JP3076845B1 - Organosilicon polymer having functional group and method for producing the same - Google Patents

Abstract

【wrap up】 PROBLEM TO BE SOLVED: To provide a polymer having a low band gap value,
Provided are a silicon polymer having a functional group and a method for producing the same.
Offer. SOLUTION: The following general formula (1) Embedded image (Where R¹Is a substituted or unsubstituted alkyl group,
Represents an aryl group; ²Represents a hydrogen atom, an alkyl group,
Represents a reel group, an alkoxycarbonyl group or an acyl group.
You. Also, R³Is an alkyl group, an aryl group, an alkoxy
Represents an amino group or an amino group. x and y are repeating units
And the relation of 1 ≧ y> 0.01 and x + y = 1
Meet the clerk. A) a functional group having a repeating unit represented by
A silicon polymer having the following general formula (2): Embedded image (Where R¹, X and y are defined by the general formula (1).
And the silicon polymer represented by
And the following general formula (3) Embedded image (Where R²And R³Is defined by the general formula (1)
With a rhodium compound
Reaction in the presence of a catalyst or rhodium metal salt
The functional group-containing silicon poly according to claim 1,
Manufacturing method of mer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon polymer having a functional group, which is useful as a conductive material, a photoelectric conversion material or a light emitting material, and a method for producing the same.

[0002]

2. Description of the Related Art Polysilanes are known as polymers having a main chain structure composed of silicon atoms [Chem.
v., Vol. 89, p. 1359 (1989)]. As a polymer having a silicon atom as a main chain and having a crosslinked structure, polysilins [J. Am. Chem. Soc., Vol. 110, p. 2342 (1988
Year); Macromolecules, Vol. 22, 1697 (1989); Ma
cromolecules, 23, 3423 (1990); Chem. Mate
r., Vol. 5, p. 245 (1993)], and poly [silylene-cylin] s [Macro
molecules, 29, 7362 (1996); Journal of
Polymer Science: Part A: Polymer Chemistry, Part 3
3, 771 (1995)]. These compounds exhibit useful physical properties due to having a silicon chain in the main chain, and are expected to be used as conductive materials, photoelectric conversion materials, or luminescent materials. However, since the band gap value that greatly affects the functional properties is as large as 3.1 eV or more, the excitation efficiency by light or the excitation efficiency by electric field is low, and it has not been applied to practical materials.

[0003]

SUMMARY OF THE INVENTION The present invention introduces a functional group into a side chain of a polymer containing silicon in its main chain structure, and thereby has a low band gap having high industrial utility as an optical / electronic functional material. It is intended to obtain a polymer having a value.

[0004]

Means for Solving the Problems The present inventors have found that the introduction of a carbonyl group into the side chain of a silicon polymer changes the tertiary structure of the polymer and exhibits a remarkably low band gap value. The present invention has been completed.

That is, the present invention provides the following general formula (1)

Embedded image (Wherein, R ¹ represents a substituted or unsubstituted alkyl group or an aryl group, R ² represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, or an acyl group. In addition, R ³ represents an alkyl group, Represents an aryl group, an alkoxyl group or an amino group, and x and y represent the composition ratio of the repeating unit, and satisfy the relationship of 1 ≧ y> 0.01 and x + y = 1. A silicon polymer, preferably having a weight average molecular weight of 1
× 10 ³ or more polymers are provided. The present invention further provides the following general formula (2)

Embedded image (Wherein R ¹ , x and y have the same meanings as defined in the above general formula (1)) and a silicon polymer having a repeating unit represented by the following general formula (3)

Embedded image (Wherein R ² and R ³ have the same meaning as defined in the above general formula (1)), wherein the diazo compound is reacted in the presence of a rhodium catalyst or a rhodium metal salt. Provided is a method for producing a polymer having a repeating unit represented by the general formula (1).

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The silicon polymer having a repeating unit represented by the general formula (2) used as a reaction raw material in the present invention is obtained by a dehydrogenative coupling reaction of trihydrosilanes using a Group 4 transition metal catalyst [J. Am. Ceram. Soc., Vol. 74, p. 630 (199
1 year); Organometallics, Vol. 16, p. 2765 (1997)
)], And a polycondensation reaction of dichlorohydrosilanes using an alkali metal [Macromolecules, Vol. 28, p. 7235 (1995)].

[0007] R1 in the general formula (2) represents a substituted or unsubstituted alkyl group or aryl group. The alkyl group preferably has 1 to 10 carbon atoms and may be linear, branched or cyclic. These alkyl groups may have one or more substituents, and the substituents are not particularly limited as long as they do not inhibit the reaction of the present invention.
Examples thereof include a halogen and an alkoxyl group.
Specific examples include, for example, methyl, ethyl, propyl, butyl, hexyl, isobutyl, cyclohexyl, benzyl, chloromethyl, methoxymethyl, and the like. The substituted or unsubstituted aryl group is preferably a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and specific examples include, for example, a phenyl group, a tolyl group, and a methoxyphenyl group. In the general formula (2), x and y indicate the composition ratio of the repeating unit, and satisfy the relationship of 1 ≧ y> 0.01 and x + y = 1. Preferably, 1 ≧ y> 0.5.

