JPH06256355A - New silanol compound, and production of liquid crystal group-bearing monomer using the same - Google Patents

Abstract

PURPOSE:To obtain a polymerizable group-bearing silanol compound useful as a precursor for side chain-type polymeric liquid crystals having flexible chemical structure in its spacer region. CONSTITUTION:A compound of formula I (R is H, halogen, cyano, alkyl or phenyl; R<1> & R<2> are each alkyl or phenyl; 2-10), e.g. 3- methacryloxypropyldimethylsilanol. The compound of formula I can be obtained by dissolving a polymerizable group-bearing chlorosilane compound of formula II in an organic solvent (e.g. hexane) followed by conducting reaction with a large excess of water or an organic solvent-contg. water under a chilled state at 0 deg.C or so. Using the compound of the formula I, a liquid crystal group- bearing monomer of formula III (R<1>-R<6> are each alkyl or phenyl; X is single bond, O, COO or OCO; Q is liquid crystal group; (q) is 2-10; (m) is 0-5) can be derived. The polymer obtained by polymerizing this monomer is useful as a display material in the electronics industry, recording material, nonlinear optical material, material for light-modulating glass, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel silanol compound having a polymerizing group and, by using the same, a spacer portion connecting the polymerizing group and the liquid crystal group with a siloxane unit having 3 units.
The present invention relates to a method for producing a monomer having a liquid crystal group, in which a chemical bond containing at least one polysiloxane component is introduced. The monomer having a liquid crystal group obtained by the production method of the present invention is used for synthesizing a side chain type polymer liquid crystal in which a spacer portion connecting a main chain and a side chain liquid crystal group has a chemical bond including a flexible polysiloxane bond. It is particularly useful as a synthetic intermediate.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a side chain type polymer liquid crystal having a liquid crystal group in a side chain has a function used as a display element or a recording material in the field of electronics, and recently as a non-linear optical material or a light control glass. A wide range of applications have been studied as a flexible material. A conventionally known side chain type polymer liquid crystal has a structure in which a liquid crystal group is bonded to a polymer main chain skeleton through a spacer. In this case, polymers such as polymethacrylate, polyacrylate, polyether, polyorganosiloxane and polyester are known as the main chain skeleton, and many side chain type polymer liquid crystals have been proposed. (For example, Naoyuki Koide, Liquid Crystal Polymer, CMC (1987); R. Zentel, "Liquid Crystalli
nePolymers ", Kem. Ind., Volume 37, p.355 (1988);
VP Shibaev, "Synthesis and Structure of Liquid-
crystalline side-chain polymers ", Pure & Appl. Che
m., Volume 57, p. 1589 (1985); T. Chung, "The Rece
nt Developments of Thermotropic Liquid Crystalline
Polymers ", Polym. Eng. Sci., Volume 26, p.901 (1986
)) In addition, since the mobility of the main chain skeleton and the liquid crystal group are independent via the spacer, the alignment state of the liquid crystal can be easily expressed, and the spacer can be lengthened or the spacer with high mobility is used. Is said to develop a more stable liquid crystal phase. (Naoyuki Koide, "Synthesis of Polymer Liquid Crystal", Polymer, No. 1
36, p.98 (1987)) Conventionally, most of the chemical bonds known as spacers are alkylene groups and oxyalkylene groups. However, when such a spacer is used for the above-mentioned main chain skeleton, in general, the temperature at which liquid crystallinity is exhibited is high, and in most cases, the glassy state is obtained without exhibiting liquid crystallinity near room temperature. On the other hand, the present inventors have reported a side chain type polymer liquid crystal having a main chain skeleton of polymethacrylate and a liquid crystal group bonded via a spacer containing a siloxane component known as a flexible chemical bond. (Japanese Patent Laid-Open No. 4-218513; Y. Nagase
and Y. Takamura, "Side-chain liquid-crystalline po
lymers containing a siloxane spacer, 1: Synthesis
ofside-chain liquid-crystalline polymers containin
g siloxane bond in the spacer unit ", Makromol. Che
m., 193, p.1225 (1992))

[0003]

However, in most of the conventional cases, a disiloxane component having two siloxane units was introduced as the siloxane bond, and a polysiloxane having three or more siloxane units due to difficulty in synthesis. There are very few examples of introducing components. We have
In the above-mentioned published patent publications and papers, the synthesis of a side chain type polymer liquid crystal in which a polysiloxane component is introduced into a spacer is reported. In the production of the monomer, a silanol compound having a liquid crystal group as a raw material is reacted with a strong base to form a silanolate anion, then a cyclosiloxane compound is subjected to ring-opening polymerization, and the reaction is terminated with a chlorosilane compound having a polymerizable group. It is done by things. However, in this method, since the polysiloxane component is formed by ring-opening polymerization of cyclosiloxane, there is a problem that the number of siloxane units in the polysiloxane component cannot be made uniform. As a result, the polymer obtained by polymerizing the monomer did not exhibit liquid crystallinity because the alignment of the liquid crystal group could not be achieved because the length of the spacer portion was different for each monomer unit. Further, in this conventional production method, since the silanol compound having a liquid crystal group is first reacted with a strong base, there is a drawback that a substituent such as an ester group which is easily hydrolyzed cannot be introduced into the liquid crystal group.

An object of the present invention is to introduce a chemical bond containing a polysiloxane component having extremely high mobility into a spacer so that a side chain exhibiting stable liquid crystallinity at a relatively low temperature, that is, room temperature or lower. In the case of synthesizing a high-molecular liquid crystal, a simple and versatile method for producing a monomer as a raw material, that is, a monomer in which a polysiloxane component having a uniform length is introduced into a spacer part connecting a polymerization group and a liquid crystal group To provide.

