed of electron-donating compounds including thioethers include dialkyl sulfides such as dimethyl sulfide, diethyl sulfide, and dibutyl sulfide, alkylaryl sulfides such as methylphenyl sulfide, and diphenyl sulfide. And cyclic sulfides such as diaryl sulfides, tetrahydrothiophene, and thiophene.

  A ligand composed of these electron donating compounds may be used alone or in combination of two or more. Among these ligands made of an electron donating compound containing amine, pyridine, phosphine, ether, or thioether, a ligand made of an electron donating compound containing amine, pyridine, or phosphine is preferable, and an electron containing phosphine A ligand composed of a donor compound is more preferable.

  In the transition metal alkyl complex represented by (A2) general formula (2) of the present invention, M is a transition metal of Group 5 of the periodic table, more specifically vanadium, niobium, or tantalum. is there. Of these periodic table Group 5 transition metals, vanadium is preferred.

R ⁵ in the general formula (2) is an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and a part of these is a halogen atom, an oxygen atom, a nitrogen atom, or a silicon atom. May be substituted. Specific examples of these groups include the groups exemplified as specific examples of R ^{1 in} the general formula (1). R ⁵ is preferably aryl among these alkyl, aryl, or arylalkyl. Among aryl, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6-bis (trifluoromethyl) phenyl, , 6-dimethoxyphenyl and 2,6-bis (trimethylsilyl) phenyl are more preferred.

Further, R ⁶ in the general formula (2) is an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and a part of these is a halogen atom, an oxygen atom, a nitrogen atom, or a silicon atom. May be substituted. Specific examples of these groups include the same groups as those exemplified as specific examples of R ^{1 in} the general formula (1). R ⁶ is preferably alkyl or aryl among these alkyl, aryl, or arylalkyl, and among them, t-butyl, cyclohexyl, tris (trifluoromethyl) methyl, 2,6-dimethylphenyl, 2,6 -Diisopropylphenyl, 2,6-di-t-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-bis (trifluoromethyl) phenyl 2,6-dimethoxyphenyl and 2,6-bis (trimethylsilyl) phenyl are more preferred.

In the general formula (2), R ⁷ and R ⁸ are each independently an alkyl having 1 to 20 carbon atoms or an arylalkyl group, and a part of these is a halogen atom, an oxygen atom, It may be substituted with a nitrogen atom or a silicon atom. R ⁷ and R ⁸ may be bonded to each other.

  Specific examples of the alkyl include linear or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and n-hexyl, alicyclic alkyl such as cyclohexyl, fluoromethyl, Alkyl substituted with a halogen atom such as chloromethyl, difluoromethyl, dichloromethyl, 2,2,2-trichloroethyl, alkyl having a substituent containing an oxygen atom such as methoxymethyl, methoxyethyl, dimethylaminomethyl, diethylaminomethyl, etc. And alkyl having a substituent containing a silicon atom such as trimethylsilylmethyl, triethylsilylmethyl, and the like.

  Specific examples of the arylalkyl include, for example, phenylmethyl, linear arylalkyl such as 2-phenylethyl and 3-phenylpropyl, 1-phenylethyl, 1-phenylpropyl and 1,1-diphenylmethyl. Branched arylalkyl such as (2,6-dimethylphenyl) methyl, (2,6-diisopropylphenyl) methyl, (2,6-di-t-butylphenyl) methyl, etc. Arylalkyl substituted with a halogen atom such as -1-phenylmethyl, (2,6-dichlorophenyl) methyl, 1-trifluoromethyl-1-phenylmethyl, [2,6-bis (trifluoromethyl) phenyl] methyl, 1-methoxy-1-phenylmethyl, (2,6-dimethoxyphenyl) methyl, etc. Arylalkyl having a substituent containing an oxygen atom, arylalkyl having a substituent containing a nitrogen atom such as 1-trimethylamino-1-phenylmethyl, [2,6-bis (trimethylamino) phenyl] methyl, 1-trimethylsilyl Examples thereof include arylalkyl having a substituent containing a silicon atom such as -1-phenylmethyl and [2,6-bis (trimethylsilyl) phenyl] methyl.

Specific examples of the group in which R ⁷ and R ⁸ are bonded to each other include ethylene, butylene, hexylene, methylene-1,2-phenylene-methylene, and the like.
R ⁷ and R ⁸ are preferably a linear or branched alkyl, an alkyl having a substituent containing a silicon atom, or a linear arylalkyl group among these alkyls having 1 to 20 carbon atoms or arylalkyl.