Specific examples of the silicon polymer represented by the general formula (2) are as follows. Poly (methylsilylene), poly (ethylsilylene), poly (propylsilylene), poly (hexylsilylene), poly (cyclohexylsilylene), poly (phenylsilylene),
Poly (tolylsilylene), poly (methoxyphenylsilylene), poly (methylsilin-methylsilylene), poly (ethylsilin-ethylsilylene), poly (propylsilin-propylsilylene), poly (butylsilin-butylsilylene), poly (hexylcillin) -Hexylsilylene), poly (isobutylsiline-isobutylsilylene), poly (cyclohexylsilin-cyclohexylsilylene), poly (benzylsilin-benzylsilylene), poly (chloromethylsilin-chloromethylsilylene), poly (methoxymethylsilyl-methoxy) Methylsilylene) and the like.

The diazo compound represented by the general formula (3) used in the present invention is a compound easily synthesized from various industrially available raw materials such as tosyl azide [Chem. Rev., 94, 1091 (1994)]. In the general formula (3), R ² represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group or an acyl group.
R ³ represents an alkyl group, an aryl group, an alkoxyl group or an amino group, and an alkoxyl group is particularly preferred.

The alkyl group in R ² and R ³ preferably has 1 to 10 carbon atoms and may be linear, branched or cyclic. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an isobutyl group, a cyclohexyl group, a benzyl group, and the like. The aryl group in R ² and R ³ is particularly preferably a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and specific examples include, for example, a phenyl group, a tolyl group, a methoxyphenyl group, and a fluorophenyl group. Is mentioned. The alkoxycarbonyl group for R ² preferably has 2 to 9 carbon atoms, and specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a t-butoxycarbonyl group. The alkoxyl group in R ³ preferably has 1 to 6 carbon atoms and may be linear, branched or cyclic. Specific examples include a methoxy group, an ethoxy group, a t-butoxy group and the like. R ³
May have a substituent, and the substituent is preferably an alkyl group or an aryl group having 1 to 10 carbon atoms, specifically, for example, a dimethylamino group, a diethylamino group, a diphenylamino group and the like. No. R
The acyl group in ² preferably has 2 to 10 carbon atoms, and specific examples include an acetyl group, a propanoyl group, and a benzoyl group.

Specific examples of the diazo compound represented by the general formula (3) are as follows. Ethyl diazoacetate, methyl diazoacetate, t-butyl diazoacetate, t-butyl diazo (fluorophenyl) acetate, dimethyl diazomalonate, diethyl diazomalonate, di-t-butyl diazomalonate, ethyl diazoacetoacetate, diazo-N, N-dimethyl Acetamide, diazo-N, N-diethylacetamide, diazo-N, N-diphenylacetamide, ethyl 2-diazobutanoate, ethyl 2-diazopropanoate, ethyl diazobenzoyl acetate, and the like.

Various metal complexes or metal salts of rhodium used in the present invention are easily available industrially, and specific examples are as follows. Rhodium acetate dimer, rhodium trifluoroacetate dimer, rhodium octanoate dimer, rhodium benzoate dimer, rhodium pentafluorobenzoate dimer, rhodium heptafluoropropanoate dimer, rhodium chloride, rhodium Acetoacetonate and the like.

The reaction of the present invention is desirably performed in a solvent from the viewpoint of reaction efficiency. Examples of the solvent that can be used in the present invention include halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, and tetrachloroethylene; aromatic hydrocarbon solvents such as toluene and benzene; and aliphatic solvents such as pentane, hexane, and decane. Hydrocarbon solvents are mentioned. The reaction can be carried out at a temperature in the range of -50 to 100 ° C, but is desirably carried out at room temperature to 100 ° C from the viewpoint of reaction efficiency. The amount of the rhodium metal complex or metal salt used is a so-called catalytic amount, and is preferably 0.001 to 0.05 mol per 1 mol of the compound represented by the general formula (3). The reaction time is usually 1 to 12 hours.
The product after the reaction can be easily purified by a reprecipitation method, gel filtration chromatography, or the like.

According to the present invention, a silicon polymer having a functional group represented by the general formula (1) is obtained. R ¹ , R ² , R ³ , x and y in the general formula (1) are the same as those shown in the general formulas (2) and (3).