[0005]

[Means for Solving the Problems] The present inventors have conducted earnest studies to synthesize a monomer as a raw material of a side chain type polymer liquid crystal having a polysiloxane component having three or more siloxane units in a spacer. . As a result, it was found that a novel silanol compound having a polymerizing group can be synthesized, and by using the obtained silanol compound as a raw material, a monomer in which a polymerizing group and a liquid crystal group are bonded via a spacer containing a polysiloxane component can be obtained. Can be composed,
Moreover, they have found that a side chain type polymer liquid crystal having a polysiloxane component in a spacer and exhibiting liquid crystallinity at a relatively low temperature can be produced by polymerizing the monomer, and thus reached the present invention.

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

[0007]

[Chemical 6]

(Wherein R is a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a phenyl group, R ¹ and R ² may be the same or different, an alkyl group or a phenyl group, and p is an integer of 2 to 10). And a silanol compound having a polymerizing group represented by the following general formula (I
I)

[0009]

[Chemical 7]

(Wherein R ³ and R ⁴ may be the same or different, an alkyl group or a phenyl group, X is a single bond, an oxygen atom, or a group represented by --COO-- or --OCO--, and Q is a liquid crystal. Group, q is an integer of 2 to 10, and a silanol compound having a liquid crystal group represented by the following general formula (III)

[0011]

[Chemical 8]

(Wherein R ^{5 to} R ⁸ may be the same or different and are an alkyl group or a phenyl group, m is an integer of 0 to 5), and then the above-mentioned reaction is carried out. Reacting with a silanol compound having a polymerizing group represented by general formula (I), represented by the following general formula (IV)

[0013]

[Chemical 9]

(Wherein R is a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a phenyl group, R ^{1 to} R ⁸ may be the same or different, an alkyl group or a phenyl group, X is a single bond or an oxygen atom. , Or -COO- or -OCO-
Is a liquid crystal group, p and q are integers of 2 to 10, and m is an integer of 0 to 5. And a method for producing a monomer having a liquid crystal group represented by the formula (1).

Of the substituents represented by R in the above general formulas (I) and (IV), the alkyl group is a methyl group,
A lower alkyl group such as an ethyl group, a propyl group, an isopropyl group and a butyl group is preferable from the viewpoint of the polymerizability of the resulting monomer. Further, in the above general formulas (I) to (IV), R ^{1 to} R ⁸
The substituents represented by may be the same or different, for example, linear or branched such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group and hexyl group. And a phenyl group and the like. However, the methyl group is most preferable among the above-mentioned substituents in order to facilitate the synthesis and to utilize the characteristics of the side chain type polymer liquid crystal having a polysiloxane component in the spacer, which is derived from these compounds. Further, the methylene chains in the above general formulas (I), (II) and (IV) need to have a certain length, and therefore the number of methylene groups represented by p and q in these formulas is 2-10. It is a range. However, p is preferably in the range of 3 to 6 in order to facilitate the synthesis and to take advantage of the characteristics of the side chain type polymer liquid crystal having a polysiloxane component in the spacer derived from the silanol compound. Further, the above general formulas (III) and (IV)
The number of siloxane units represented by m is in the range of 0 to 5, and particularly preferably in the range of 0 to 3 in order to facilitate the synthesis and to utilize the characteristics of the resulting side chain polymer liquid crystal. .

The liquid crystal group represented by Q in the general formulas (II) and (IV) may be any of the conventionally known liquid crystallinity imparting groups, and the structure thereof is not particularly limited. Examples of the liquid crystal group include biphenyl, biphenyl ether, phenyl benzoate,
Benzoic acid biphenyl ester, benzylidene aniline,
Removes one hydrogen atom from liquid crystal molecules such as stilbene, azoxybenzene, azobenzene, Schiff base, cyclohexylphenyl ether, cyclohexylbenzene, cyclohexylcarboxylic acid phenyl ester, cyclohexylcarboxylic acid biphenyl ester, cholesterin, cholestane and their derivatives. The group consisting of Further, by bonding a polar group such as an alkyl group having an optically active group, an alkoxy group, a fluoroalkyl group, a cyanoalkyl group, or a cyanoalkoxy group to the liquid crystal molecule, the polymer obtained by the production method of the present invention is ferroelectric. It is also possible to add special effects such as sex.

The silanol compound having a polymerizing group represented by the general formula (I) of the present invention can be produced, for example, by the following method. That is, the following general formula (V)

[0018]

[Chemical 10]

(Wherein R is a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a phenyl group, R ¹ and R ² may be the same or different, an alkyl group or a phenyl group, and p is an integer of 2 to 10). A chlorosilane compound having a polymerizing group represented by the general formula (I) is dissolved in an organic solvent and reacted with a large excess of water or water containing an organic solvent. The silanol compound can be easily synthesized. As the organic solvent used here, hexane, heptane,
Diethyl ether, ethyl acetate, benzene, toluene,
Xylene, chloroform, dichloromethane, dichloroethane, acetone, tetrahydrofuran, etc. are preferably used, but not limited thereto. Further, it is preferable to carry out this reaction by cooling to around 0 ° C. in order to suppress side reactions.

