JP2003252999A - Ferrocenylene silylene polymer having functional group and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ferrocenylene silylene polymer having an amide functional group, which has been difficult to synthesize, and its manufacturing method. <P>SOLUTION: This ferrocenylene silylene polymer has a repeating unit represented by general formula (1) (wherein R<SP>1</SP>and R<SP>2</SP>represent each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, aralkyl group, or the like, R<SP>3</SP>-R<SP>10</SP>represent each independently a hydrogen atom, alkyl group, aralkylsilyl group, or the like, and X represents a halogen atom). The manufacturing method of the ferrocenylene silylene polymer comprises cation ring- opening polymerization of a silaferrocenophane having an amide functional group, in the presence of a cation polymerization initiator. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ferrocenylene silylene polymer having an amide functional group on silicon, which is useful as a surface modifier of a metal electrode used in an electrochemical reaction, and a method for producing the same.

[0002]

2. Description of the Related Art Ferrocenylene silylene polymers having functional groups are compounds useful as surface modifiers for metal electrodes used in electrochemical reactions [Journal of the American Society].
rican Chemical Society), 101, 6501 (1979)
); Ibid., Vol. 100, p. 7264 (1978), etc.], and further applications as semiconductor materials, sensor materials and electrochromic materials are expected [Macromolecular.
Rapid Communications (Macromolecular Rapi
d Communications), Vol. 22, pp. 711 (1997); Chemical Communications,
857 (1999), etc.]. As a conventional method for producing a ferrocenylene silylene polymer, a method in which silaferrocenophanes are used as a monomer, and thermal ring-opening polymerization is performed under a high temperature condition of about 170 ° C., and an organolithium compound is used as a polymerization initiator. Methods such as anionic ring-opening polymerization of cenophans are known [Macromolecular Rapid Communications (Macromolecular Rapid
Communications), Vol. 22, pp. 711 (1997); Advances in Organometallic Chemistry (Advan
ces in Organometallic Chemistry), Vol. 37, p. 131 (1
995) etc.]. However, the thermal ring-opening polymerization makes it difficult to synthesize a ferrocenylene silylene polymer having a functional group such as an amide group because the functional group is decomposed by high heat. Further, in the anionic ring-opening polymerization, since an active lithium reactant is used, it is difficult to synthesize a ferrocenylene silylene polymer having a reactive functional group such as an amide group.

[0003]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, an object of the present invention is to provide a ferrocenylene silylene polymer having an amide functional group, which has been difficult to synthesize until now, and a method for producing the same. To do.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that silaferrocenophane having an amide group is subjected to cationic ring-opening polymerization in the presence of a cationic polymerization initiator. By doing so, it was found that a ferrocenylene silylene polymer having an amide group can be easily obtained in a high yield without damaging the functional group of the monomer, and the present invention has been completed. That is, the present invention provides the following general formula (1)

[Chemical 3] (In the formula, R ¹ and R ² are each independently a hydrogen atom,
Represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group which may have a substituent, and R ³ and R
⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group or a silyl group. Also,
R ¹ and R ² may be bonded to each other to form a ring with the adjacent atoms. X represents a halogen atom. ) Relates to a ferrocenylene silylene polymer having a repeating unit represented by

The present invention also provides the following general formula (2):

