JP2000248068A - Organic silicon homo- and copolymer having chiral substituent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organic silicone homopolymer useful e.g. as an enantiomer-recognizing material, a model standard substance for studying the structure of an one-dimensional semiconductor.quantum fine line by introducing a specific chiral substituent. SOLUTION: The objective polymer is obtained by introducing a chiral substituent of formula I [wherein R1 is an alkyl (preferably methyl, ethyl or n-hexyl), an aralkyl, an aryloxyalkyl or an alkyl ether; R* is a position isomer (preferably p-[(S)-2-methylbutoxy]phenyl or p-[(R)-2-methylbutoxy]phenyl) of an aryloxyalkyl containing a chiral alkyl having an asymmetric center at the β-position; (n) is 10-100,000]. The polymer can be produced e.g. by the desalting condensation of an optically active organic dichlorosilane of formula II with metallic sodium in toluene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel chiral substituent which is expected to have thermochromism, piezochromism, electroluminescence, enantiomer molecular recognition ability, or physical properties and functions as a one-dimensional quantum wire semiconductor or exciton substance. The present invention relates to organosilicon homopolymers and copolymers having

[0002]

2. Description of the Related Art Many organic silicon compounds are industrially useful, and include surface treatment agents, water-repellent and oil-repellent agents, electric insulators,
All of them are polymers containing silicon as a part of the skeleton, such as a precursor of a ceramic material. In recent years, the main chain skeleton is composed of only silicon. Solvent-soluble organic polysilanes are attracting attention as a new type of functional material, and many studies directed to photoresists and optical waveguide materials are being advanced.

[0003] Organopolysilanes are generally from 300 to 400
It has an ultraviolet absorption band based on the main chain skeleton peculiar to the Si—Si chain near nm. Conventional polysilanes have a main chain absorption of about 5000 to 10000 (monomer units / liter) ^-1 cm ^-1 and a half width of 0.5 to ⁰ in a solution at room temperature because the main chain skeleton is in a random coil shape. 0.6 eV (about 40 to 6
0 nm).

On the other hand, a series of recently reported organopolysilanes having an alkyl group having a branched structure at the β-position have a molecular absorption coefficient of about 40,000 to 110,000 (because the main chain skeleton is a rigid rod shape). Monomer unit / liter) ^-1 cm ^-1 , half width 0.1 to 0.05 eV (about 8 to 4
nm) of the main chain. For example,
(1) M. Fujiki, Journal of American Chemical Society (J. Am. Chem. Soc.), No. 1
16, 1617 (1994), (2) M.P.
Fujiki, Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 116, No. 11976 (1994), (3) Fujiki,
Applied Physics Letters (Appl.
s. Lett. ), Volume 65, Page 3251 (19
1994), (4) M.P. Fujiki, Journal of American Chemical Society (J. Am. Chem. So
c. ), Vol. 118, p. 7424 (1996)
Year), (5) M.P. Fujiki, polymer preprint (P
olym. Prep. ), Vol. 37, p. 454 (1996), etc., have already been reported. That is, the absorption spectrum intensity and half width of the organic polysilane are
It has become known to vary significantly depending on the morphology of the main chain.

On the other hand, there have been only a few reports on organic polysilanes having an aromatic substituent having a polar oxygen introduced into the structure, with respect to various organic polysilanes having an alkyl substituent. -Methoxyphenylsilane]. M. Zeigler et al., Macromolecules
s), Volume 20, Page 601 (1987); K
akimoto et al., Journal of Polymer Science Part A Polymer Chemistry (J. Poly)
m. Sci. , Part A, Polym. Che
m. ), Volume 34, Page 2753 (1996),
M. Kakimoto et al., Mater Research Society, Symposium Proceedings (Mat.
s. Soc. Sy mp. Proc. ), Vol. 328, pp. 267 (1994)], and no systematic studies have been made on the optical properties and morphology of silicon backbones. Optical properties of organic polysilanes having aromatic substituents not only show absorption and fluorescence based on σ conjugation of the silicon main chain,
It also depends on the interaction between the π orbital of the aromatic substituent and the 3p orbital of silicon. The introduction of polar oxygen can be expected to change the electronic structure of silicon constituting the main chain more greatly.

[0006] These facts indicate that if an aromatic substituent having polar oxygen is introduced into the side chain and the π orbital level of the aromatic substituent is manipulated by a change in the structure, the absorption maximum wavelength of the interacting silicon main chain can be improved. It can be easily changed over a wide range of about several tens of nanometers, that is, there is a possibility that the optical properties of the silicon main chain can be remotely controlled by a substituent effect. This effect is of great interest in the future for precise control of optical functionality. In addition, regarding the form of this organic polysilane, the balance of the side chains can be changed by a combination of a relatively bulky aromatic substituent and various alkyl substituents, and the shape of the random coil is changed from a considerably contracted random coil shape to a rigid rod shape. To a wide range depending on the substituent.

[0007] Since organic polysilane is a macromolecule in which the main chain itself is composed only of silicon, the main chain is relatively easily decomposed by ultraviolet irradiation, and the molecular weight is reduced or the siloxane conversion proceeds. Actually, an application example as a photoresist utilizing this is reported. Therefore, it is unsuitable in terms of life as a light-related functional material such as a nonlinear optical material or a light-emitting material that directly utilizes the main chain absorption or light-emitting phenomenon of organic polysilane. However, if a property that functions on the longer wavelength side than the main chain absorption band of the organic polysilane is found, this drawback can be overcome. This is because the organic polysilane itself is very stable in a dark place.

On the other hand, as a polymer material recognizing an enantiomer, a main chain such as poly (triphenylmethyl methacrylate) and poly (diphenylpyridylmethyl methacrylate) which have been synthesized using spartin-n-butyllithium as a polymerization initiator has been known. Carbon skeleton polymers having a unidirectional spiral winding property are known [for example, Y. Okamoto (Y. Okamoto), Journal of
American Chemical Society (J. Am. Che
m. Soc. 103, p. 6971 (198
1)]. These unilateral helically wound organic polymers are marketed as high-performance liquid chromatography column materials for separating and separating enantiomers in the form of being actually supported on a silica gel surface [Daicel Chemical Co., Ltd. Chiralpak- OT, Chiralpak-O
P]. However, these poly (triphenylmethyl methacrylate) -based materials have the disadvantage that when the side chain fixing the main chain helical structure is eliminated by hydrolysis or solvolysis, the ability to recognize enantiomers is also lost.