As the chlorosilane compound having a polymerizing group represented by the general formula (V) used in the above reaction, 2- (acryloxy) ethyldimethylchlorosilane, 2- (methacryloxy) ethyldimethylchlorosilane, 2- (α- Ethylacryloxy) ethyldimethylchlorosilane, 2- (α-butylacryloxy) ethyldimethylchlorosilane, 2- (α-chloroacryloxy) ethyldimethylchlorosilane, 2- (α-fluoroacryloxy) ethyldimethylchlorosilane, 2- ( α-Cyanoacryloxy) ethyldimethylchlorosilane, 2- (α-phenylacryloxy) ethyldimethylchlorosilane, 3-
(Acryloxy) propyldimethylchlorosilane, 3-
(Methacryloxy) propyldimethylchlorosilane, 3-
(Α-ethylacryloxy) propyldimethylchlorosilane, 3- (α-butylacryloxy) propyldimethylchlorosilane, 3- (α-chloroacryloxy) propyldimethylchlorosilane, 3- (α-fluoroacryloxy) propyldimethylchlorosilane, 3- (α-cyanoacryloxy) propyldimethylchlorosilane, 3- (α-
Phenylacryloxy) propyldimethylchlorosilane, 4- (methacryloxy) butyldimethylchlorosilane, 5- (methacryloxy) pentyldimethylchlorosilane, 6- (methacryloxy) hexyldimethylchlorosilane, 3- (methacryloxy) propyldiethylchlorosilane, 3-methacryloxypropyldibutyl Chlorosilane,
Examples include 3- (methacryloxy) propyldihexylchlorosilane, 3- (methacryloxy) propylmethylbutylchlorosilane, 3- (methacryloxy) propylmethylhexylchlorosilane, 3- (methacryloxy) propylmethylphenylchlorosilane, 3- (methacryloxy) propyldiphenylchlorosilane can do. Some of these are commercially available or can be synthesized by the hydrosilylation reaction of the corresponding α-substituted or unsubstituted alkenyl ester of acrylic acid with diorganochlorosilane.

In the method for producing a monomer having a liquid crystal group represented by the general formula (IV) according to the present invention, the silanol compound having a liquid crystal group represented by the general formula (II) is added to the general formula (III). It is preferable to use at least 2 equivalents or more of the dichloro compound represented by In addition, this reaction is preferably carried out by diluting the compound represented by the general formula (II) in an organic solvent.
As the organic solvent used here, hexane, heptane, diethyl ether, ethyl acetate, benzene, toluene, xylene, chloroform, dichloromethane, dichloroethane, acetone, tetrahydrofuran and the like are preferably used, but are not limited thereto. . Also,
It is preferable to carry out this reaction by cooling to around 0 ° C. in order to suppress side reactions. Furthermore, since hydrogen chloride is generated in this reaction, triethylamine, N,
The reaction suitably proceeds in the presence of an organic base such as N-dimethylaniline or pyridine.

In the production method of the present invention, following the above reaction, a silanol compound having a polymerizing group represented by the general formula (I) is reacted to give a monomer having a liquid crystal group represented by the general formula (IV). When synthesizing, the dichloro compound represented by the general formula (III) is preferably distilled out of the reaction system in advance. Also,
This reaction is also preferably carried out in an organic solvent, and the organic solvent preferably used is the same as described above. Further, since hydrogen chloride is similarly generated in this reaction, the reaction proceeds suitably by carrying out it in the presence of an organic base such as triethylamine, N, N-dimethylaniline or pyridine as a scavenger.

The silanol compound having a liquid crystal group represented by the general formula (II) used in the production method of the present invention can be produced, for example, by the following method. That is, the following general formula (VI)

[0024]

[Chemical 11]

(In the formula, X is a single bond, an oxygen atom, or -C
A group represented by OO- or -OCO-, Q is a liquid crystal group, and q is an integer of 2 to 10. ) An alkenyl compound having a liquid crystal group represented by the following general formula (VII)

[0026]

[Chemical 12]

(Wherein R ³ and R ⁴ may be the same or different, and are an alkyl group or a phenyl group, and R ′ is an alkyl group), and the reaction is carried out in the presence of a hydrosilylation catalyst. The following general formula (VIII)

[0028]

[Chemical 13]

(In the formula, R ³ and R ⁴ may be the same or different, an alkyl group or a phenyl group, R is an alkyl group, X is a single bond, an oxygen atom, or —COO— or —OC.
A group represented by O-, Q is a liquid crystal group, and q is an integer of 2 to 10. ), And by further hydrolyzing the compound represented by the general formula (VIII), a silanol compound having a liquid crystal group represented by the general formula (II) can be produced.

In the above manufacturing method, the above general formula (V
I) and the above-mentioned general formula (VI)
The hydrosilylation catalyst used when the compound represented by the general formula (VIII) is reacted with the alkoxysilane represented by I) is platinum, platinum carbon,
Most commonly, platinum-based catalysts such as chloroplatinic acid and dicyclopentadienyl platinum dichloride are used, but other metal complexes containing palladium or rhodium can be used. For example, (Ph ₃ P) ₄ Pd ,, (P
h ₃ P) ₂ PdCl ₂ ,, (PhCN) ₂ PdCl ₂ ,, (Ph
₃ P) ₃ RhCl, (Ph ₂ PH) ₂ RhCl, (Ph
₃ P) ₂ (CO) RhCl, [(C ₂ H ₅ ) ₃ P] ₂ (CO) Rh
Cl or the like can be used as a catalyst. The amount of the catalyst used is usually about 1/100 to 1/1000 equivalent with respect to the alkenyl compound represented by the general formula (VI). In order to complete this reaction, the compound represented by the general formula (VII) is a compound represented by the general formula (V).
It is necessary to mix the compound represented by I) in an equimolar amount or more. This reaction is preferably carried out in a solvent, and as the solvent, hexane, benzene, toluene, acetone, trichloroethylene, carbon tetrachloride, tetrahydrofuran or the like can be used. The reaction temperature is usually in the temperature range of 40 ° C. to 100 ° C., and preferably in an inert gas atmosphere such as argon or nitrogen.

The synthesis of the alkenyl compound having a liquid crystal group represented by the general formula (VI) is carried out by introducing the alkenyl group directly into the above-mentioned liquid crystal group, as will be shown later in Reference Examples.
Alternatively, it can be easily achieved by introducing an alkenyl group in one step in synthesizing the above liquid crystal group.