  (B) of the present invention is at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers. These are coordinating compounds having a lone pair of electrons, and have the feature that they can coordinate as a ligand E composed of an electron donating compound to a transition metal alkylidene complex formed from a transition metal alkyl complex. A catalyst is stabilized by coordinating to the transition metal alkylidene complex which these produced | generated. Furthermore, it was found that the catalyst of the present invention in which E is coordinated has significantly higher catalytic activity than a catalyst that does not coordinate, and the living polymerization system can be controlled.

    Specific examples of the amines include alkylamines such as trimethylamine, triethylamine, tri-n-butylamine, diisopropylethylamine, N, N-dimethylaniline, N, N, 2,4,6-pentamethylaniline. Alkyl arylamines such as triphenylamine, cyclic amines such as 1-methylpiperidine, N, N, N ′, N′-tetramethylethylenediamine, polyvalent such as 1,4-dimethylpiperazine Examples include amines.

  Specific examples of pyridines include pyridine, such as 2,6-dimethylpyridine, 2,4-dimethylpyridine, 2,6-di-t-butylpyridine, 4- (dimethylamino) pyridine, and the like. Substituted pyridines, and polyvalent pyridines such as bipyridine.

  Specific examples of phosphines include trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tri-n-hexylphosphine, and tricyclohexylphosphine. Substituted or unsubstituted aryl phosphines such as triphenylphosphine, tris (4-methoxyphenyl) phosphine, tris [4- (trifluoromethyl) phenyl] phosphine, 1,2-bis And polyvalent phosphines such as (diphenylphosphino) ethane.

  Specific examples of ethers include dialkyl ethers such as dimethyl ether and diethyl ether, alkylaryl ethers such as methylphenyl ether, diaryl ethers such as diphenyl ether, cyclic ethers such as tetrahydrofuran, 1,4- And polyvalent ethers such as dioxane and 1,2-dimethoxyethane.

  Specific examples of thioethers include dialkyl sulfides such as dimethyl sulfide, diethyl sulfide, and dibutyl sulfide, alkylaryl sulfides such as methylphenyl sulfide, diaryl sulfides such as diphenyl sulfide, tetrahydrothiophene, and thiophene. Examples thereof include cyclic sulfides.

  Of these amines, pyridines, phosphines, ethers, or thioethers, amines, pyridines, and phosphines are preferable, and phosphines are more preferable.

  In the transition metal halogen complex represented by (A3) general formula (3) of the present invention, M is a transition metal of Group 5 of the periodic table, more specifically, vanadium, niobium, or tantalum. is there. Of these periodic table Group 5 transition metals, vanadium is preferred.

R ⁹ in the general formula (3) is an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and a part of these is a halogen atom, an oxygen atom, a nitrogen atom, or a silicon atom. May be substituted. Specific examples of these groups include the same groups as those exemplified as specific examples of R ^{1 in} the general formula (1). R ⁹ is preferably aryl among these alkyls, aryls, or arylalkyls, and among aryls, phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6-bis (trifluoromethyl) phenyl, , 6-dimethoxyphenyl and 2,6-bis (trimethylsilyl) phenyl are more preferred.

Further, R ¹⁰ in the general formula (3) is an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and a part of them is a halogen atom, an oxygen atom, a nitrogen atom, or a silicon atom. May be substituted. Specific examples of these groups include the same groups as those exemplified as specific examples of R ^{1 in} the general formula (1). R ¹⁰ is preferably alkyl or aryl among these alkyl, aryl, or arylalkyl, and among them, t-butyl, cyclohexyl, tris (trifluoromethyl) methyl, 2,6-dimethylphenyl, 2,6 -Diisopropylphenyl, 2,6-di-t-butylphenyl, 2,4,6-trimethylphenyl, 2,6-di-t-butyl-4-methylphenyl, 2,6-bis (trifluoromethyl) phenyl 2,6-dimethoxyphenyl and 2,6-bis (trimethylsilyl) phenyl are more preferred.

X ¹ and X ² each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Of these, a chlorine atom is preferred.