A high-speed liquid used in a dark place or under a condition of deoxygenation can be used by taking advantage of the feature that the silicon main chain skeleton and the hydrocarbon side chain of the organic polysilane are resistant to hydrolysis and solvolysis. It can be used as a column material for chromatography (abbreviated as HPLC) and gas chromatography (abbreviated as GC). Currently, as a means for separation and analysis by HPLC, most of the enantiomer recognition column materials that can be used even under reversed phase conditions are derived from biological substances, and most of them are alkyl derivatives having an amide bond.
Again, the problem of column degradation due to hydrolysis remains. Here, if a completely artificial organic polysilane introduced with an aromatic substituent having polar oxygen can be used as a column carrier, external stimuli (chemical changes such as acid / alkali, hydrolysis, heat, pressure, etc.) Change), the column retains its ability to recognize enantiomers derived from one-way helicity of the main chain even after long-term repeated use, and can suppress column degradation. A highly functional CSP (chiral stationary phase) for HPLC or a CSP column material for GC can be provided.

Various interactions between the enantiomer to be recognized and the polysilane (π-π interaction, dipole-
Multipoint recognition by means of dipole interaction, hydrogen bonding, electron donating and attracting properties between a polar pair of a lone pair and a substrate, etc. becomes possible, and it is expected that the affinity will be dramatically improved. This is very similar to how enzymes in a living body recognize nutrients in food taken into the body at multiple points and select and isolate only necessary ones. In addition, if the optical properties and morphology of the organic polysilane can be precisely controlled by the type of alkyl substituent introduced and the position of polar oxygen in the aromatic substituent, a polysilane column carrier that matches the properties of the enantiomer to be recognized Can be selectively synthesized and used.

If the main chain itself can stably maintain a one-way helicity structure in a solution at room temperature by introducing an optically active group, the first step toward practical use of an enantiomer-recognizing polymer material can be taken. Chiral reagents are further developed in various fields including the pharmaceutical and pharmaceutical industries,
Great progress will be made in both number and nature.
Therefore, if complete enantiomeric separation, which is an issue, can be performed using a polysilane column, great technical and commercial advantages are expected.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel enantiomer-recognizing material, particularly a CS for HPLC or GC.
It has an organic substituent containing a chiral center and an aromatic substituent having polar oxygen in its side chain, which is useful as a P column material and a model standard for one-dimensional semiconductor and quantum wire structure research. Another object of the present invention is to provide a novel organosilicon homopolymer and copolymer in which the one-way helix is stably maintained.

[0013]

SUMMARY OF THE INVENTION In general, the present invention is directed to a first aspect of the present invention which relates to an organosilicon homopolymer having a chiral substituent and has the following general formula (I):
Is an organic silicon homopolymer represented by

[0014]

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Here, R ₁ is selected from the group consisting of an alkyl group, an aralkyl group, an aryloxyalkyl group, and an alkyl ether group, and R ^* is an alkyl containing a chiral alkyl group having a chiral center at the β-position. Selected from positional isomers of the oxyaryl group, and n is 10 to 1
Up to 00000.

According to a second aspect of the present invention, in the general formula (I), R ₁ is selected from the group consisting of a methyl group, an ethyl group and an n-hexyl group, and R ^* is p-｛(S) -2. Chiral substitution according to the first aspect, wherein the chiral substitution is selected from the group consisting of -methylbutoxy} phenyl and p-{(R) -2-methylbutoxy} phenyl, and wherein n is in the range of 10 to 100,000. It is an organic silicon homopolymer having a group.

The third aspect of the present invention relates to an organosilicon copolymer having a chiral substituent, and comprises an optically active chiral substituent represented by the following general formula (II): Unit is included in a part of the main chain skeleton, and n is 1
An optically active organosilicon copolymer characterized by being in the range of 0 to 100000,

[0018]

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Here, R ₁ is selected from the group consisting of an alkyl group, an aralkyl group, an aryloxyalkyl group and an alkyl ether group, and R ₂ and R ₃ are the same or different positional isomers of the aryloxyalkyl group. , R ^* represents a chiral aralkyl group having an asymmetric center at the β-position, and x represents 0.001 ≦ x ≦ 0.999.

According to a fourth aspect of the present invention, in the general formula (II), R ₁ is an n-hexyl group, R ₂ and R ₃ are p-methoxyphenyl groups, and R ^* is (S)- An optically active chiral compound selected from the group consisting of 2-methylbutyl and (R) -2-methylbutyl, wherein x is 0.001 ≦ x ≦ 0.999, and n is in the range of 10 to 100,000. It is an organic silicon copolymer into which an organic substituent has been introduced.

According to a fifth aspect of the present invention, in the general formula (II), R ₁ is an n-hexyl group, R ₂ is a p-methoxyphenyl group, and R ₃ is an m-methoxyphenyl group. , R ^* is a (S) -2-methylbutyl group and (R)
An organic compound selected from the group consisting of -2-methylbutyl groups, wherein x is 0.001 ≦ x ≦ 0.999, and n is in the range of 10 to 100,000 and an optically active chiral organic substituent is introduced. It is a silicon copolymer.

The first and second aspects correspond to the first aspect of the present invention.
The invention relates to: It is characterized by an organosilicon homopolymer having both an alkyl substituent and an alkyloxyaryl substituent containing a chiral aralkyl group having an asymmetric center at the β-position.

On the other hand, the third to fifth aspects relate to the second invention of the present invention. It is characterized by a silane monomer unit having an alkyl substituent and an alkyloxyaryl substituent, and a silane having a chiral alkyl group having an asymmetric center at the β-position or a positional isomer of the same or different alkyloxyaryl group. It is an optically active organosilicon copolymer with a monomer unit.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The asymmetrically substituted chlorosilanes used in the present invention are synthesized based on the following general reaction formula (III).