Examples of the alkoxysilane compound represented by the general formula (VII) include dimethylmethoxysilane and
Dimethylethoxysilane, dimethylpropoxysilane,
Examples thereof include dimethylisopropoxysilane, diethylethoxysilane, dipropylethoxysilane, dibutylethoxysilane, dihexylethoxysilane, methylethylethoxysilane, methylphenylethoxysilane and diphenylethoxysilane. Some of these are commercially available, and can be easily synthesized by a condensation reaction between a corresponding commercially available chlorosilane compound and an alcohol.

The hydrolysis reaction carried out when the silanol compound represented by the general formula (II) is produced from the compound represented by the general formula (VIII) is usually carried out in the presence of a basic or acidic substance. The reaction proceeds smoothly. As the basic or acidic substance used here, basic substances such as lithium hydroxide, potassium hydroxide, sodium hydroxide, aluminum hydroxide, potassium carbonate, sodium carbonate, potassium acetate, sodium acetate or hydrochloric acid, sulfuric acid, nitric acid, Acidic substances such as acetic acid, calcium sulfate, calcium nitrate and magnesium sulfate are preferably used. In particular, when a liquid crystal group Q in the general formula (VIII) has a bond such as an ester bond that is susceptible to hydrolysis, a weakly basic or weakly acidic substance among the above basic or acidic substances is used. Is preferred. It is preferable to use these basic or acidic substances in the range of 0.1 to 5.0 equivalents relative to the compound represented by the general formula (VIII). Further, this reaction is essential to be carried out in the presence of water, but when the compound represented by the general formula (VIII) is insoluble in water, methanol, ethanol,
The reaction proceeds properly by using a water-soluble organic solvent such as propanol, acetone, tetrahydrofuran, or acetonitrile in combination. The reaction temperature is usually around room temperature, but if the temperature is high, the disiloxane compound, which is a dimer of the target silanol, may be obtained as a by-product. Further, when the dimerization reaction is likely to proceed, it is necessary to control the reaction temperature in the range of −100 ° C. to room temperature in order to minimize the amount of by-products produced.

Examples of the dichloro compound represented by the general formula (III) used in the production method of the present invention include dichlorodimethylsilane, dichlorodiethylsilane, dichlorodipropylsilane, dichlorodibutylsilane, dichlorodiisopropylsilane, dichlorodihexylsilane, Dichloromethylethylsilane, dichloromethylphenylsilane, dichlorodiphenylsilane, 1,3-dichlorotetramethyldisiloxane, 1,3-dichlorotetraethyldisiloxane, 1,3-dichlorotetraphenyldisiloxane, 1,5-dichlorohexamethyl Trisiloxane,
Examples thereof include 1,7-dichlorooctamethyltetrasiloxane, 1,9-dichlorodecamethylpentasiloxane, and 1,11-dichlorododecamethylhexasiloxane, which are commercially available.

When the monomer having a liquid crystal group represented by the general formula (IV) obtained by the production method of the present invention is polymerized, two or more kinds of monomers may be mixed, and radical polymerization may be carried out. Well-known polymerization methods such as anionic polymerization and cationic polymerization can be used. However, in this case, the radical polymerization method is preferably used as the simplest polymerization method. When the radical polymerization method is used, known methods such as bulk polymerization, solution polymerization and emulsion polymerization can be used. The radical polymerization reaction is initiated simply by irradiation with heat, ultraviolet rays or addition of a radical initiator. As the radical initiator preferably used in the reaction,
Organic peroxides such as dilauroyl peroxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl hydroperoxide and cumene hydroperoxide, or α, α ',-azobisisobutyronitrile and azobiscyclohexanecarbonitrile. An azo compound etc. can be illustrated. Moreover, the molecular weight of the obtained polymer can be controlled to some extent by adding a chain transfer agent during the polymerization reaction. As the chain transfer agent used here, carbon tetrachloride, bromotrichloromethane, p-benzoquinone, chloroanil, n-butanethiol, n-
Examples include dodecanethiol and the like. Organic solvents that can be used in the radical polymerization reaction in this case include, for example, benzene, toluene, chlorobenzene, tetrahydrofuran,
Chloroform, methyl ethyl ketone, fluorobenzene, methanol, ethanol, n- or i-propanol, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used, but not limited thereto. The reaction is usually 40 ° C to 100
It progresses smoothly in the range of ℃.

As described above, by using the silanol compound having a polymerizing group represented by the general formula (I) of the present invention, represented by the general formula (IV),
A monomer having a liquid crystal group in which a polymerizing group and a liquid crystal group are bonded via a chemical bond containing a polysiloxane component having three or more siloxane units can be easily produced. In addition, the polymer obtained by polymerizing this monomer has a polysiloxane component having high mobility in the spacer, so that the glass transition temperature is as low as room temperature or lower, and as will be shown later as a use example, a relatively low temperature, that is, room temperature. Alternatively, it has been found that stable liquid crystallinity is exhibited in a wide temperature range from a temperature lower than that. Therefore, the polymer obtained by polymerizing the monomer obtained by the production method of the present invention can be applied to various uses such as a display material, a recording material, a non-linear optical material and a material for light control glass in the electronics field.

The present invention will be described in more detail with reference to Reference Examples, Examples and Usage Examples. However, it goes without saying that the present invention is not limited to these.