[Chemical 4] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ , R ¹⁰ and X are the same as defined above. In the presence of a cationic polymerization initiator, silaferrocenophane represented by
The present invention relates to a method for producing a ferrocenylene silylene polymer represented by the above general formula (1), which is characterized by carrying out cationic ring-opening polymerization.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
In the general formulas (1) and (2), the alkyl group represented by R ¹ and R ^2, which may have a substituent, has, for example, 1 to 20 carbon atoms, preferably 1 carbon atom. ~
10, more preferably a linear, branched or cyclic alkyl group of 1 to 6, and more specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group. , Secondary butyl group, tertiary butyl group, pentyl group, hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. In addition, examples of the alkenyl group of the alkenyl group which may have a substituent include those having an unsaturated group such as one or more double bonds in the above-mentioned alkyl group having 2 or more carbon atoms, More specifically, vinyl group, allyl group, 1
-Propenyl group, isopropenyl group, 2-butenyl group,
1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group,
A cyclohexenyl group etc. are mentioned. Further, the aryl group of the aryl group which may have a substituent is, for example, a monocyclic, polycyclic or condensed cyclic group having 6 to 30, preferably 6 to 20 and more preferably 6 to 14 carbon atoms. Examples thereof include aromatic hydrocarbon groups, and more specific examples thereof include phenyl group, tolyl group, xylyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group, and biphenyl group. Furthermore, the aralkyl group of the aralkyl group which may have a substituent has, for example, 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, and more preferably 7 to 1 carbon atoms.
The monocyclic, polycyclic or condensed ring aralkyl group of 5 is mentioned, and more specifically, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and the like can be mentioned.

As the substituents of these alkyl group, alkenyl group, aryl group and aralkyl group, any substituents may be used as long as they do not interfere with the reaction according to the present invention. For example, methoxy group, Alkoxy groups such as ethoxy group, isopropoxy group and tert-butoxy group, for example, alkylthio groups such as methylthio group and ethylthio group, for example trimethylsilyl group, triethylsilyl group,
trialkylsilyl groups such as t-butyldimethylsilyl group and triphenylsilyl group, for example, chlorine, bromine, fluorine,
Examples thereof include halogen atoms such as iodine. In addition, when R ¹ and R ² are bonded to each other to form a ring together with the adjacent atoms, specific examples of the ring include a 2-pyrrolidone ring and a 2-piperidone ring. To be

In the general formulas (1) and (2), R^Three,
R^Four, R⁵, R⁶, R⁷, R⁸, R ⁹And R¹⁰Represented by
Alkyl of an alkyl group which may have a substituent
Group and aralkyl group which may have a substituent
As the rukyl group, the above R¹, R^TwoSame as those in
And the substituents are also R¹, R^TwoThose in
The same thing as is mentioned. R^Three, R^Four, R⁵, R⁶, R
⁷, R⁸, R⁹And R¹⁰Represented by, having a substituent
The silyl group that may be substituted is a silyl group.
1 to 3 of the hydrogen atoms of
Some of them have been replaced, and among them, tri-substituted products are preferred.
More specifically, trimethylsilyl group, triethyl
Silyl group, t-butyldimethylsilyl group, triphenyl
Examples thereof include a silyl group. In general formulas (1) and (2)
And the halogen atom represented by X is fluorine atom.
Child, chlorine atom, bromine atom, iodine atom and the like.

In the production method of the present invention, the amide group-containing silaferrocenophan represented by the general formula (2) used as a starting material is chloro (halomethyl).
It can be easily synthesized by a known method of reacting silaferrocenophanes with N-silylamides [Proceedings of the 79th Annual Meeting of the Chemical Society of Japan, page 28, 1B447 (2
001) etc.].

Specific examples of the silaferrocenophane represented by the general formula (2) include, for example, 1,1'-ferrocenediyl [(N-methylacetylamino) methyl] chlorosilane, 1,1'-ferrocenediyl [ (N-methylacetylamino) methyl] iodosilane, 1,1′-ferrocenediyl [(N-methylacetylamino) methyl] fluorosilane, 1,1′-ferrocenediyl [(N-methylacetylamino) methyl] bromosilane, 1,1′-ferrocenediyl [(N-methylformylamino) methyl] chlorosilane, 1,1 ′-(2,4,5,2 ′, 4 ′, 5′-hexamethylferrocenediyl) [(N-methyl Acetylamino) methyl] chlorosilane, 1,1 '-(2,4,5-trimethylferrocenediyl) [(N-methylacetylamino) methyl] chlorosilane, 1,1'-(2,3,4,5-
Tetramethylferrocenediyl) [(N-methylacetylamino) methyl] chlorosilane, 1,1 ′-(2,3,
4,5,2 ′, 3 ′, 4 ′, 5′-octamethylferrocenediyl) [(N-methylacetylamino) methyl] chlorosilane, 1,1 ′-[2,4,5-tris (trimethylsilyl) ferrocene Diyl] [(N-methylacetylamino) methyl] chlorosilane, 1,1 '-[2,4,5,2',
4 ', 5'-hexakis (trimethylsilyl) ferrocenediyl] [(N-methylacetylamino) methyl] chlorosilane, N- [chloro (1,1'-ferrocenediyl)]
Silyl] methyl-2-pyrrolidone, N- [chloro (1,1 '
-Ferrocenediyl) silyl] methyl-2-piperidone,
1,1′-ferrocenediyl [(N-methylphenylcarbonylamino) methyl] chlorosilane, 1,1′-ferrocenediyl [(N-phenylphenylcarbonylamino) methyl] chlorosilane, 1,1′-ferrocenediyl [(N -Methylethenylcarbonylamino) methyl] chlorosilane, 1,1'-ferrocenediyl [(N-methylethylcarbonylamino) methyl] chlorosilane, 1,
1'-ferrocenediyl [(N-methylpropylcarbonylamino) methyl] chlorosilane, 1,1'-ferrocenediyl [(N-methylisopropylcarbonylamino)
Methyl] chlorosilane and the like.

As the cationic polymerization initiator used in the production method of the present invention, various industrially available ones are easily available. Specific examples include, for example, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, and tetrafluoromethanesulfonic anhydride. Fluoroboric acid, p-toluenesulfonic acid,
Examples include perchloric acid, hexafluoroantimonic acid, hexafluorophosphoric acid, and triethyloxonium tetrafluoroborate. Also, Tetrakis [3,
5-bis (trifluoromethyl) phenyl] boric acid 2,
3,5,5-Tetramethyl-5-silaoxazolinium, 1
-Carbadodecaboric acid 2,3,5,5-tetramethyl-
Cationic silicon compounds such as 5-silaoxazolinium and tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2,3-dimethyl-5,5-bis (trimethylsilyl) -5-silaoxazolinium It can also be used as a polymerization initiator in the production method of the present invention. These cationic silicon compounds can be easily produced by a known method of reacting amidomethyl (chloro) silanes with a metal salt [Proceedings of the 79th Annual Meeting of the Chemical Society of Japan, page 25, 1B435 (2001). Year) etc.].

The polymerization reaction according to the present invention is preferably performed in an organic solvent from the viewpoint of reaction efficiency. Examples of the organic solvent used in the production method of the present invention include halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane and tetrachloroethylene, aromatic hydrocarbon solvents such as toluene and benzene, such as pentane. ,
Examples thereof include aliphatic hydrocarbon solvents such as hexane and decane. The polymerization reaction according to the present invention is usually carried out under an atmospheric pressure in an atmosphere of an inert gas such as nitrogen or argon. The reaction temperature can be usually in the range of −50 to 200 ° C., but it is preferably room temperature to 100 ° C. for easy operation. The reaction time naturally varies depending on the reaction temperature, the type of the polymerization initiator used, other reaction conditions and the like, but it is usually several ten minutes to several hundred hours. A so-called catalyst amount is sufficient for the amount of the polymerization initiator to be used, but it is preferable that the amount is 0.1 to 0.005 mol per mol of the compound represented by the general formula (2). The product after the reaction is easily purified by the reprecipitation method or the column chromatography method.

According to the production method of the present invention, the ferrocenylenesilylene polymer represented by the above general formula (1) and having an amide group can be easily obtained in a high yield.

Specific examples of the ferrocenylene silylene polymer represented by the general formula (1) obtained by the production method of the present invention are as follows. Poly [1,
1'-ferrocenylene- (N-methylacetylaminomethyl) chlorosilylene], poly [1,1'-ferrocenylene
-(N-methylacetylaminomethyl) iodosilylene], poly [1,1'-ferrocenylene- (N-methylacetylaminomethyl) fluorosilylene], poly [1,
1'-ferrocenylene- (N-methylacetylaminomethyl) bromosilylene], poly [1,1'-ferrocenylene
-(N-methylformylaminomethyl) chlorosilylene], poly [1,1 '-(2,4,5,2', 4 ', 5'-hexamethylferrocenylene)-(N-methylacetylaminomethyl ) Chlorosilylene], poly [1,1 '-(2,4,5-
Trimethylferrocenylene)-(N-methylacetylaminomethyl) chlorosilylene], poly [1,1 ′-(2,3,
4,5,2 ′, 3 ′, 4 ′, 5′-octamethylferrocenylene)-(N-methylacetylaminomethyl) chlorosilylene], poly [1,1 ′-(2,4,5-tris (Trimethylsilyl) ferrocenylene)-(N-methylacetylaminomethyl) chlorosilylene], poly [1,1 ′-(2,4,
5,2 ', 4', 5'-Hexakis (trimethylsilyl) ferrocenylene)-(N-methylacetylaminomethyl) chlorosilylene], poly [1,1'-ferrocenylene- (2-
Piperidone-1-yl) methylchlorosilylene], poly [1,1'-ferrocenylene- (2-pyrrolidone-1-yl)
Methylchlorosilylene], poly [1,1′-ferrocenylene- (N-methylphenylcarbonylamino) methylchlorosilylene], poly [1,1′-ferrocenylene- (N-phenylphenylcarbonylamino) methylchlorosilylene], poly [1,1′-ferrocenylene- (N-methylethenylcarbonylamino) methylchlorosilylene], poly [1,1′-ferrocenylene- (N-methylethylcarbonylamino) methylchlorosilylene], poly [1,1 ′ -Ferrocenylene- (N-methylpropylcarbonylamino)
Methylchlorosilylene], poly [1,1′-ferrocenylene- (N-methylisopropylcarbonylamino) methylchlorosilylene] and the like.

[0015]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1

[0017]

[Chemical 5]

Tetrakis [3] as a polymerization initiator was added to a dichloromethane solution (7 ml) of 1,1′-ferrocenediyl [(N-methylacetylamino) methyl] chlorosilane (65 mg, 0.17 mmol) under an inert gas atmosphere. 2,5-Bis (trifluoromethyl) phenyl] borate 2,3,5,5-tetramethyl-5-silaoxazolinium (2.0 mg, 0.002 mmol) was added, and the mixture was allowed to stand at room temperature for 20 minutes.
Stir for 0 hours. After that, anhydrous hexane (5 ml) was added to precipitate the produced polymer, and thus poly [1,
1'-ferrocenylene- (N-methylacetylaminomethyl) chlorosilylene] 58 mg (yield: 89%) was obtained. The weight average molecular weight of the obtained polymer was 9000 when measured by a light scattering method. Various spectrum data are as follows. ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ 1.
5-2.6 (br, 3H), 2.6-3.7 (br, 5
H), 3.7-4.9 (br, 8H). ²⁹ Si NMR (59.6 MHz, CD ₂ Cl ₂ ): δ
-59.78.

Example 2

[0020]

[Chemical 6]

Under an inert gas atmosphere, 1,1'-ferrocenediyl [(N-methylacetylamino) methyl] chlorosilane (65 mg, 0.17 mmol) in dichloromethane solution (7 ml) was added to trifluoromethanesulfone as a polymerization initiator. 0.050 ml of acid solution in dichloromethane
(Containing 0.002 mmol of trifluoromethanesulfonic acid) was added, and the mixture was stirred at room temperature for 200 hours. After that, anhydrous hexane (5 ml) was added to precipitate the produced polymer, whereby poly [1,1'-ferrocenylene-
(N-methylacetylaminomethyl) chlorosilylene]
46 mg (yield: 71%) was obtained. Various spectral data of the produced polymer were in agreement with those obtained in Example 1. The weight average molecular weight of the produced polymer was 1,600 as measured by a light scattering method.

Example 3

[0023]

[Chemical 7]

1,1'-ferrocenediyl [(N-methylphenylcarbonylamino) methyl] chlorosilane under an inert gas atmosphere, (79 mg, 0.20 mmol)
In dichloromethane solution (7 ml) of tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2,3,5,5-tetramethyl-5-silaoxazolinium as a polymerization initiator (2.0 mg, 0.002 mmol),
The mixture was stirred at room temperature for 200 hours. Then, anhydrous hexane (5 ml) was added to precipitate the produced polymer, so that poly [1,1′-ferrocenylene- (N-methylphenylcarbonylamino) methylchlorosilylene] 63 mg was obtained.
(Yield: 80%) was obtained. When the weight average molecular weight of the produced polymer was measured by a light scattering method, it was about 14,000.
Met. Various spectrum data are as follows. ¹ H NMR (300 MHz, CD ₂ Cl ₂ ): δ 2.
5-3.5 (br, 5H), 3.9-4.9 (br, 8)
H), 7.2-8.0 (br, 5H). ²⁹ Si NMR (59.6 MHz, CD ₂ Cl ₂ ): δ
-60.62.

[0025]

INDUSTRIAL APPLICABILITY According to the production method of the present invention, a ferrocenylenesilylene polymer having a functional group without impairing the amide functional group of the monomer has the functional group which can be easily obtained in a high yield. Ferrocenylene silylene polymer is
It has an extremely high industrial value as a surface modifier for metal electrodes used in electrochemical reactions, semiconductor materials, sensor materials, electrochromic materials, and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masato Tanaka             1-1-1 Higashi 1-1-1 Tsukuba City, Ibaraki Prefecture             National Institute of Advanced Industrial Science and Technology Tsukuba Center F-term (reference) 4J030 CC30 CD02 CE02 CE11

Claims (8)

[Claims] 1. The following general formula (1) [Chemical 1] (In the formula, R¹And R^TwoAre each independently a hydrogen atom,
Alkyl group which may have a substituent and alkenyl thereof
Group, the same aryl group or the same aralkyl group, R ^Three, R
^Four, R⁵, R⁶, R⁷, R⁸, R⁹And R¹⁰Is that
Independently of each other, a hydrogen atom or an alkyl which may have a substituent.
It represents a kill group, the same aralkyl group or the same silyl group. Also,
R¹And R^TwoAnd are linked to each other, and
It may form a ring with the child. X is a halogen atom
Represent ) Ferrocenile having a repeating unit represented by
Nsilylene polymer. 2. The following general formula (2): (In the formula, R ¹ and R ² are each independently a hydrogen atom,
Represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group which may have a substituent, and R ³ and R
⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group or a silyl group. Also,
R ¹ and R ² may be bonded to each other to form a ring with the adjacent atoms. X represents a halogen atom. The method for producing a ferrocenylene silylene polymer according to claim 1, wherein the silaferrocenophane represented by the formula (4) is subjected to cationic ring-opening polymerization in the presence of a cationic polymerization initiator. 3. The cationic polymerization initiator is trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, tetrafluoroboric acid, p-toluenesulfonic acid,
The production method according to claim 2, which is perchloric acid, hexafluoroantimonic acid, hexafluorophosphoric acid, or triethyloxonium tetrafluoroborate. 4. The method according to claim 2, wherein the cationic polymerization initiator is a cationic silicon compound. 5. The cationic silicon compound is tetrakis [3,5-bis (trifluoromethyl) phenyl] borate 2,3,5,5-tetramethyl-5-silaoxazolinium, 1-carbadodecaborane. Acid 2,3,5,5-tetramethyl-5-silaoxazolinium or tetrakis [3,5-
Bis (trifluoromethyl) phenyl] boric acid 2,3-
The production method according to claim 4, which is dimethyl-5,5-bis (trimethylsilyl) -5-silaoxazolinium. 6. The production method according to claim 2, wherein the reaction is performed in an organic solvent. 7. The production method according to claim 6, wherein the reaction is carried out in a halogenated hydrocarbon organic solvent. 8. The method according to claim 7, wherein the halogenated hydrocarbon organic solvent is dichloromethane.