[0025]

(The following general reaction formula (III) is represented by the following (i) to (i)
v) is included) THF indicates tetrahydrofuran, and Et ₂ O indicates diethyl ether.

In the present invention, among the substituents represented by R ₁ , examples of the alkyl group include CH ₃ , C ₂ H ₅ , n
_{-C 3 H 7, n-C} 4 H 9, n-C 5 H 11, n-C 6 H
_{13, n-C 7 H 15} , n-C 8 H 17, n-C 9 H 19, n-
_{C 10 H 21, n-C} 11 H 23, n-C 12 H 25, n-C
_{13 H 27, n-C 14} H 20, n-C 15 H 31, n-C 16 H 33,
_{n-C 17 H 35, n} -C 18 H 37, n-C 19 H 39, n-C 20
Such as H ₄₁ and the like. Examples of the aralkyl group include CH ₂ CH ₂ Ph (Ph represents a phenyl group; the same applies hereinafter), CH ₂ CH ₂ CH ₂ Ph, CH ₂ CH ₂ CH
₂ CH ₂ Ph and the like. Examples of the aryloxyal group include CH ₂ CH ₂ OPh and CH ₂ CH ₂
CH ₂ OPh, such as _{CH 2 CH 2 CH 2 CH 2} OPh , and the like. And as an example of an alkyl ether group,
CH ₂ CH ₂ OCH ₂ CH ₂ OC ₂ H ₅ , CH ₂ CH ₂
O (CH ₂ CH ₂ O) ₂ C ₂ H _{5 and the} like. In the present invention, examples of the substituent represented by R ₂ or R ₃ include o- (CH ₃ O) Ph and m- (CH ₃ O) P
h, p- (CH ₃ O) Ph and the like.

N represents the degree of polymerization of the optically active silicon homopolymer and copolymer of the present invention. n is 10 to 1000
00 range.

X represents the ratio of achiral monomers to all monomers in the optically active silicone copolymer of the present invention.
x can be in the range of 0.001 to 0.999.

The optically active dichlorosilane monomer used in the present invention has an enantiomeric excess of 99.6% ee (ie,
Alkyloxyaryl halides and alkyl halides (corresponding to optical purity) having the general formula (I
It was synthesized by the reaction of II). Also, M. Fujiki, Polymer Prep. 37
Vol., P. 454 (1996), 20% ee for dialkyl-substituted optically active organic polysilanes.
It has been reported that even those having a low optical purity can obtain optical properties equivalent to those having a high optical purity. From this, it can be expected that the optically active organic polysilanes having an aromatic substituent this time can have the same optical properties as those having high optical purity even if they have low optical purity.

In the first invention of the present invention, among the groups represented by R ^* in the general formula (I), examples of the group represented by R ^* in the (S) -form or the (R) -form Is a group represented by the following formula (IV).

[0031]

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In the above, only the m-form is shown.
The o- and p-forms are also effective groups.

In the second invention of the present invention, among the groups represented by R ^* , examples of the group represented by (S) -R ^* include groups represented by the following formula (V): No.

[0034]

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In the second invention of the present invention, among the groups represented by R ^* , examples of the group represented by (R) -R ^* include groups represented by the following formula (VI): No.

[0036]

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The data of ¹³ C-, ²⁹ Si-NMR (CDCl ₃ , 30 ° C.), boiling point and specific rotation of the organic dichlorosilanes used in this case are summarized below.

1) Methyl-p-{(S) -2-methylbutoxy} phenyldichlorosilane ¹³ C-NMR: 5.709, 11.284, 16.486, 26.114, 34.647,7
2.773,114.612,124.153,134.823,1162.146ppm ²⁹ Si-NMR: 18.637ppm Boiling point 122 ° C-125 ° C / 1.00mmHg [α] _D 7.51 ° (neat liquid, 24.0 ° C) 2) Ethyl-p-｛(S)- 2-methylbutoxy} phenyl dichlorosilane ¹³ C-NMR: 6.310,11.291,13.307,16.506,26.14
1,34.681,72.787,114.632,123.085,135,170,162.146 ppm ²⁹ Si-NMR: 20.570 ppm Boiling point 102 ° C-105 ° C / 0.15mmHg [α] _D 7.26 ° (neat liquid, 23.0 ° C) 3) n-hexyl-p- ｛ (S) -2- methylbutoxy} phenyl dichlorosilane ¹³ C-NMR: 11.298,14.049,16.512,21.006,22.488,2
2.542,26.147,31.329,32.110,34.687,72.787,114.605,1
23.465,135.137,162.099 ppm ²⁹ Si-NMR: 19.283 ppm Boiling point 140 ° C.-145 ° C./0.35 mmHg [α] _D 6.09 ° (neat liquid, 22.0 ° C.) 4) (S) -2-methylbutyl-m-methoxyphenyldi Chlorosilane ¹³ C-NMR: 11.147,21.798,28.361,30.322,32,309,5
5.284,117.088,118.578,125.516,129.630,134.746,159.
263 ppm ²⁹ Si-NMR: 18.781 ppm Boiling point 80 ° C.-85 ° C./0.18 mmHg [α] _D 14.91 ° (neat liquid, 25.0 ° C.) 5) (S) -2-methylbutyl-p-methoxyphenyldichlorosilane ¹³ C-NMR ： 11.156,21.789,28.614,30.366,32.309,5
5.101,114.020,124.330,135.138,162.209 ppm ²⁹ Si-NMR: 19.069 ppm Boiling point 84 ° C-87 ° C / 0.10 mmHg [α] _D 14.99 ° (neat liquid, 25.0 ° C) 6) n-hexyl-p-methoxyphenyldi Chlorosilane ¹³ C-NMR: 14.040, 20.904, 22.459, 31.279, 32.074,5
5.181,114.008,123.749,135.146,162.226 ppm ²⁹ Si-NMR: 19.340 ppm Boiling point 122 ° C.-125 ° C./0.50 mmHg The organosilicon homopolymer in the first invention of the present invention is obtained by converting an optically active organic dichlorosilane into a metal in toluene. The corresponding organic silicon homopolymer is synthesized by desalting and condensing with sodium, and is represented by the following general formula (Vll).