[0038]

【Example】

 Example 1 Synthesis of silanol compound having a polymerizing group

[0039]

[Chemical 14]

10.0 g (45.3 mmol) of 3-methacryloxypropyldimethylchlorosilane was added to 50 ml of anhydrous tetrahydrofuran.
Dissolved in water, and the solution was added to 100 m of water cooled to 0 ° C on an ice bath.
It was slowly added dropwise to a mixed solution of 1 and 200 ml of diethyl ether. After the dropping was completed, the mixture was further stirred at 0 ° C. for 1 hour.
The organic phase was extracted with diethyl ether, the solvent was distilled off, and the residue was purified by silica gel column chromatography. 4.
27 g of a colorless transparent liquid was obtained. For the product obtained,
It was confirmed to be 3-methacryloxypropyldimethylsilanol represented by the above chemical formula (1) by performing ¹ H-NMR, IR and Mass spectrum analysis.
(Yield; 46.6%)

¹ H-NMR, δ (CDCl ₃ , ppm); 0.05 (s, 6H),
0.89-0.98 (m, 2H), 2.19-2.28 (m, 2H), 2.29 (s, 3
H), 3.27 (bs, 1H), 4.48 (t, 2H, J = 7.0Hz), 5.90 (m,
1H), 6.45 (m, 1H). IR (cm ^-1 ); 3450 (-OH), 2980, 2910, 1730 (C = O), 164
0, 1455, 1410, 1330, 1300, 1260 (Si-C), 1200, 1170
(Si-O), 1145, 1110, 980, 940, 870, 840, 780. Mass (m / e); 187 (M ⁺ -Me), 143, 75 (HOMe ₂ Si ⁺ ), 69 (C
H ₂ = C (CH ₃ ) CO ⁺ ), 41 (CH ₂ = C (CH ₃ ) ⁺ ).

Reference Example 1 Synthesis of silanol compound having liquid crystal group 1

[0043]

[Chemical 15]

Methyl p-hydroxybenzoate 15.0 g (98.6 m
mol), 13.0 g (94.1 mmol) of potassium carbonate, 150 ml of acetone
To the solution mixed therein, 13 ml (150 mmol) of allyl bromide was added, and the mixture was stirred at 80 ° C. for 2 hours under an argon gas atmosphere. After adding water to this solution and extracting with ethyl acetate, the organic phase was washed with a 5% sodium hydroxide aqueous solution and saturated saline. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain 18.6 g of a colorless transparent liquid. The obtained product was analyzed by ¹ H-NMR, IR and Mass spectra, and was confirmed to be methyl p-allyloxybenzoate represented by the above chemical formula (2). (yield;
(96.6%)

¹ H-NMR, δ (CDCl ₃ , ppm); 3.88 (s, 3H),
4.58 (d, 2H, J = 5.0Hz), 5.32 (m, 1H), 5.43 (m, 1
H), 5.86 ~ 6.22 (m, 1H), 6.92 (d, 2H, J = 6.9Hz), 7.9
8 (d, 2H, J = 6.8Hz). IR (cm ^-1 ); 2960, 1720 (C = O), 1610, 1510, 1435, 128
0, 1255, 1170, 1110, 1020, 845, 770. Mass (m / e); 192 (M ⁺ ), 161, 41 (CH ₂ = CHCH ₂ ⁺ ).

14.0 g (93.6 mmol) of methyl p-allyloxybenzoate obtained here was dissolved in 600 ml of ethanol, and this solution was poured into a solution of 12.0 g (300 mmol) of sodium hydroxide in 80 ml of water and 100 ml of methanol. The mixture was further refluxed at 80 ° C for 2 hours. The solvent was distilled off, the obtained white solid was dissolved in water, and hydrochloric acid was added until it became acidic, whereby a white precipitate was produced. This was extracted with methylene chloride, the organic phase was washed with saturated saline and then dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was purified by silica gel column chromatography to obtain 14.7 g of white solid. The obtained product is analyzed by ¹ H-NMR, IR and Mass spectrum, and is represented by the above chemical formula (3).
It was confirmed to be p-allyloxybenzoic acid. (yield;
(88.1%)

¹ H-NMR, δ (CDCl ₃ , ppm); 4.61 (d, 2H,
J = 5.0Hz), 5.44 (m, 1H), 5.51 (m, 1H), 5.77 to 6.23
(m, 1H), 6.97 (d, 2H, J = 7.0Hz), 8.07 (d, 2H, J = 6.9
Hz). IR (cm ^-1 ); 2450 ~ 3000 (-OH), 1680 (C = O), 1600, 155
0, 1430, 1350, 1250, 1180, 1010, 1000, 930, 850, 7
70. Mass (m / e); 178 (M ⁺ ), 41 (CH ₂ = CHCH ₂ ⁺ ).

Chloroform pentoxide (90 g) was added with chloroform (100 ml) and diethyl ether (200 ml), refluxed at 60 ° C. for 2 days in an argon gas atmosphere, and the solvent was distilled off to give polyphosphoric acid ester (hereinafter abbreviated as PPE) viscous. Obtained as a colorless liquid. 26.4 g of this PPE, 5.88 g (33.0 mmol) of p-allyloxybenzoic acid and 8.00 g (33.0 mmol) of 4-butoxy-4′-hydroxybiphenyl were dissolved in 150 ml of chloroform under an argon gas atmosphere and stirred overnight at room temperature. After adding water and extracting with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 12.8 g of a white solid. Regarding the obtained product, ¹ H-NMR,
IR and Mass spectrum analyzes were performed, and 4- (4'-butoxybiphenyl) p- represented by the above chemical formula (4) was obtained.
It was confirmed to be allyloxybenzoate. (Yield; 96.4%)

¹ H-NMR, δ (CDCl ₃ , ppm); 0.99 (t, 3H,
J = 6.6Hz), 1.35 ~ 1.95 (m, 4H), 4.01 (t, 2H, J = 6.3H
z), 4.64 (dt, 2H, J = 5.1Hz), 5.18-5.50 (m, 2H), 5.7
8 to 6.23 (m, 1H), 6.96 (d, 2H, J = 8.5Hz), 7.00 (d, 2
H, J = 9.0Hz), 7.23 (d, 2H, J = 8.6Hz), 7.51 (d, 2H, J
= 8.8Hz), 7.58 (d, 2H, J = 8.8Hz), 8.16 (d, 2H, J = 9.0
Hz). IR (cm ^-1 ); 2960, 2940, 2880, 1720 (C = O), 1600, 151
0, 1470, 1320, 1245, 1210, 1160, 1070, 1040, 940,
840, 810, 760. Mass (m / e); 402 (M ⁺ ), 161, 41 (CH ₂ = CHCH ₂ ⁺ ).