  (B) used together with the transition metal halogen complex represented by formula (3) of the present invention (A3) is at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers. . Specific examples thereof include (A2) at least one compound selected from (B) amines, pyridines, phosphines, ethers, and thioethers used together with the transition metal alkyl complex represented by the general formula (2). Specific examples of the compound can be exemplified. Of these amines, pyridines, phosphines, ethers, or thioethers, amines, pyridines, and phosphines are preferable, and phosphines are more preferable.

  As the metal of the (C) alkyl metal compound of the present invention, a metal belonging to Group 1 of the periodic table, specifically lithium, sodium, etc., or a metal belonging to Group 2 of the periodic table, specifically magnesium, etc. Periodic table group 12 metals, specifically zinc, etc., or periodic table group 13 metals, specifically aluminum, or periodic table group 14 metals, specifically tin, etc. Can be mentioned. The alkyl group in the alkyl metal compound may be linear, branched or cyclic, and an aryl group or a halogen atom may be substituted. Further, it may be substituted with a halogen atom, an oxygen atom, a nitrogen atom, or a silicon atom. These alkyl metal compounds may be used alone or in combination of two or more.

  Specific examples of these alkyl metal compounds include alkyl lithiums such as methyl lithium, n-butyl lithium, isobutyl lithium, benzyl lithium and (trimethylsilyl) methyl lithium, and alkyl such as n-butyl sodium and benzyl sodium. Sodium, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, phenylmethylmagnesium chloride, phenylmethylmagnesium bromide, neopentylmagnesium chloride, neopentylmagnesium bromide and other alkylmagnesium halides, dimethylmagnesium, diethylmagnesium Dialkyl magnesiums such as dimethyl zinc, diethyl zinc, etc. Zinc compounds, trimethyl aluminum, triethyl aluminum, tri-alkyl aluminum such as tri-isobutyl aluminum, tetramethyl tin, tetra-alkyl tin such as tetrabutyl tin and the like. Of these alkyl metal compounds, alkyl lithiums, alkyl magnesium halides, trialkyl aluminums, and tetraalkyl tins are preferable, and alkyl lithiums and alkyl magnesium halides are more preferable.

Specific examples of the transition metal alkylidene complex include V (CHSiMe ₃ ) (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ -C ₆ H ₃ ) (PMe _{3), V (CHSiMe 3)} (N-2,6- i Pr 2 -C 6 H 3) (O-2,6- i Pr 2 -C 6 H 3) (PMe 3), V (CHSiMe 3) ^{_{(N-2,6-Me 2 -C}} 6 H 3) (O-2,6- t Bu 2 -C 6 H 3) (PMe 3), V (CHSiMe 3) (N-2,6-Me 2 ^{_{-C 6 H 3) (O-}} 2,6- i Pr 2 -C 6 H 3) (PBu 3), and _{V (CH 2) (N-} 2,6-Me 2 -C 6 H 3) (O ^{_{-2,6- i Pr 2 -C 6 H 3}} ) (PMe 3) , and the like. Furthermore, compounds in which the central metal M of these compounds is substituted from vanadium to niobium or tantalum can be exemplified as specific examples.

Specific examples of the transition metal alkyl complex include, for example, V (CH ₂ SiMe ₃ ) ₂ (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ -C ₆ H _{3 ^{), V (CH 2 SiMe 3}} ) 2 (N-2,6- i Pr 2 -C 6 H 3) (O-2,6- i Pr 2 -C 6 H 3), V (CH 3) 2 ( ^{_{N-2,6-Me 2 -C 6}} H 3) (O-2,6- i Pr 2 -C 6 H 3), V (CH 2 Ph) 2 (N-2,6-Me 2 C 6 H ^{_{3) (O-2,6- i Pr}} 2 -C 6 H 3), and _{V (CH 2 Ph) 2 (} N-2,6-Me 2 C 6 H 3) (O-2,6- t Bu _{2 -4-Me-C 6 H} 2) , and the like. Furthermore, compounds in which the central metal M of these compounds is substituted from vanadium to niobium or tantalum can be exemplified as specific examples.

Specific examples of the transition metal halogen complex include VCl ₂ (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ -C ₆ H ₃ ), VCl ₂ (N ^{_{-2,6- i Pr 2 -C 6 H 3}} ) (O-2,6- i Pr 2 -C 6 H 3), VCl 2 (N-2,6-Me 2 -C 6 H 3) (O ^{_{-2,6- t Bu 2 -C 6 H 3}} ), VCl 2 (N-2,6- i Pr 2 -C 6 H 3) (O-2,6- t Bu 2 -C 6 H 3), And VCl ₂ (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ^t Bu ₂ -4-Me-C ₆ H ₂ ) and the like. Furthermore, compounds in which the central metal M of these compounds is substituted from vanadium to niobium or tantalum can be exemplified as specific examples.