[0039]

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The organosilicon copolymer according to the second aspect of the present invention is obtained by subjecting an optically active organic dichlorosilane and an optically inactive organic dichlorosilane to desalting condensation with metallic sodium in toluene to form a corresponding organic polysilane. It synthesizes a polymer and is represented by the following general formula (VIII). At that time, the helical winding property of the obtained copolymer is determined only by the absolute configuration of the optically active organic dichlorosilane used. That is, if an optically active organic dichlorosilane having a chiral alkyl group of (S) -configuration is incorporated into a part of the copolymer, it can be synthesized only from an optically active organic dichlorosilane having a chiral alkyl group of (S) -configuration. It has the same helical winding properties as the polymer.

[0041]

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In the above, the optically active organic dichlorosilanes used do not have a possibility of racemization or rearrangement in the course of Na desalination condensation reaction because the branching portion is at the β-position. According to the findings of the present inventors, a very small amount of β-position chiral carbon fixes the main chain of the entire organosilicon homopolymer or copolymer having a chain skeleton in almost one direction and at a constant pitch helix. Is remarkable. On the other hand, in the case of the branched structure at the α-position carbon, for example, an isopropyl group or a cyclohexyl group, steric requirements are extremely high, and as a result, the molecular weight is extremely low, usually 1000 or less and the main chain absorption maximum is 300 to 3
Only an organic polysilane homopolymer or copolymer having an extremely wide absorption band at 20 nm was obtained.

[0043]

EXAMPLES Specific examples of the synthesis of the optically active organosilicon homopolymer or copolymer according to the present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Poly [methyl-p-｛(S)
-2-methylbutoxy {phenylsilane]]. After the inside of the reaction vessel was sufficiently dehydrated and degassed and purged with argon gas, 0.66 g of metallic sodium, 0.3 ml of diglyme (diethylene glycol dimethyl ether) and 10 ml of toluene were placed in a flask. Oil bath temperature 110 ° C
After activating sodium by dropping -p-{(S) -2-methylbutoxy} phenyldichlorosilane little by little in the above, the oil bath temperature was lowered to 75 ° C and the remaining methyl-
p-{(S) -2-Methylbutoxy} phenyldichlorosilane was dropped at once. The reaction time is 2 hours. Thereafter, ethyl alcohol was added to the reaction solution to treat unreacted sodium, and then sufficiently washed with ethyl alcohol and water, and a white fixed product was obtained by absorption filtration.
For further purification, the product was redissolved in toluene, and the solution was filtered, followed by fractional reprecipitation using isopropanol and ethyl alcohol. The resulting white precipitate was collected by a centrifuge, and dried at 90 ° C. for 5 hours under vacuum. The yield is 0.0
9 g and a yield of 4.3% based on methyl-p-{(S) -2-methylbutoxy} phenyldichlorosilane.
Met.

As a result of measuring the weight average molecular weight by the GPC method, it was found to be 10,000 monomodal. FIG. 1 shows the absorption spectrum, fluorescence spectrum, and fluorescence anisotropy (at 23.0 ° C. in tetrahydrofuran) of the poly [methyl-p-{(S) -2-methylbutoxy} phenylsilane] obtained in Example 1.
Shown in

In FIG. 1, the horizontal axis represents the photon energy (e
V), the left vertical axis indicates the extinction coefficient [ε (monomer unit / liter) ^-1 cm ^-1 ], and the right vertical axis indicates the fluorescence anisotropy value. In the UV spectrum, the Si main chain absorption maximum (λmax) is 3.5.
It was observed at 3 eV (351.2 nm), and its absorption coefficient (ε) was 7,400. In addition, 4.42 eV (28
The absorption maximum observed around 0.5 nm) is due to the aromatic substituent. When the UV spectrum and the fluorescence spectrum in the vicinity of the Si main chain were compared, the UV peak was broad with respect to the fluorescence peak, and a non-mirror image relationship in which the half width of the spectrum was different. In addition, the fluorescence anisotropy value near the silicon main chain is strongly dependent on the excitation wavelength, and the wavelength is 330 nm.
From (3.76 eV) to 360 nm (3.44 eV), there was a tendency of monotonic increase from ０0 to 0.20. These absorption and fluorescence characteristics are related to the Si-Si conjugate length of the main chain skeleton, and the poly [methyl-p-
The form of the main chain of [(S) -2-methylbutoxy {phenylsilane]] can be estimated to be a random structure with many twists and bends. In fact, poly [methyl-p-｛(S) -2-
Methylbutoxy diphenylsilane] viscosity index value (α)
Showed α = 0.60, a value close to that of a random coil in a good solvent found in ordinary vinyl polymers.

Further, this time, the circular two-color (CD) spectrum was also measured (not shown), but the positional isomerism of the poly [methyl-p-{(S) -2-methylbutoxy} phenylsilane] of Example 1 was measured. Poly [methyl-m-｛(S)-
2-methylbutoxydiphenylsilane] Negative cotton CD absorption band [3.86 eV (321.2 n ⁾ observed in ¹⁾
m)] did not appear in the product of Example 1. [Note 1] This sample has already been filed in Japanese Patent Application No. 10-35153.
Patent No. 8 is pending. This indicates that the form of the main chain is controlled by the position of the chiral substituent. That is, poly [methyl-m-
In ({S) -2-methylbutoxy} phenylsilane], the silicon main chain has a helical structure with unidirectional winding due to the steric effect of the side chain chiral substituent, and a circular two-color peak is observed. Is done. On the other hand, since the position of the chilan substituent of the poly [methyl-p-{(S) -2-methylbutoxy} phenylsilane] shown in Example 1 is the p-position, the silicon main chain and the chiral side chain group It is concluded that the distance to is far away and that the main chain structure cannot be controlled remotely.

Example 2 Poly [ethyl-p-｛(S)]
-2-methylbutoxydiphenylsilane] was synthesized according to Example 1. The yield was 0.30 g, and the yield was 14.9% based on ethyl-p-{(S) -2-methylbutoxy} phenyldichlorosilane.