The obtained 4- (4'-butoxybiphenyl) p-allyloxybenzoate (8.75 g, 21.0 mmol) and dimethylethoxysilane (7.30 ml, 53.0 mmol) were added to tetrahydrofuran (10).
It was dissolved in 0 ml, 0.50 ml of a methylene chloride solution of dicyclopentadienylplatinum dichloride (0.1 mol / l) was added, and the mixture was stirred at 50 ° C. for 3 hours under an argon gas atmosphere. After the solvent was distilled off, 4- (4'-butoxybiphenyl) p- (3-dimethylethoxysilylpropoxy) benzoate represented by the above chemical formula (5) was obtained as a crude product.

The crude product obtained here was dissolved in 35 ml of acetone and 50 ml of tetrahydrofuran, and this solution was poured at room temperature into a solution of 9.0 g (65.1 mmol) of potassium carbonate in 15 ml of water and 45 ml of acetone. An aqueous solution in which 9.0 g (65.1 mmol) of potassium carbonate was dissolved in 45 ml of water was added to the solution. After stirring at room temperature for 8 hours, the reaction solution was poured into an excess amount of ice water containing 30 g of potassium dihydrogen phosphate, extracted with methylene chloride, and the organic phase was dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain 4.38 g of white solid. The obtained product was analyzed by ¹ H-NMR, IR and Mass spectrum to obtain the above chemical formula (6).
Was confirmed to be 4- (4'-butoxybiphenyl) p- (3-dimethylhydroxysilylpropoxy) benzoate. (Yield; 42.2% in 2 steps)

¹ H-NMR, δ (CDCl ₃ , ppm); 0.12 (s, 6H),
0.52-0.82 (m, 2H), 0.98 (t, 3H, J = 3.8Hz), 1.12-
1.92 (m, 7H), 3.97 (t, 2H, J = 6.5Hz), 4.00 (t, 2H,
J = 6.5Hz), 6.92 (d, 4H, J = 8.0Hz), 7.20 (d, 2H, J = 7.
8Hz), 7.84 (d, 2H, J = 8.6Hz), 7.92 (d, 2H, J = 8.6Hz),
8.15 (d, 2H, J = 8.9Hz). IR (cm ^-1 ); 3400 (-OH), 2960, 2940, 2880, 1740 (C =
O), 1720, 1620, 1510, 1490, 1440, 1410, 1260 (Si-
C), 1220, 1175, 1090, 1060 (Si-O), 1010, 990,900,
840, 820, 780. Mass (m / e); 478 (M ⁺ ), 416, 362, 242, 186, 121, 75
(HOMe ₂ Si ⁺ ).

Example 2 Monomer Synthesis 1

[0054]

[Chemical 16]

1.48 g (8.15 mmol) of 4- (4'-butoxybiphenyl) p- (3-dimethylhydroxysilylpropoxy) benzoate obtained in Reference Example 1 was dissolved in 100 ml of anhydrous tetrahydrofuran under an argon gas atmosphere, and this solution was prepared. To the mixture was added 0.43 ml (3.09 mmol) of triethylamine. 30.0 ml (247 mmol) of dichlorodimethylsilane was placed in a 500 ml three-necked flask, cooled to 0 ° C on an ice bath, and the above solution was slowly added dropwise from an addition funnel under an argon gas atmosphere, and after the addition was completed, the temperature was further increased to 0 ° C. And stirred for 1 hour. Next, this reaction vessel was connected to a vacuum pump, and excess dichlorodimethylsilane and the solvent were distilled off under reduced pressure at room temperature to dry the intermediate product. After adding 30 ml of anhydrous tetrahydrofuran again to dissolve the product, 0.75 g (3.71 mmol) of 3-methacryloxypropyldimethylsilanol obtained in Example 1 was added and stirred overnight at room temperature. Since a white salt is formed, it is filtered off while washing with diethyl ether, the solvent is distilled off, and then purified by silica gel column chromatography 1.
57 g of white solid was obtained. For the product obtained, ¹ H
-NMR, IR and Mass spectrum analyzes were performed, and it was confirmed that the monomer was represented by the above chemical formula (7). (Yield; 68.8%)

¹ H-NMR, δ (CDCl ₃ , ppm); 0.20 (s, 18
H), 0.54-0.86 (m, 4H), 1.01 (t, 3H, J = 6.2Hz), 1.20-
2.22 (m, 8H), 2.25 (s, 3H), 4.36 (m, 6H), 6.08 (m,
1H), 6.68 (m, 1H), 7.43 (d, 4H, J = 7.9Hz), 7.70
(d, 2H, J = 7.9Hz), 7.94 (d, 2H, J = 8.6Hz), 8.05 (d, 2
H, J = 8.6Hz), 8.60 (d, 2H, J = 8.9Hz). IR (cm ^-1 ); 2970, 2940, 2900, 1730 (C = O), 1640, 160
5, 1580, 1515, 1500, 1475, 1420, 1320, 1290, 1260
(Si-C), 1220, 1170, 1110-1000 (SiOSi), 970,940, 90
0, 840, 800. Mass (m / e); 736 (M ⁺ ), 635, 561, 487, 439, 291, 21
7, 69 (CH ₂ = C (CH ₃ ) CO ⁺ ), 41 (CH ₂ = C (CH ₃ ) ⁺ ).