  The catalyst of the present invention may be a transition metal alkylidene complex of the present invention in which a coordination compound such as amines, pyridines, phosphines, ethers, or thioethers is previously coordinated, or polymerization. In this case, the transition metal alkyl complex of the present invention and the above coordinating compound are combined, or the transition metal halogen complex of the present invention, the above coordinating compound and the alkyl metal compound are combined and added together with the monomer. It may be a form.

  Here, (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers is mixed with a transition metal alkyl complex represented by (A2) general formula (2). When used in polymerization, it is considered that a catalyst corresponding to (A1) general formula (1) is formed under the conditions of the polymerization reaction. Similarly, when (B) is used in combination with (A3) a transition metal halogen complex represented by general formula (3) and (C) an alkyl metal compound, (A2) in general formula (2) It is considered that a catalyst corresponding to (A1) general formula (1) is formed under the polymerization reaction conditions through the generation of the transition metal alkyl complex represented.

  The method for preparing the transition metal alkylidene complex represented by (A1) general formula (1) of the present invention is not particularly limited, but (A2) a transition metal alkyl complex represented by general formula (2) and (B) amine Or at least one compound selected from pyridines, phosphines, ethers and thioethers, or (A3) a transition metal halogen complex represented by the general formula (3) and (B) amines In addition, at least one compound selected from pyridines, phosphines, ethers, and thioethers and (C) an alkyl metal compound may be mixed to prepare. The preparation temperature at this time is 0-150 degreeC, Preferably it is 20-100 degreeC. The preparation time is preferably about 0.1 to 50 hours.

  (A2) The transition metal alkyl complex represented by the general formula (2) of the present invention and (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers. In the ring-opening metathesis polymerization catalyst characterized by the above, the molar ratio represented by (A2) / (B) is usually 100/1 to 1/1000, preferably 10/1 to 1/100, and more Preferably it is 5/1-1/10. When the ratio (A2) / (B) is within the above range, it is possible to achieve good catalytic activity.

  (A3) the transition metal halogen complex represented by the general formula (3) of the present invention, and (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers; C) In the ring-opening metathesis polymerization catalyst characterized by containing an alkyl metal compound, the molar ratio represented by (A3) / (B) is usually 100/1 to 1/1000, preferably 10 / 1 to 1/100, more preferably 5/1 to 1/10. When the ratio (A3) / (B) is within the above range, it is possible to achieve good catalytic activity.

  The molar ratio represented by (A3) / (C) is usually 2/1 to 1/100, preferably 1/1 to 1/50, more preferably 1/2 to 1/10. Is done. When the ratio (A3) / (C) is within the above range, it is possible to achieve good catalytic activity.

  The cyclic olefins that can be subjected to ring-opening polymerization using the ring-opening metathesis polymerization catalyst in the present invention are not particularly limited as long as they are olefins having a cyclic structure, but usually a monocyclic ring having 3 to 40 carbon atoms. And cyclic cycloalkenes, monocyclic cycloalkadienes, polycyclic cycloalkenes, and polycyclic cycloalkadienes. Further, these cyclic olefins may have a substituent containing an oxygen atom, a sulfur atom or a nitrogen atom, a hydrocarbon group or a halogen atom.

Among these substituents, specific examples of the substituent containing an oxygen atom include a substituent such as an alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group, such as a phenoxy group and a 2,6-dimethylphenoxy group. An unsubstituted phenoxy group, for example, an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group, an oxo group (—O— group) and the like can be mentioned.
Specific examples of the substituent containing a sulfur atom include thioalkoxy groups such as thiomethoxy group and thiobutoxy group, substituted or unsubstituted thiophenoxy groups such as thiophenoxy group and 2-methylthiophenoxy group, such as methoxythiocarbonyl. And a thioalkoxycarbonyl group such as a group, and a sulfide group (—S— group).