As a result of measuring the weight average molecular weight by the GPC method, it was found to be 1.4 million monomodal. FIG. 2 shows the absorption spectrum, fluorescence spectrum and fluorescence anisotropy (in tetrahydrofuran, 23.0 ° C.) of the poly [ethyl-p-{(S) -2-methylbutoxy} phenylsilane] obtained in Example 2. Show.

In FIG. 2, the horizontal axis represents the photon energy (e
V), the left vertical axis indicates the extinction coefficient [ε (monomer unit / liter) ^-1 cm ^-1 ], and the right vertical axis indicates the fluorescence anisotropy value. In the UV spectrum, the Si main chain absorption maximum (λmax) is 3.5.
It was observed at 2 eV (352.0 nm), and its absorption coefficient (ε) was 7,900. Also, 4.43 eV (28
The absorption maximum observed near 0.0 nm) is due to the aromatic substituent. When the UV spectrum and the fluorescence spectrum in the vicinity of the Si main chain were compared, the UV peak was broad with respect to the fluorescence peak, and a non-mirror image relationship in which the half width of the spectrum was different. In addition, the fluorescence anisotropy value near the silicon main chain is strongly dependent on the excitation wavelength, and the wavelength is 320 nm.
From (3.88 eV) to 370 nm (3.35 eV), there was a tendency of monotonic increase from about 0 to about 0.3.
These absorption and fluorescence characteristics are related to the Si-Si conjugate length of the main chain skeleton, and the poly [ethyl-p
-{(S) -2-methylbutoxy} phenylsilane] can be assumed to have a structure close to a random coil as in the methyl form of Example 1. In fact, the viscosity index value (α) of poly [ethyl-p-{(S) -2-methylbutoxy} phenylsilane] is α = 0.78, which is considered to be in a form close to a random coil.

Further, this time, the circular two-color (CD) spectrum was also measured (not shown). As in Example 1, poly [ethyl-p-{(S) -2-methylbutoxy}, which is a p-isomer, was used. Phenylsilane] did not show a CD absorption band despite having a chiral substituent on the side chain. The reason may be the same as in the first embodiment.

Example 3 Poly [n-hexyl-p-
{(S) -2-methylbutoxy} phenylsilane] was synthesized according to Example 1. However, while keeping the oil bath temperature at 110 ° C., dichlorosilane monomer was added dropwise to carry out the reaction. The yield was 0.23 g and the yield was n-hexyl-
It was 11.5% based on p-{(S) -2-methylbutoxy} phenyldichlorosilane.

The weight average molecular weight was measured by the GPC method. As a result, it was 1.5 million monomodal. Absorption spectrum, fluorescence spectrum and fluorescence anisotropy of poly [n-hexyl-p-{(S) -2-methylbutoxy} phenylsilane] obtained in Example 3 (23.0 in tetrahydrofuran)
C) are shown in FIG.

In FIG. 3, the horizontal axis is the photon energy (e
V), the left vertical axis indicates the extinction coefficient [ε (monomer unit / liter) ^-1 cm ^-1 ], and the right vertical axis indicates the fluorescence anisotropy value. In the UV spectrum, the Si main chain absorption maximum (λmax) is 3.4.
It was observed at 5 eV (359.0 nm), and its absorption coefficient (ε) was 14000. Also, 4.35 eV (28
The absorption maximum observed near (5.0 nm) is due to the aromatic substituent. When the UV spectrum and the fluorescence spectrum in the vicinity of the Si main chain were compared, the shapes of the UV peak and the fluorescence peak both had a narrow line width and had a perfect mirror image relationship. The fluorescence anisotropy value in the vicinity of the silicon main chain ranges from 318 nm (3.9 eV) to 354 nm (3.5 eV).
The gradient of the excitation wavelength was weak and gradually increased toward around V), and tended to increase monotonically on the longer wavelength side. Its value increased from 0.05 to around 0.3.
These absorption and fluorescence characteristics are related to the Si-Si conjugate length of the main chain skeleton, and the poly [n-hexyl-p-{(S) -2-methylbutoxy} phenylsilane] obtained in Example 3 is used. Can be presumed to be a more elongated semi-flexible structure. However, poly [ethyl-p-｛(S)-
The viscosity index value (α) of 2-methylbutoxy {phenylsilane] is α = 0.77, which is similar to that of the ethyl form of Example 2, and is clear in the form estimated from the viscosity index and the optical spectrum. No match was found.

Further, this time, the circular two-color (CD) spectrum was also measured (not shown). As in Example 1, poly [n-hexyl-p-｛(S) -2-methyl) was used as the p-isomer. Butoxy {phenylsilane]], the CD absorption band did not appear despite having a chiral substituent on the side chain. The reason may be the same as in the first embodiment.

[Other Examples] Although not described in detail here, the present inventors synthesize the homopolymer having a chiral substituent at the p-position shown in Examples 2 and 3 and also obtain a chiral polymer at the m-position. Homopolymer having a substituent (poly [ethyl-m-
{(S) -2-methylbutoxy} phenylsilane] and poly [n-hexyl-m-{(S) -2-methylbutoxy} phenylsilane]) were also tried. However, these products were only low molecular weight oligomers, and high molecular weight polymers could not be obtained. The reason for this is that the steric hindrance between the alkyl substituent of the ethyl group and the n-hexyl group and the bulky (S)-(2-methylbutoxy) phenyl substituent is very strong, and the polymerization of the main chain is inhibited. Is raised.