USE EXAMPLE 1 Polymer Synthesis 1

[0058]

[Chemical 17]

0.50 g (0.678 g) of the monomer obtained in Example 2
mmol) was dissolved in 7 ml of tetrahydrofuran, and 4.45 mg (0.0271 mmol) of azobisisobutyronitrile was added to this solution. After this solution was sufficiently degassed by freezing, a polymerization reaction was carried out at 60 ° C. for 24 hours. The reaction solution was poured into 400 ml of methanol, the obtained precipitate was recovered, further dissolved in tetrahydrofuran, and reprecipitation was repeated twice in methanol. As a result, 0.27 g of a white solid polymer was obtained.
(Yield; 54.0%) For the obtained polymer, ¹ H-NM
An R spectrum analysis was performed, and it was confirmed that the polymer was represented by the above chemical formula (8). The number average molecular weight and the weight average molecular weight determined by gel permeation chromatography are 3.
It was 91x10 ³ and 5.02x10 ³ . Further, the glass transition temperature of this polymer was −6 ° C. by DSC measurement and polarization microscope observation, and a smectic liquid crystal phase was exhibited in a wide temperature range from −6 ° C. to 156 ° C.

¹ H-NMR, δ (CDCl ₃ , ppm); 0.20 (s, 18
H), 0.54-0.86 (m, 4H), 1.15-2.42 (m, 14H), 4.34-4.6
0 (m, 6H), 7.43 (d, 4H, J = 6.6Hz), 7.63 (d, 2H, J =
6.7Hz), 7.95 (d, 2H, J = 6.7Hz), 8.05 (d, 2H, J = 6.8H
z), 8.61 (d, 2H, J = 6.6Hz).

Reference Example 2 Synthesis of silanol compound having liquid crystal group 2

[0062]

[Chemical 18]

15.0 g of PPE and p-allyloxybenzoic acid 2.
65 g (15.2 mmol) and 4.50 g (13.4 mmol) of 4-octyloxy-4′-hydroxybiphenyl were dissolved in 120 ml of chloroform under an argon gas atmosphere, and the mixture was stirred overnight at room temperature. After adding water and extracting with methylene chloride, the organic phase was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 5.30 g of a white solid. The obtained product was analyzed by 1 H-NMR, IR and Mass spectrum to give 4- (4′-octyloxybiphenyl) represented by the above chemical formula (9).
It was confirmed to be p-allyloxybenzoate.
(Yield; 86.2%)

¹ H-NMR, δ (CDCl ₃ , ppm); 0.89 (t, 3H,
J = 2.4Hz), 1.20-2.05 (m, 12H), 4.00 (t, 2H, J = 6.4H
z), 4.64 (d, 2H, J = 5.1Hz), 5.25-5.65 (m, 1H), 5.76
-6.45 (m, 2H), 6.96 (d, 2H, J = 8.8Hz), 7.00 (d, 2H,
J = 8.8Hz), 7.23 (d, 2H, J = 8.6Hz), 7.51 (d, 2H, J =
8.8Hz), 7.58 (d, 2H, J = 8.6Hz), 8.16 (d, 2H, J = 9.0H
z). IR (cm ^-1 ); 2960, 2930, 2850, 1725 (C = O), 1610, 150
0, 1470, 1310, 1290, 1250, 1215, 1165, 1080, 1010,
995, 930, 880, 840, 800, 760, 690. Mass (m / e); 458 (M ⁺ ), 298, 161, 41 (CH ₂ = CHCH ₂ ⁺ ).

The obtained 4- (4'-octyloxybiphenyl) p-allyloxybenzoate (5.00 g, 10.9 mmol) and dimethylethoxysilane (2.5 ml, 18.2 mmol) were dissolved in tetrahydrofuran (50 ml) to prepare dicyclopentadienylplatinum. 0.20 ml of a methylene chloride solution (0.1 mol / l) of dichloride was added, and the mixture was stirred at 50 ° C. for 3 hours under an argon gas atmosphere. After distilling off the solvent, 4- represented by the above chemical formula (10) is obtained.
(4'-Octyloxybiphenyl) p- (3-dimethylethoxysilylpropoxy) benzoate was obtained as a crude product.

The crude product obtained here was dissolved in 40 ml of acetone and 60 ml of tetrahydrofuran, and this solution was poured at room temperature into a solution of 3.5 g (25.3 mmol) of potassium carbonate in 50 ml of water and 120 ml of tetrahydrofuran. An aqueous solution in which 3.5 g (25.3 mmol) of potassium carbonate was dissolved in 100 ml of water was added to the solution. After stirring at room temperature for 2 hours,
The reaction solution was poured into an excess amount of ice water containing 12 g of potassium dihydrogen phosphate, extracted with methylene chloride, and the organic phase was dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified by silica gel column chromatography to obtain 4.01 g of white solid. About the obtained product, ¹ H-NM
By R, IR and Mass spectrum analysis, it was confirmed to be 4- (4′-octyloxybiphenyl) p- (3-dimethylhydroxysilylpropoxy) benzoate represented by the above chemical formula (11). (Yield; 68 in 2 steps.
(8%)

¹ H-NMR, δ (CDCl ₃ , ppm); 0.20 (s, 6H),
0.58 ~ 0.70 (m, 2H), 0.75 (t, 3H, J = 3.8Hz), 1.20 ~
2.10 (m, 15H), 4.30 (t, 2H, J = 6.4Hz), 4.33 (t, 2H,
J = 6.4Hz), 6.98 (d, 4H, J = 7.9Hz), 7.25 (d, 2H, J =
8.6Hz), 7.52 (d, 2H, J = 8.6Hz), 7.59 (d, 2H, J = 8.6H
z), 8.17 (d, 2H, J = 9.0Hz). IR (cm ^-1 ); 3280 (-OH), 2960, 2940, 2860, 1740 (C =
O), 1610, 1510, 1500, 1470, 1400, 1250 (Si-C), 122
0, 1160, 1075, 1040, 1000, 890, 860, 840, 800, 76
0, 680. Mass (m / e); 534 (M ⁺ ), 418, 298, 237, 195, 121, 75
(HOMe ₂ Si ⁺ ).