Specific examples of the substituent containing a nitrogen atom include alkylamino groups having 1 to 20 carbon atoms such as a methylamino group, a dimethylamino group, and a diethylamino group, such as substituted or unsubstituted arylamino groups such as a diphenylamino group. Examples thereof include N-substituted or unsubstituted aminocarbonyl groups such as aminocarbonyl group and N-methylaminocarbonyl group, and cyano groups.
Specific examples of the hydrocarbon group include groups exemplified as specific examples of the alkyl, aryl and arylalkyl groups having 1 to 20 carbon atoms represented by R ¹ in the general formula (1), vinyl group, and vinylidene. And unsaturated hydrocarbon groups such as a group.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
These substituents may substitute a part of the hydrogen atoms of the cyclic olefins, or substitute a part of the hydrocarbon groups of the cyclic olefins like the compound represented by the formula (4). It may be.

  Specific examples of monocyclic cycloalkenes having no substituent include cyclobutene, cyclopentene, cyclohexene, cyclooctene and the like.

  Specific examples of the monocyclic cycloalkadiene having no substituent include, for example, cyclobutadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cycloocta Examples include dienes.

  Examples of the polycyclic cycloalkene having no substituent include norbornene and tetracyclo [6.2.1.1/3, 6.0 / 2.7] dodec-4-ene.

  Examples of the polycyclic cycloalkadiene having no substituent include norbornadiene and dicyclopentadiene.

  Specific examples of monocyclic cycloalkenes having substituents, monocyclic cycloalkadienes, polycyclic cycloalkenes and polycyclic cycloalkadienes include, for example, monocyclics having no substituent as described above. Hydrogen atoms or hydrocarbon groups of the compounds mentioned as specific examples of the formula cycloalkenes, monocyclic cycloalkadienes, polycyclic cycloalkenes and polycyclic cycloalkadienes are oxygen atoms, sulfur atoms Or a compound substituted with a substituent containing a nitrogen atom, a hydrocarbon group or a halogen atom, and more specifically, a cyclic olefin having a substituent containing an oxygen atom such as 5-methoxynorbornene, for example, 5 -Cyclic olefins having a substituent containing a sulfur atom such as thiomethoxynorbornene, for example, a nitrogen atom such as 5-cyanonorbornene Cyclic olefins having no substituent, for example, 7-methyl norbornene, 5-cyclic olefins having a hydrocarbon group such as vinyl norbornene, cyclic olefins include having, for example, 5,5-halogen atom, such as dichloro-norbornene.

  In the ring-opening polymerization of the cyclic olefins of the present invention, a mixture of two or more of the compounds exemplified above can be copolymerized.

  Furthermore, for the purpose of adjusting the molecular weight by chain transfer, cyclic olefins can be subjected to ring-opening polymerization in the presence of chain olefins. Specific examples of the chain olefin in this case include α-olefins, dienes, silicon-containing olefins, aromatic vinyl compounds, and (meth) acrylic acid esters. More specifically, examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, hexene, and 1-octene, and examples of the diene include pentadiene, hexadiene, and octadiene as the silicon-containing olefin. For example, vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane and the like, aromatic vinyl compounds such as styrene and divinylbenzene, and (meth) acrylic acid esters such as methyl methacrylate, methyl acrylate and ethyl methacrylate. Etc.

  In the ring-opening polymerization of the cyclic olefins of the present invention, (A1) a transition metal alkylidene complex represented by the general formula (1), (A2) a transition metal alkyl complex represented by the general formula (2), or (A3) The usage-amount of the cyclic olefin with respect to the transition metal halogen complex represented by General formula (3) is 10-100,000 by molar ratio, Preferably it is 50-20,000. This polymerization can be carried out without a solvent, but a solvent may be used. Solvents used include ether solvents such as tetrahydrofuran, diethyl ether and dioxane, aromatic hydrocarbon solvents such as benzene, toluene, xylene and ethylbenzene, and aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane. Solvent, aliphatic cyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, decalin, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, tetrachloroethane, chlorobenzene, trichlorobenzene, etc., and two or more of these May be used in combination.

  The method for ring-opening polymerization of cyclic olefins in the present invention is not particularly limited, and any of batch, semi-batch and continuous flow methods may be used. When a solvent is used in the polymerization reaction, the concentration of cyclic olefins is in the range of 0.01 to 100 mol / L.