Example 4 Poly [(n-hexyl-p-
Methoxyphenyl) _0.8 -co (co)-((S) -2-
Methylbutyl-p-methoxyphenyl) _0.2 silane] is shown below. After sufficiently dehydrating and degassing the inside of the reaction vessel and purging with argon gas, 3.32 g of metallic sodium and 0.1 g of diglyme (diethylene glycol dimethyl ether) were added.
3 ml and 30 ml of toluene were placed in a flask. At an oil bath temperature of 110 ° C., 8.40 g (80 mol%) of n-hexyl-p-methoxyphenyldichlorosilane and (S)-
After activating sodium by dropwise adding a mixture of 2.00 g (20 mol%) of 2-methylbutyl-p-methoxyphenyldichlorosilane little by little, the remaining dichlorosilane monomer was kept at an oil bath temperature of 110 ° C. Was dripped at once. The reaction time is 2 hours. Thereafter, trimethylchlorosilane having a molar ratio of 10% to the raw material monomer (n-hexyl-p-methoxyphenyldichlorosilane + (S) -2-methylbutyl-p-methoxyphenyldichlorosilane) was added, and the mixture was stirred for 1 hour, and the polymer was stirred. The ends were capped with trimethylsilane (TMS). Ethyl alcohol was added to the reaction solution to treat unreacted sodium, and then sufficiently washed with ethyl alcohol and water, followed by suction filtration to obtain a white solid product. For further purification, the product was redissolved in toluene, and the solution was filtered, followed by fractional reprecipitation using isopropanol and ethyl alcohol. The resulting white precipitate was collected by a centrifuge, and 90
Vacuum dried at 5 ° C. for 5 hours. The yield was 0.45 g, and the yield was 5.7% in terms of dichlorosilane.

As a result of measuring the weight average molecular weight by the GPC method, it was found to be 590,000 and 5,000 bimodal.
5%, the latter 5%. FIG. 4 shows an ultraviolet absorption spectrum and a circular two-color (CD) spectrum of the obtained polysilane.
FIG. 5 shows the absorption spectrum, the fluorescence spectrum, and the fluorescence anisotropy (in tetrahydrofuran, 24.0 ° C.). That is, FIG. 4 shows poly [(n-hexyl-p-methoxyphenyl) _0.8 -co (co)-obtained in Example 4.
((S) -2-methylbutyl-p-methoxyphenyl)
_0.2 silane] absorption, circular dichroism absorption spectrum (in tetrahydrofuran, 25 ° C.), FIG. 5 shows absorption spectrum, fluorescence spectrum and fluorescence anisotropy (in tetrahydrofuran,
24.0 ° C.).

In FIG. 4, the horizontal axis is the photon energy (e
V), the left vertical axis represents the extinction coefficient [ε (monomer unit / liter) ⁻¹ cm ⁻¹ ], and the right vertical axis represents the circular two-color extinction coefficient [Δε (monomer unit / liter) ⁻¹ cm ⁻¹ ]. In the UV spectrum, the Si main chain absorption maximum (λmax) is 3.44 eV.
(360.2 nm), and its absorption coefficient (ε) was 13,000. Also, 4.38 eV (283.1n
The absorption maximum observed near m) is due to aromatic substituents. In the CD spectrum, 3.42 eV (36
A positive cotton CD absorption band was observed around (2.6 nm), which was found to be almost similar to the main chain absorption band at 3.44 eV (360.2 nm), and that the maximum absorption was almost the same. At the photon energy at which the circular dichroism absorption spectrum has a maximum value, an asymmetry factor that is very sensitive to helix (value obtained by dividing CD absorption intensity by UV absorption intensity)
Was about 9.7 × 10 ⁻⁵ .

The poly [(n-hexyl-m) previously studied
-Tolyl) _x -co (co)-((S) -2-methylbutyl-phenyl) _1- xsilane] as a function of chiral monomer concentration (Toyoda, Fujiki, Japanese Patent Application No. 9-299)
No. 47) (FIG. 6), the chiral monomer content is 40 to
It was found that the asymmetry factor was almost saturated at 50%.
Furthermore, poly [(n-hexyl-m-tolyl) _x -co (c
o)-((S) -2-methylbutyl-phenyl) _1-x silane] asymmetry factor of poly (n-hexyl- (S) -2-methylbutyl silane) to give a one-way helix
In comparison with that of the above, 1.4% by 50% copolymer
0 ^-4 , about 2.3 × 10 ^-4 for poly (n-hexyl- (S) -2-methylbutylsilane), and about the same as homopolymer poly ((S) -2-methylbutyl-phenylsilane). It became clear that they had the same winding property, spiral pitch, and rigid polymer structure.

The poly [(n-hexyl-p-methoxyphenyl) _0.8 -co (co)-((S) -2-methylbutyl-p-methoxyphenyl) 0.2silane] used herein is poly [(n-hexyl-p-methoxyphenyl) _0.2 ]. Phenyl) _x -co-
((S) -2-methylbutyl-phenyl) _1-x silane]
It is considered that the similar tendency is exhibited because the structure is very similar to the above, and the value of the asymmetry factor is saturated at a content of (S) -chiral monomer of about 40 to 50%, and a single weight is not obtained at that content. The same winding property as that of the unified poly ((S) -2-methylbutyl-p-methoxyphenylsilane), spiral pitch,
It is presumed that it will take a rigid polymer structure.

In the absorption spectrum, the fluorescence spectrum and the fluorescence anisotropy of FIG. 5, the shapes of the UV spectrum and the fluorescence spectrum in the vicinity of the Si main chain both have a narrow line width and have a perfect mirror image relationship. The fluorescence anisotropy value in the vicinity of the silicon main chain is 318 nm (3.9 eV) to 354 nm.
The excitation wavelength dependence showed a gradual increase in the weakness toward the vicinity of m (3.5 eV), and showed a monotonic increase on the longer wavelength side. Its value increased from 0.05 to around 0.3. These absorption and fluorescence characteristics are based on Si-
The poly [(n-hexyl-p-methoxyphenyl) _0.8 -co (co)-((S) -2-methylbutyl-p-methoxyphenyl) _0.2 obtained in Example 4 is related to the Si conjugate length. The main chain of [silane] can be presumed to have a structure close to semiflexibility.

Example 5 Poly [(n-hexyl-p-
Methoxyphenyl) _0.8 -co (co)-((S) -2-
Methylbutyl-m-methoxyphenyl) _0.2 silane] was synthesized according to Example 4. The yield was 1.37 g, and the yield was 17.5% in terms of dichlorosilane.