Specific examples of the crosslinked silicon polymer having a functional group represented by the general formula (1) are as follows. Poly [methyl (ethoxycarbonylmethyl) silylene], poly [ethyl (ethoxycarbonylmethyl)
Silylene], poly [propyl (methoxycarbonylmethyl) silylene], poly [hexyl (methoxycarbonylmethyl) silylene], poly [benzyl (methoxycarbonylmethyl) silylene], poly [phenyl (t-butoxycarbonylmethyl) silylene], poly [Tolyl (methoxycarbonylmethyl) silylene], poly [methoxyphenyl (methoxycarbonylmethyl) silylene], poly [methyl {(t-butoxycarbonyl) fluorophenylmethyl} silylene], poly [methylsilin-methyl (methoxycarbonylmethyl) silylene] ], Poly [methylsilin-methyl (ethoxycarbonylmethyl) silylene], poly [methylsilin-methyl (t-butoxycarbonylmethyl) silylene], poly [methylsilin-methyl (dimethoxycarbonylmethyl) L) silylene], poly [methylsilin-methyl (N, N-dimethylaminocarbonylmethyl) silylene], poly [methylsilin-methyl (N, N
N-diphenylaminocarbonylmethyl) silylene],
Poly [methylsilin-methyl (1-ethoxycarbonylpropyl) silylene], poly [methylsilin-methyl (1-
Ethoxycarbonylethyl) silylene], poly [ethylsilin-ethyl (ethoxycarbonylmethyl) silylene], poly [propylsilin-propyl (ethoxycarbonylmethyl) silylene], poly [butylsilin-butyl (ethoxycarbonylmethyl) silylene], poly [hexyl Syrin-hexyl (ethoxycarbonylmethyl)
Silylene], poly [cyclohexylsilin-cyclohexyl (ethoxycarbonylmethyl) silylene], poly [benzylsilin-benzyl (ethoxycarbonylmethyl) silylene], poly [chloromethylsilin-chloromethyl (ethoxycarbonylmethyl) silylene], poly [methoxy Methylsilin-methoxymethyl (ethoxycarbonylmethyl) silylene] and the like.

[0016]

EXAMPLES 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 The reaction in this example is shown by the following formula.

[0018]

Embedded image

Under a nitrogen atmosphere, 486 mg of poly (methylsilin-methylsilylene) (weight average molecular weight 4800,
Dispersion ratio 2.5, composition ratio of methylsilyl repeating unit to methylsilylene repeating unit is 0.14: 0.86), and 135 mg of rhodium acetate (0.3 mmol) were previously dried with calcium hydride in dichloromethane (8.3). 6 ml). Add 6.
3 g of t-butyl diazoacetate (44 mmol) were added dropwise over 5 hours. After completion of the dropping, the rhodium catalyst was removed with a celite column, and then dichloromethane was distilled off under reduced pressure. The obtained crude product was purified by gel filtration chromatography using toluene as an elution solvent, to obtain 813 mg of poly [methylsilin-methyl (t-butoxycarbonylmethyl) silylene] as a yellow solid. This was soluble in organic solvents such as tetrahydrofuran, methanol and chloroform. When the molecular weight of the polymer was measured by gel filtration chromatography, the weight average molecular weight was 10,000 in terms of polystyrene, and the dispersity was 2.2. From the measurement of the integrated value of each peak in 1H NMR, the composition ratio of the repeating units of methylsilin and the repeating units of methyl (t-butoxycarbonyl) methylsilylene in the obtained polymer was 0.14: 0.86. Was.

1H NMR (300 MHz, C6D6): δ0.2-1.1 (b
rs), 1.4 (s), 2.3 (br.s); IR (KBr): 2980,1711,1396,
1371,1259,1152,1093,853,766 cm-1.

Example 2 The reaction in this example is shown by the following formula.

[0022]

Embedded image

In a nitrogen atmosphere, 62 mg of poly (methylsilin-methylsilylene) (weight average molecular weight 2100, dispersity 5.0, composition ratio of methylsilyl repeating unit to methylsilylene repeating unit 0.20: 0.80), and 16 mg of rhodium acetate (0.04 mmol) were dissolved in dichloromethane (1 ml) which had been dried over calcium hydride. 240m at room temperature
g of ethyl diazoacetate (2.1 mmol) was added dropwise over 4 hours. After completion of the dropping, the rhodium catalyst was removed with a celite column, and then dichloromethane was distilled off under reduced pressure. The obtained crude product was purified by gel filtration chromatography using toluene as an elution solvent, to obtain 115 mg of poly [methylsilin-methyl (ethoxycarbonylmethyl) silylene] as a yellow solid. This was soluble in organic solvents such as tetrahydrofuran, methanol and chloroform. When the molecular weight of the polymer was measured by gel filtration chromatography, the weight average molecular weight was 4,000 in terms of polystyrene, and the dispersity was 1.7. From the measurement of the integrated value of each peak in 1H NMR, the composition ratio of the repeating unit of methylsilin and the repeating unit of methyl (ethoxycarbonyl) methylsilylene in the obtained polymer was determined to be 0.2.
0: 0.80.