  In the ring-opening polymerization of the cyclic olefins of the present invention, the transition metal alkylidene complex represented by the general formula (1) of the present invention (A1) in which ligands composed of different types of electron donating compounds are coordinated Two or more ring-opening metathesis polymerization catalysts may be used in combination. Moreover, the temperature at the time of performing a polymerization reaction is the range of -30-150 degreeC, Preferably it is the range of 0-100 degreeC.

  The (A2) transition metal alkyl complex represented by the general formula (2) of the present invention and (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers. The temperature at which the polymerization reaction is carried out using the resulting ring-opening metathesis polymerization catalyst is in the range of 0 to 150 ° C, preferably in the range of 20 to 100 ° C.

  And (A3) the transition metal halogen complex represented by the general formula (3) of the present invention, and (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers, (C) The temperature at which the polymerization reaction is carried out using a ring-opening metathesis polymerization catalyst comprising an alkyl metal compound is in the range of 0 to 150 ° C, preferably in the range of 20 to 100 ° C. The polymerization time is in the range of 0.1 to 50 hours. The pressure during the polymerization reaction can be any of reduced pressure, normal pressure or increased pressure. Furthermore, aldehydes, ketones, alcohols, water and the like may be used to stop the polymerization reaction.

  Examples of the method for separating the polymer after the ring-opening polymerization in the present invention include a method in which the polymer is precipitated by adding the polymerization reaction solution to a poor solvent such as alcohol or water, and the polymer is recovered by filtration or centrifugation. Can do. The present invention will be described in detail by the following examples, but the present invention is not limited to these examples.

  Regarding the average molecular weight of the polymers shown in the examples, the obtained ring-opening metathesis polymer was dissolved in tetrahydrofuran, SCL-10A and RID-10A manufactured by Shimadzu Corporation as GPC detectors, and ShimPAC GPC-806 as columns. 804 and 802 were used, and measurement was performed at 40 ° C. under a flow rate of 1.0 mL / min. The measured value is a value calibrated with polystyrene standards.

[Complex Synthesis Example 1]
_{(V (CHSiMe 3) (N} -2,6-Me 2 -C 6 H 3) (O-2,6- i Pr 2 -C 6 H 3) ( Synthesis of _{PMe 3) 0.89)
VCl 2 (N-2,6-Me} 2 -C 6 H 3) (O-2,6- i Pr 2 -C 6 H 3) (Macromoleculs, pp 1583-1590, Vol. 35, according to the method described in 2002 Synthesis) An n-hexane solution of LiCH ₂ SiMe ₃ (2.48 mmol) was added dropwise at −25 ° C. to an n-hexane solution (75 mL) containing (1.18 mmol). The reaction mixture was gradually warmed to room temperature and then stirred for 6 hours. After completion of the reaction, the reaction mixture was filtered through Celite, and the solvent was distilled off to remove V (CH ₂ SiMe ₃ ) ₂ (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr the ₂ -C ₆ H ₃₎ was obtained as a dark red solid. The structure of this alkyl complex was confirmed by ¹ H-NMR and ⁵¹ V-NMR, and subjected to the next reaction without purification.
The resulting _{V (CH 2 SiMe 3) 2} (N-2,6-Me 2 -C 6 H 3) (O-2,6- i Pr 2 -C 6 H 3) of dark red solid benzene (15mL ), PMe ₃ (5.9 mmol) was further added, and the mixture was heated at 80 ° C. for 40 hours. The reaction mixture was filtered through celite, the solvent was evaporated, and recrystallization from n-hexane gave red microcrystals. Elemental analysis and V (CHSiMe the red crystallites _{V (CHSiMe 3) (N-} 2,6-Me 2 -C 6 H 3) (O-2,6- i Pr 2 -C 6 H 3) ₃ ) A mixture of (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ -C ₆ H ₃ ) (PMe ₃ ), wherein the former complex and the latter complex The abundance ratio was 0.11 / 0.89 in molar ratio. Hereinafter, this complex is expressed as V (CHSiMe ₃ ) (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ -C ₆ H ₃ ) (PMe ₃ ) _0.89 . . ¹ H-NMR, ⁵¹ V-NMR and ³¹ P-NMR of this complex were as follows.
¹ H-NMR (C ₆ D ₆ ): 0.27, 0.40 (s, 9H, CHSi (CH ₃ ) ₃ ), 0.90 (br, PMe ₃ ), 1.18, 1.34 (d _{, 12H, (CH 3) 2} CH -), 2.74,2.83 (s, 6H, N-2,6-Me 2 -C 6 H 3), 3.37,3.83 (br, m , Me ₂ CCH-), 6.78 (t), 6.97 (t), 7.06 (d), 7.24 (d), 16.08, 16.37 (br, 1H, CHSiMe ₃ ).
⁵¹ V-NMR (C ₆ D ₆ ): −108, −58 ppm
³¹ P-NMR (C ₆ D ₆ ): −10.6 ppm (br)

[Example 1]
V (CHSiMe ₃ ) (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ -C ₆ H ₃ ) (PMe ₃ ) _0.89 was weighed out in 5.0 mg (10 μmol) and dissolved in 1.0 mL of benzene to prepare a polymerization catalyst solution (a). After weighing 200 mg (2.12 mol) of norbornene in a 50 mL pressure-resistant glass container and dissolving it in 9.5 mL of benzene, 0.1 mL of the above-mentioned polymerization catalyst solution (1.0 μmol as a vanadium complex) is added, and 1 at 80 ° C. Time reaction was performed. After adding benzaldehyde (10.4 mg, 0.098 mmol) and stirring for 30 minutes, the polymerization solution was added to 100 mL of methanol with stirring to precipitate the polymer. Filtration and drying were performed to obtain 131 mg (produced polymer mass / charged monomer mass; yield 66 wt%) of a white solid. ^{As a result of 1} H-NMR and ¹³ C-NMR measurements, this white solid was a norbornene ring-opening metathesis polymer. When the obtained polymer was subjected to GPC analysis, the chromatogram was unimodal, the number average molecular weight (Mn) was 484,000, the weight average molecular weight (Mw) was 900,000, and the molecular weight distribution (Mw / Mn) was 1.86. The turnover number (hereinafter abbreviated as TON. TON = (consumed norbornene (mmol)) / (calculated vanadium complex (mmol))), which was an index of polymerization activity, was 1391.

[Example 2]
V (CHSiMe ₃ ) (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ -C ₆ H ₃ ) (PMe ₃ ) _0.89 was weighed out in 5.0 mg (10 μmol) and dissolved in 1.0 mL of benzene to prepare a polymerization catalyst solution (a). After weighing 399 mg (4.24 mol) of norbornene in a 50 mL pressure-resistant glass container and dissolving it in 4.7 mL of benzene, 0.1 mL of the above-mentioned polymerization catalyst solution (1.0 μmol as a vanadium complex) was added, and the mixture was stirred at room temperature for 1 hour. Reaction was performed. After adding benzaldehyde (10.4 mg, 0.098 mmol) and stirring for 30 minutes, the polymerization solution was added to 100 mL of methanol with stirring to precipitate the polymer. Filtration and drying yielded 14 mg (yield 3.5 wt%) of a ring-opening metathesis polymer. When the obtained polymer was subjected to GPC analysis, the chromatogram was unimodal, the number average molecular weight (Mn) was 28,400, the weight average molecular weight (Mw) was 31,000, and the molecular weight distribution (Mw / Mn) was 1.09. The TON was 149.

[Example 3]
The same operation as in Example 2 was carried out except that the reaction time was 2 hours, and 24 mg (yield 6.0 wt%) of a ring-opening metathesis polymer was obtained. When the obtained polymer was subjected to GPC analysis, the chromatogram was unimodal, the number average molecular weight (Mn) was 43,600, the weight average molecular weight (Mw) was 48,000, and the molecular weight distribution (Mw / Mn) was 1.10. The TON was 255.

[Example 4]
The same operation as in Example 2 was conducted except that the reaction time was 3 hours, and 37 mg (yield 9.3 wt%) of a ring-opening metathesis polymer was obtained. When the obtained polymer was subjected to GPC analysis, the chromatogram was unimodal, the number average molecular weight (Mn) was 60,900, the weight average molecular weight (Mw) was 67,000, and the molecular weight distribution (Mw / Mn) was 1.10. The TON was 393.

[Example 5]
The same operation as in Example 2 was performed except that the reaction time was changed to 6 hours. As a result, 66 mg (yield 17 wt%) of a ring-opening metathesis polymer was obtained. When the obtained polymer was subjected to GPC analysis, the chromatogram was unimodal, the number average molecular weight (Mn) was 94,800, the weight average molecular weight (Mw) was 110,000, and the molecular weight distribution (Mw / Mn) was 1.16. The TON was 701.

[Example 6]
The same operation as in Example 2 was carried out except that the reaction time was 10 hours. As a result, 126 mg (yield 32 wt%) of a ring-opening metathesis polymer was obtained. When the obtained polymer was subjected to GPC analysis, the chromatogram was unimodal, the number average molecular weight (Mn) was 138,000, the weight average molecular weight (Mw) was 170,000, and the molecular weight distribution (Mw / Mn) was 1.23. The TON was 1338.

[Comparative Example 1]
In a glove box, 235 mg (2.50 mmol) of norbornene was weighed into a 10 mL eggplant type flask and dissolved in 2.9 g of toluene. Toluene containing 13.2 mg (25 μmol) of V (CH ₂ Ph) ₂ (N-2,6-Me ₂ -C ₆ H ₃ ) (O-2,6- ⁱ Pr ₂ -C ₆ H ₃ ) in this solution 1.0 g of solution was added. After stirring at room temperature for 11 hours, the resulting reaction solution was poured into methanol to precipitate the polymer. Filtration and drying yielded 87 mg (yield 37 wt%) of the ring-opening metathesis polymer. When the obtained polymer was subjected to GPC analysis, the number average molecular weight (Mn) was 2,430,000, the weight average molecular weight (Mw) was 4,690,000, and the molecular weight distribution (Mw / Mn) was 1. 93. TON was 37 and the polymerization activity was low.

From the above results, it can be seen that the catalyst of the present invention has significantly higher polymerization activity than the catalyst of Comparative Example 1. Further, as shown in FIG. 1, the molecular weight distribution (Mw / Mn) of the produced polymer is about 1, which is kept almost constant with respect to the polymer yield. That is, it became clear that the polymerization is highly controlled by the coordination of PMe ₃ and high living polymerizability is achieved.

  It can be used as a polymerization catalyst suitable for production of a ring-opening metathesis polymer resin useful for optical resins and the like.

It is a graph which shows the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the production | generation polymer with respect to a polymer yield. In the figure, diamond (♦) points represent Mn, and square (■) points represent Mw / Mn.

Claims (6)

(A1) A ring-opening metathesis polymerization catalyst containing a transition metal alkylidene complex represented by the following general formula (1).

(In the formula, M represents a transition metal of Group 5 of the periodic table. R ¹ represents an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and R ² represents an alkyl having 1 to 20 carbon atoms. , Aryl or an arylalkyl group, R ³ and R ⁴ each independently represents hydrogen, an alkyl, aryl, arylalkyl or alkylsilyl group having 1 to 20 carbon atoms, and R ³ , R ⁴ may be bonded to each other, and E represents a ligand composed of an electron-donating compound containing an amine, pyridine, phosphine, ether, or thioether. The ring-opening metathesis polymerization catalyst according to claim 1, wherein the transition metal M in the general formula (1) is vanadium. The ring-opening metathesis polymerization catalyst according to claim 2, wherein E in the general formula (1) is a ligand comprising an electron donating compound containing phosphine. (A2) Ring opening comprising a transition metal alkyl complex represented by the following general formula (2) and (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers Metathesis polymerization catalyst.

(In the formula, M represents a transition metal of Group 5 of the periodic table. R ⁵ represents an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and R ⁶ represents an alkyl having 1 to 20 carbon atoms. Represents an aryl or arylalkyl group, R ⁷ and R ⁸ each independently represents an alkyl having 1 to 20 carbon atoms or an arylalkyl group, and R ⁷ and R ⁸ are bonded to each other. May be.) (A3) a transition metal halogen complex represented by the following general formula (3); (B) at least one compound selected from amines, pyridines, phosphines, ethers, and thioethers; and (C) A ring-opening metathesis polymerization catalyst comprising an alkyl metal compound.

(In the formula, M represents a transition metal of Group 5 of the periodic table. R ⁹ represents an alkyl, aryl, or arylalkyl group having 1 to 20 carbon atoms, and R ¹⁰ represents an alkyl having 1 to 20 carbon atoms. Represents an aryl group or an arylalkyl group, and X ¹ and X ² each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.) The manufacturing method of the ring-opening metathesis polymer which ring-opening-polymerizes cyclic olefins using the ring-opening metathesis polymerization catalyst in any one of Claims 1-5.

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