As a result of measuring the weight average molecular weight by the GPC method, it was found to be 750,000 monomodal. FIG. 7 shows an ultraviolet absorption spectrum and a circular two-color (CD) spectrum of the obtained polysilane.
FIG. 8 shows the absorption spectrum, fluorescence spectrum, and fluorescence anisotropy (in tetrahydrofuran, 24.0 ° C.).
That is, FIG. 7 shows poly [(n-hexyl-p-methoxyphenyl) _0.8 -co (co)-obtained in Example 5.
((S) -2-methylbuticle-m-methoxyphenyl) _0.2 silane] absorption, circular dichroism absorption spectrum (at 25 ° C. in tetrahydrofuran), FIG.
It is a graph which shows a fluorescence spectrum and fluorescence anisotropy (24.0 degreeC in tetrahydrofuran).

In FIG. 7, the horizontal axis represents the photon energy (e
V), the left vertical axis represents the extinction coefficient [ε (monomer unit / liter) ⁻¹ cm ⁻¹ ], and the right vertical axis represents the circular two-color extinction coefficient [Δε (monomer unit / liter) ⁻¹ cm ⁻¹ ]. In the UV spectrum, the Si main chain absorption maximum (λmax) is 3.45 eV.
(359.0 nm), and its absorption coefficient (ε) was 9,400. 4.36 eV (284.4n
The absorption maximum observed near m) is due to aromatic substituents. In the CD spectrum, 3.44 eV (36
A positive cotton CD absorption band was observed around (0.5 nm), which was found to be almost similar to the main chain absorption band at 3.45 eV (359.0 nm), and that the maximum absorption was almost the same. At the photon energy at which the circular dichroic absorption spectrum has a maximum value, the asymmetry factor (the value obtained by dividing the CD absorption band by the UV absorption band) which is very sensitive to helix is
It was about 8.1 × 10 ^-5 .

The poly [(n-hexyl-p-methoxyphenyl) _0.8 -co (co)-((S) -2-methylbutyl-m-methoxyphenyl) _0.2 silane] used in this case is the poly [(n-hexyl-p-methoxyphenyl) _0.2 silane] described above. Hexyl-phenyl) _x -co-
((S) -2-methylbutyl-phenyl) _1-x silane]
(Toyoda, Fujiki, Japanese Patent Application No. 9-29947) is considered to show a similar tendency because of a very similar structure, and an asymmetry factor with a (S) -chiral monomer content of about 40 to 50%. Is presumed to be saturated, and its content will take the same winding, spiral pitch, and rigid polymer structure as the homopolymer poly ((S) -2-methylbutyl-m-methoxyphenylsilane). Is done.

In the absorption spectrum, the fluorescence spectrum and the fluorescence anisotropy of FIG. 8, the shapes of the UV spectrum and the fluorescence spectrum in the vicinity of the Si main chain both have a narrow line width and have a perfect mirror image relationship. Further, the fluorescence anisotropy value in the vicinity of the silicon main chain is 371 nm from the wavelength of 345 nm (3.59 eV).
Although the excitation wavelength dependence was slightly strong toward nm (3.34 eV) and showed a tendency of monotonic increase, the value increased from ０0 to around 0.3. These absorption and fluorescence characteristics are related to the Si—Si conjugate length of the main chain skeleton.
The poly [(n-hexyl-p-methoxyphenyl) _0.8 -co (co)-((S) -2-methylbutyl-
m-methoxyphenyl) _0.2 silane]
It can be presumed that the structure is between a random coil and a semi-flexible structure.

[Notable differences in spectra between Examples 4 and 5] In the absorption spectra of Examples 4 and 5,
4.38, 4.36 eV (283.1, 28
(4.4 nm), an absorption maximum considered to be an aromatic substituent is observed. The circular two-color absorption band in this region is a p-type (S)
2-methylbutyl-p-methoxyphenylsilane
Negative in the system copolymerized with 0% (Example 4), and weakly positive in the system copolymerized with 20% of m-form (S) -2-methylbutyl-m-methoxyphenylsilane (Example 5). It can be seen that the sign is completely reversed. The reason for this code reversal is not clear at this time. However, by introducing only about 20% of a chiral component, the helical winding property of the silicon main chain skeleton can be controlled, and the other side chain of the chiral component (methoxyphenyl group)
The fact that the sign of the spectrum of the aromatic ring region can be inverted while maintaining the spectrum of the main chain by manipulating the position of the alkoxy group in the middle is a very interesting phenomenon that has never been seen in the past.

[Other Examples] Although not described in detail here, the present inventors used p-type poly (n-hexyl-p-methoxyphenylsilane) of 80% as the main component shown in Examples 4 and 5. %, And a poly [(n-hexyl-m-methoxyphenyl) _0.8 -co (co)-((S) -2-methylbutyl-m-methoxyphenyl) having an m-form as a main component. Synthesis of _0.2 silane] and poly [(n-hexyl-m-methoxyphenyl) _0.8 -co (co)-((S) -2-methylbutyl-p-methoxyphenyl) _0.2 silane] was also attempted. However, these products were only low molecular weight oligomers, and high molecular weight polymers could not be obtained. The reason for this is that in poly (n-hexyl-m-methoxyphenylsilane) whose main component is m-form, side chain substituents (n-hexyl group, (S) -2-methylbutyl group having a branched structure, bulky methoxyphenyl) Steric hindrance to the group) is very strong, and polymerization of the main chain is inhibited.

[0070]

As shown in the present invention, in an organosilicon homopolymer having both an alkyl substituent and an aryloxyalkyl substituent containing a chiral alkyl group having an asymmetric center at the β-position, poly [methyl -M-{(S) -2-methylbutoxy} phenylsilane] showed optical activity (patent pending as Japanese Patent Application No. 10-351538), while p-form poly (methyl or ethyl or n- Hexyl-p-{(S) -2-methylbutoxy} phenylsilane) did not show optical activity. This indicates that the helical structure of the silicon main chain can be easily controlled by the position of the chiral substituent. When dichlorosilane having a chiral alkyl group having a chiral center at the β-position and a methoxyphenyl derivative group is used as a raw material,
If the optically active chiral monomer is contained in a small amount relative to the achiral monomer, it can give almost the same helical structure, main chain absorption, and circular dichroic absorption spectrum characteristics as the homopolymer synthesized from the chiral monomer having a purity of 100%. Clarified. It is expected that similar results can be obtained by using an optically active chiral monomer having a low optical purity. That is,
Industrially, a small amount of chiral monomer can be used as a raw material for the synthesis of a copolymer, so that it is possible to provide an organic polysilane having a phenyl derivative group containing polar oxygen having a uniform spiral winding property and a uniform spiral pitch at a very low cost. It is now possible. In addition to controlling the helical structure of the silicon main chain, by controlling the position of the alkoxy group in the methoxyphenyl side chain, the inventors have also found a phenomenon in which only the spectrum of the aromatic ring region is inverted while the main chain spectrum is completely maintained.

The optically active organic polysilane prepared completely artificially in this manner has a silicon main chain skeleton and a hydrocarbon side chain having sufficient resistance to hydrolysis and solvolysis, and an aromatic group. Taking advantage of the characteristic that various interactions derived from H
It is expected to be used as a new type of enantiomer-recognizing polymer material such as a PLC or GC column material. Also, by changing the π orbital level of the aromatic substituent, it is possible to easily control the maximum absorption of the interacting silicon main chain over a wide area, and is also very interested in the precise control of optical functionality. Is held.

[Brief description of the drawings]

FIG. 1 shows the poly [methyl-p-
[(S) -2-Methylbutoxy {phenylsilane]] shows absorption, fluorescence spectrum, and fluorescence anisotropy (in tetrahydrofuran, 23.0 ° C.).

FIG. 2 shows the poly [ethyl-p- obtained in Example 2.
[(S) -2-Methylbutoxy {phenylsilane]] shows absorption, fluorescence spectrum, and fluorescence anisotropy (in tetrahydrofuran, 23.0 ° C.).

FIG. 3 shows poly [n-hexyl-p- obtained in Example 3.
[(S) -2-Methylbutoxy {phenylsilane]] shows absorption, fluorescence spectrum, and fluorescence anisotropy (in tetrahydrofuran, 23.0 ° C.).

FIG. 4 shows poly [(n-hexyl-p) obtained in Example 4.
-Methoxyphenyl) _0.8 -co (co)-((S) -2
-Methylbutyl-p-methoxyphenyl) _0.2 silane]
FIG. 2 is a graph showing the absorption spectrum and circular dichroic absorption spectrum (in tetrahydrofuran, at 25.0 ° C.).

FIG. 5 shows the poly [(n-hexyl-p) obtained in Example 4.
-Methoxyphenyl) _0.8 -co (co)-((S) -2
-Methylbutyl-p-methoxyphenyl) _0.2 silane]
FIG. 2 is a graph showing the absorption, fluorescence spectrum, and fluorescence anisotropy (at 24.0 ° C. in tetrahydrofuran) of the present invention.

FIG. 6. Poly [(n-hexyl-m-tolyl) _x -co (co)-((S) -2-methylbutyl-
Dependence of Asymmetry Factor on Chiral Monomer Concentration of Phenyl) _1- xsilane] (Toyoda, Fujiki, Japanese Patent Application No. 9-2994)
7) (25.0 ° C. in tetrahydrofuran).

FIG. 7 shows the poly [(n-hexyl-p) obtained in Example 5.
-Methoxyphenyl) _0.8 -co (co)-((S) -2
-Methylbutyl-m-methoxyphenyl) _0.2 silane]
FIG. 2 is a graph showing the absorption spectrum and circular dichroic absorption spectrum (in tetrahydrofuran, at 25.0 ° C.).

FIG. 8 shows the poly [(n-hexyl-p) obtained in Example 5.
-Methoxyphenyl) _0.8 -co (co)-((S) -2
-Methylbutyl-m-methoxyphenyl) _0.2 silane]
FIG. 2 is a graph showing the absorption, fluorescence spectrum, and fluorescence anisotropy (at 24.0 ° C. in tetrahydrofuran) of the present invention.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Hiromi Takigawa 1-3-1 Gotenyama, Musashino-shi, Tokyo F-term in NTT Advanced Technology Co., Ltd. (reference) 4J035 JA01 JB10 LB20

Claims (5)

[Claims] 1. An organosilicon homopolymer having a chiral substituent represented by the following general formula (I). Embedded image Wherein R ₁ is selected from the group consisting of an alkyl group, an aralkyl group, an aryloxyalkyl group, and an alkyl ether group, and R ^* is an aryloxyalkyl containing a chiral alkyl group having a chiral center at the β-position. Selected from regioisomers of the group, and n ranges from 10 to 100,000. ] 2. In the general formula (I), R ₁ is selected from the group consisting of a methyl group, an ethyl group and an n-hexyl group, and R ^* is a p-{(S) -2-methylbutoxy} phenyl group. And a chiral substituent according to claim 1, characterized in that it is selected from the group consisting of and p-{(R) -2-methylbutoxy} phenyl, and wherein n is in the range from 10 to 100,000. Organic silicon homopolymer. 3. An optically active chiral substituent-containing silicon unit represented by the following general formula (II) is included in a part of the main chain skeleton, and n is in the range of 10 to 100,000. Characteristic optically active organosilicon copolymer. Embedded image [Where R ₁ is selected from the group consisting of an alkyl group, an aralkyl group, an aryloxyalkyl group, and an alkyl ether group, R ₂ and R ₃ are selected from the same or different regioisomers of an alkyloxyaryl group, R
^* Represents a chiral alkyl group in which the β-position is an asymmetric center,
x indicates 0.001 ≦ x ≦ 0.999. ] 4. In the general formula (II), R ₁ is n-
A hexyl group; R ₂ and R ₃ represent a p-methoxyphenyl group; R ^* is selected from the group consisting of a (S) -2-methylbutyl group or a (R) -2-methylbutyl group; 001 ≦ x ≦ 0.999, and n
The optically active organosilicon copolymer according to claim 3, wherein is in the range of 10 to 100,000. 5. In the general formula (II), R ₁ is n-
A hexyl group; R ₂ is a p-methoxyphenyl group; R ₃ is an m-methoxyphenyl group; and R ^* is a group consisting of (S) -2-methylbutyl and (R) -2-methylbutyl. And x is 0.001 ≦ x
≦ 0.999, and n is 10 to 100000
The optically active organosilicon copolymer according to claim 3, wherein