1H NMR (300 MHz, C6D6): δ0.2-0.8 (br.
s), 1.1 (s), 2.2-2.8 (br.s), 3.8-4.42 (br.s); IR (KBr):
3500,2928,2364,2086,1719,1406,1255,1096,1035,868,
772,660 cm-1.

Example 3 The reaction in this example is shown by the following formula.

[0026]

Embedded image

Under a nitrogen atmosphere, 73 mg of poly (methylsilylene) (weight average molecular weight 1900, dispersity 2.0),
And 16 mg of rhodium acetate (0.04 mmol)
Was dissolved in dichloromethane (1 ml) previously dried with calcium hydride. Add this solution at room temperature
240 mg of ethyl diazoacetate (2.1 mmol) in 4
Dropped over time. After completion of the dropping, the rhodium catalyst was removed with a celite column, and then dichloromethane was distilled off under reduced pressure. The obtained crude product was purified by gel filtration chromatography using toluene as an eluent, to give 140 mg of poly [methyl (ethoxycarbonylmethyl) silylene] as a yellow solid. This was soluble in organic solvents such as tetrahydrofuran, methanol and chloroform. When the molecular weight of the polymer was measured by gel filtration chromatography, the weight average molecular weight was 3500 and the dispersity was 2.4 in terms of polystyrene.

Example 4 The reaction in this example is represented by the following formula.

[0029]

Embedded image

Under a nitrogen atmosphere, 63 mg of poly (phenylsilylene) (weight average molecular weight: 2,000, dispersity: 1.
8), and 8 mg of rhodium acetate (0.02 mmol
l) was dissolved in dichloromethane (1 ml) previously dried over calcium hydride. To this solution, at room temperature, 259 mg of butyl diazoacetate (1.8 mmol)
Was added dropwise over 4 hours. After completion of the dropping, the rhodium catalyst was removed with a celite column, and then dichloromethane was distilled off under reduced pressure. The obtained crude product was purified by gel filtration chromatography using toluene as an elution solvent, to obtain 132 mg of poly [phenyl (t-butoxycarbonylmethyl) silylene] as a yellow solid. This was soluble in organic solvents such as tetrahydrofuran, methanol and chloroform. When the molecular weight of the polymer was measured by gel filtration chromatography, the weight average molecular weight was 4,400 in terms of polystyrene, and the dispersity was 1.7.

[0031]

TEST EXAMPLE To show that the functionalized silicon polymer according to the invention has a lower bandgap value compared to the non-functional silicon polymer, the poly [methylsilin-methyl (t- [Butoxycarbonylmethyl) silylene] (weight average molecular weight 10,000, dispersion ratio 2.2) was used as a cast film on a quartz plate, and an ultraviolet absorption spectrum was measured. As a result, the absorption edge reached 500 nm.
FIG. 1 shows the obtained ultraviolet spectrum. When the absorption edge wavelength is converted into a band gap value, it corresponds to 2.48 eV.
Accordingly, it was shown that the polymer obtained according to the present invention has a lower band gap value as compared with the conventional compound.

[0032]

According to the present invention, there is provided a silicon polymer having a functional group, which exhibits a remarkably low band gap value, and a method for producing the same. This polymer has high industrial value as a conductive material, a photoelectric conversion material, or a light emitting material.

[0033]

[Brief description of the drawings]

FIG. 1 is an ultraviolet absorption spectrum of a cast film of a quartz plate of poly [methylsilin-methyl (t-butoxycarbonylmethyl) silylene] obtained in Example 1.

Continuation of the front page (56) References Vysokomol. Soedin. , Ser. B (1970), Vol. 12, No. 1, pp. 6-10 (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 77/00-77/62 C08L 83/00-83/16 REGISTRY (STN) CA (STN)

Claims (2)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ represents a substituted or unsubstituted alkyl group or an aryl group, R ² represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group, or an acyl group. In addition, R ³ represents an alkyl group, Represents an aryl group, an alkoxyl group or an amino group, and x and y represent the composition ratio of the repeating unit, and satisfy the relationship of 1 ≧ y> 0.01 and x + y = 1. Having a silicon polymer. 2. A compound represented by the following general formula (2): (Wherein R ¹ , x and y have the same meanings as defined in the general formula (1)), and a silicon polymer having a repeating unit represented by the following general formula (3): (Wherein R ² and R ³ have the same meanings as defined in formula (1)) in the presence of a rhodium catalyst or a rhodium metal salt. Item 10. A method for producing a silicon polymer having a functional group according to Item 1.