Example 3 Monomer Synthesis 2

[0069]

[Chemical 19]

2.00 g (3.74 mmol) of 4- (4'-octyloxybiphenyl) p- (3-dimethylhydroxysilylpropoxy) benzoate obtained in Reference Example 2 was dissolved in 100 ml of anhydrous tetrahydrofuran under an argon gas atmosphere. To the solution was added triethylamine 0.55 ml (3.95 mmol). 500 ml
Dichlorodimethylsilane 30.0 ml (247
mmol) and cooled to 0 ° C. on an ice bath, the above solution was slowly added dropwise from an addition funnel under an argon gas atmosphere, and after completion of addition, the mixture was further stirred at 0 ° C. for 1 hour. Next, this reaction vessel was connected to a vacuum pump, and excess dichlorodimethylsilane and the solvent were distilled off under reduced pressure at room temperature to dry the intermediate product. Again, anhydrous tetrahydrofuran 30 ml
Was added to dissolve the product, and 0.76 g (3.74 m) of 3-methacryloxypropyldimethylsilanol obtained in Example 1 was added.
mol) was added and the mixture was stirred at room temperature overnight. Since a white salt was formed, it was filtered off while washing with diethyl ether, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.88 g of a white solid. The obtained product was analyzed by ¹ H-NMR, IR and Mass spectra, and was confirmed to be a monomer represented by the above chemical formula (12). (Yield; 63.4%)

¹ H-NMR, δ (CDCl ₃ , ppm); 0.20 (s, 18
H), 0.55-0.88 (m, 4H), 1.01 (t, 3H, J = 6.2Hz), 1.30-
2.12 (m, 16H), 2.34 (s, 3H), 4.54 (m, 6H), 5.93
(m, 1H), 6.50 (m, 1H), 7.58 (d, 4H, J = 7.6Hz), 7.64
(d, 2H, J = 7.9Hz), 7.94 (d, 2H, J = 8.1Hz), 8.12 (d, 2
H, J = 8.1Hz), 8.55 (d, 2H, J = 9.0Hz). IR (cm ^-1 ); 2980, 2940, 2880, 1730 (C = O), 1640, 161
0, 1580, 1510, 1500, 1480, 1420, 1330, 1330, 1260
(Si-C), 1220, 1170, 1110-1000 (SiOSi), 940,900, 84
0, 800. Mass (m / e); 793 (M + H ⁺ ), 587, 496, 439, 365, 291, 2
17, 69 (CH ₂ = C (CH ₃ ) CO ⁺ ), 41 (CH ₂ = C (CH ₃ ) ⁺ ).

USE EXAMPLE 2 Polymer Synthesis 2

[0073]

[Chemical 20]

0.50 g (0.630) of the monomer obtained in Example 3
mmol) was dissolved in 6 ml of tetrahydrofuran, and 4.50 mg (0.0274 mmol) of azobisisobutyronitrile was added to this solution. After this solution was sufficiently degassed by freezing, a polymerization reaction was carried out at 60 ° C. for 24 hours. The reaction solution was poured into 400 ml of methanol, the obtained precipitate was recovered, further dissolved in tetrahydrofuran, and reprecipitation was repeated twice in methanol. As a result, 0.30 g of a white solid polymer was obtained.
(Yield; 60.0%) For the obtained polymer, ¹ H-NM
An R spectrum analysis was performed, and it was confirmed that the polymer was represented by the above chemical formula (13). The number average molecular weight and the weight average molecular weight obtained by gel permeation chromatography are polystyrene conversion values, respectively.
It was 4.27x10 ³ and 5.75x10 ³ . Further, the glass transition temperature of this polymer was −5 ° C. by DSC measurement and polarization microscope observation, and a smectic liquid crystal phase was exhibited in a wide temperature range from −5 ° C. to 167 ° C.

¹ H-NMR, δ (CDCl ₃ , ppm); 0.20 (s, 18
H), 0.55-0.83 (m, 4H), 1.10-2.44 (m, 22H), 4.25-4.6
9 (m, 6H), 7.35 (d, 4H, J = 6.8Hz), 7.62 (d, 2H, J =
6.8Hz), 7.92 (d, 2H, J = 6.9Hz), 8.03 (d, 2H, J = 6.8H
z), 8.58 (d, 2H, J = 6.6Hz).

Claims (2)

[Claims] 1. The following general formula (I): (In the formula, R is a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a phenyl group, R ¹ and R ² may be the same or different, an alkyl group or a phenyl group, and p is 2
It is an integer of -10. ) The silanol compound which has a polymeric group represented by these. 2. The following general formula (II): (In the formula, R ³ and R ⁴ may be the same or different,
An alkyl group or a phenyl group, X is a single bond, an oxygen atom,
Alternatively, a group represented by -COO- or -OCO-, Q is a liquid crystal group, and q is an integer of 2 to 10. And a silanol compound having a liquid crystal group represented by the following general formula (III): (In the formula, R ^{5 to} R ⁸ may be the same or different, an alkyl group or a phenyl group, and m is an integer of 0 to ^5. )
After reacting with a dichloro compound represented by the following general formula (I): (In the formula, R is a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a phenyl group, R ¹ and R ² may be the same or different, an alkyl group or a phenyl group, and p is 2
It is an integer of -10. ), A silanol compound having a polymerizing group represented by the formula (IV): (In the formula, R is a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a phenyl group, R ^{1 to} R ⁸ may be the same or different, an alkyl group or a phenyl group, X is a single bond, an oxygen atom, or- A group represented by COO- or -OCO-, Q is a liquid crystal group, p and q are integers from 2 to 10, and m is 0.
Is an integer of ~ 5. ) A method for producing a monomer having a liquid crystal group represented by: