JPH08301859A - Oxetane compound and its polymer - Google Patents

Abstract

PURPOSE: To obtain an oxetane compound capable of forming a side-chain type liquid crystal polymer having independently controllable liquid crystal transition temperature and glass transition temperature. CONSTITUTION: This oxetane compound is expressed by formula I [R is a univalent hydrocarbon group, a halogenated hydrocarbon group or an Si-containing group of formula II ((b) is 2-20; (c) is 0-20); (a) is 1-20; L is liquid crystalline substituent], e.g. 3- [-3-(pentamethyldisiloxanyl)propoxy]methyl}-3- ]4-(4- cyanobiphenyl-4-yloxy)butoxy]methyl}oxetane of formula III. The compound can be produced e.g. by reacting an oxetane compound of formula IV (X is a halogen) with a compound of formula MO-L (M is an alkali metal) at a molar ratio of 1:0.5-2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxetane compound having a liquid crystal substituent on its side chain and a polymer thereof.

[0002]

2. Description of the Related Art Conventionally, as a liquid crystalline polymer, a liquid crystal forming group, that is, a main chain type liquid crystalline polymer having a mesogen group in its main chain, a side chain type liquid crystalline polymer having the group in its side chain,
A composite type liquid crystalline polymer having the group in both the main chain and the side chain is known. Among them, a side chain type liquid crystalline polymer has a mesogen group and a polymer skeleton that can function separately, so that the side chain mesogenic group has the same function as a low molecular weight liquid crystalline compound, and a normal polymer. It also has molding processability, mechanical characteristics, etc. that are possessed by
It can be expected to be put to practical use in a wide range of fields such as measurement and sensor materials, and in recent years, earnest development has been made. As a skeleton of such a side chain type liquid crystalline polymer, poly (meth) acrylic acid type, polystyrene type, polydiene type, polysiloxane type, etc. have been proposed, and the liquid crystal transition temperature of the side chain mesogenic group, etc. In addition to thermal properties, thermal properties such as the glass transition temperature of the polymer skeleton are also important factors depending on the usage form and application. The conventional side chain type liquid crystalline polymer has a temperature (hereinafter referred to as “liquid crystal transition temperature”) at which a mesogen group forms a liquid crystal, which is a very important characteristic value in developing a functional material such as a display device. It is closely related to the glass transition temperature of the polymer skeleton, and if the liquid crystal transition temperature is lowered,
It has been recognized that the glass transition temperature of the polymer skeleton is lowered, and conversely, if the glass transition temperature of the polymer skeleton is lowered, the liquid crystal transition temperature is also lowered. Therefore, for example, depending on the structure of the polymer skeleton, the molecular design that the glass transition temperature of the matrix polymer is high and the liquid crystal transition temperature is low, which is required for polymer-dispersed liquid crystals, is based on the conventional side chain liquid crystallinity. It was difficult with polymers.

[0003]

Therefore, the present invention provides a side chain type liquid crystalline polymer capable of independently controlling the liquid crystal transition temperature and the glass transition temperature, which have been difficult with the conventional side chain type liquid crystalline polymer. An object is to provide an oxetane compound that can be formed and a polyether polymer that is produced by ring-opening polymerization of the compound.

[0004]

SUMMARY OF THE INVENTION The gist of the present invention is the first
And an oxetane-based compound represented by the following formula (1).

[0005]

[Chemical 1]

[In the formula (1), R is a monovalent hydrocarbon group, a halogenated hydrocarbon group or the following formula (2) (where, b is an integer of 2 to 20 and c is an integer of 0 to 20). .), A is an integer of 1 to 20, and L is a liquid crystal substituent.

[0007]

[Chemical formula 2]

Secondly, the gist of the present invention consists of a polyether polymer having a polystyrene-reduced weight average molecular weight of 1,000 to 1,000,000 having a repeating unit represented by the following formula (3).

[0009]

Embedded image

[In the formula (3), R is a monovalent hydrocarbon group, a halogenated hydrocarbon group or the following formula (2) (where b is an integer of 2 to 20 and c is an integer of 0 to 20). A) is a silicon-containing group, a is an integer of 1 to 20, and L is a liquid crystal substituent.

[0011]

[Chemical formula 2]

The present invention will be described in detail below. This will clarify the purpose, structure and effect of the present invention. Oxetane compound The oxetane compound of the present invention is represented by formula (1).
Examples of the liquid crystal substituent L in the formula (1) include a biphenyl-based substituent obtained by removing one hydrogen atom from a biphenyl-based compound, an aromatic carboxylic acid such as benzoic acid, naphthoic acid and fluorenoic acid, or the aromatic carboxylic acid. In addition to an aromatic carboxylic acid type substituent in the form of removing one hydrogen atom from an ester compound which is a condensation product of a carboxylic acid and an aromatic phenol, an aromatic azo type substituent, an aromatic azoxy type substituent, an aromatic Azomethine-based substituent, Phenylcyclohexane-based substituent,
Examples thereof include bicyclohexane-based substituents, phenyldimethylenecyclohexane-based substituents and cholesterol-based substituents. The bonding position of the liquid crystal substituent L with the oxygen atom in the formula (1) can be appropriately selected as long as the liquid crystal forming property of the substituent is not impaired. As the liquid crystal substituent L in the formula (1), a biphenylyl group, a phenoxycarbonylphenyl group and groups derived from these groups, specifically, from the viewpoint of easy synthesis of a predetermined oxetane compound, Formula (4) or Formula (5)
The group represented by is preferable.

[0013]

[Chemical 4]

[0014]

Embedded image

[In the formulas (4) and (5), Q is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10), an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10) Oxy group, carbon number 1-20 (preferably 1-1)
0) represents a group selected from the group consisting of an alkylcarbonyl group, a cyano group and a carboxyl group, and is preferably a methoxy group, a methylcarbonyl group or a cyano group. Next, as the monovalent hydrocarbon group of R in the formula (1), for example, a linear or branched alkyl group having 1 to 20 (preferably 1 to 10) carbon atoms, specifically a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n
-Octyl group, n-nonyl group, n-decyl group, etc .; cycloalkyl group having 3 to 20 carbon atoms (preferably 3 to 10),
Specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, and these cycloalkyl groups are methyl group, ethyl group, n-propyl group, isopropyl group, n
A group substituted with a -butyl group, a t-butyl group or the like; a cycloalkyl terminal alkylene group having 4 to 20 carbon atoms (preferably 5 to 12) or an alkyl-substituted cycloalkyl terminal alkylene group, specifically a cyclopentylmethylene group, o
-Methylcyclopentylmethylene group, cyclopentylethylene group, o-methylcyclopentylethylene group, cyclohexylmethylene group, o-methylcyclohexylmethylene group, p-methylcyclohexylmethylene group, cyclohexylethylene group, o-methylcyclohexylethylene group, p-methylcyclohexyl group Ethylene group and the like; aryl group having 6 to 20 carbon atoms (preferably 6 to 16), specifically, phenyl group, naphthyl group, anthracenyl group, and the like,
o-tolyl group, m-tolyl group, p-tolyl group, o-xylyl group, m-xylyl group, p-xylyl group, p-isopropylphenyl group, p-t-butylphenyl group, etc .; carbon number 7-20 (Preferably 7 to 14) aralkyl groups, specifically, benzyl group, phenylethyl group, (1-naphthyl) methyl group, (2-naphthyl) methyl group, (1-naphthyl) ethyl group, (2-naphthyl) ) An ethyl group etc. can be mentioned. The monovalent halogenated hydrocarbon group for R is, for example, 1 to 20 carbon atoms (preferably 1 to 20 carbon atoms).
10) alkyl group having 3 to 20 carbon atoms (preferably 3 to 20 carbon atoms)
10) cycloalkyl group, C4-20 (preferably 5-12) cycloalkyl terminal alkylene group or alkyl-substituted cycloalkyl terminal alkylene group, C6-20 (preferably 6-16) aryl group, 1 such as an aralkyl group having a carbon number of 7 to 20 (preferably 7 to 14)
Mono- or poly-fluoro substituents of valent hydrocarbon groups,
Mono- or poly-chloro substitution, mono- or poly-
A bromo substitution product etc. can be mentioned. These halogen atoms can be bonded to the aliphatic chain and / or aromatic ring of the hydrocarbon group. Further, as the monovalent silicon-containing group represented by R represented by the above formula (2), b is 2
Compounds in which 10 to 10 and c is 0 to 20 are preferable. Moreover, the preferable range of a in Formula (1) is 2-10. As a method for producing the oxetane compound of the present invention,
For example, starting from 3,3-bis (hydroxymethyl) oxetane via a cyclic carbonate compound of pentaerythritol, a liquid crystal substituent L and a group R are added to the two hydroxymethyl groups as described below. The method of introduction can be mentioned. In this case, first the group R
It is preferable to introduce the liquid crystal substituent L after the introduction of the above because the liquid crystal substituent L is less likely to be thermally affected. The liquid crystalline substituent L in the formula (1) can be basically introduced by a Williamson reaction for forming an ether by dealkalization metal halide reaction between an alkali metal alkoxide and an alkyl halide. More specifically exemplifying such a method of introducing the liquid crystal substituent L, (i) the following formula (6) (wherein R and a have the same meanings as in the formula (1), X is a chlorine atom or bromine). An oxetane compound represented by a halogen atom such as an atom, and a formula MO-L (wherein L has the same meaning as in formula (1),
M represents an alkali metal. ), And a compound represented by the formula (1) are reacted at a molar ratio of 1: 0.5 to 2 mol,

[0016]

[Chemical 6]

(Ii) An oxetane compound represented by the following formula (7) (wherein R has the same meaning as in the formula (1) and M represents an alkali metal) and the formula X- (CH ₂ ). a-O-L (where a and L have the same meanings as in formula (1), and X represents a halogen atom such as a chlorine atom or a bromine atom) and a molar ratio of 1: 0. A method of reacting at a ratio of 0.5 to 2 can be mentioned.

[0018]

[Chemical 7]

The formula X- (CH ₂ ) used in the reaction (ii) above
The compound represented by a-OL is also basically the above-mentioned Williamson reaction, for example, α, ω represented by the formula X- (CH ₂ ) a -X.
It can be obtained by reacting a dihalogenoalkane with a compound represented by the formula MO-L. Further, when R is a hydrocarbon group or a halogenated hydrocarbon group, R in the formula (1) is introduced by, for example, a Williamson reaction to form an ether of (iii) 3,3-bis (hydroxymethyl) oxetane compound. can do. When R in the formula (1) is a silicon-containing group represented by the formula (2), for example, (iv) an oxetane compound represented by the following formula (8) and a formula (9) below. The hydrosilane compound can be introduced by a hydrosilylation reaction at a molar ratio of 1: 0.5 to 2.

[0020]

Embedded image

[In the formula (8), b has the same meaning as in the formula (2). ]

[0022]

[Chemical 9]

[In the formula (9), c has the same meaning as in the formula (2). The oxetane compound represented by the formula (8) is preferably a compound in which b is 2 to 10, and specifically,-(CH ₂ ).
_b-2 -CH = CH ₂ group is vinyl group (b = 2), allyl group (b =
3), 3-butenyl group (b = 4), 4-pentenyl group (b = 5), 5-hexenyl group (b = 6), 6-heptenyl group (b = 7), 7-octenyl group (b = 8) and the like. Further, as the hydrosilane compound represented by the formula (9), any compound in which c is 0 to 20 is preferably used, and specifically, trimethylhydrosilane (c = 0) and pentamethyldisiloxane (c = 1), heptamethyltrisiloxane (c = 2),
Examples thereof include nonamethyltetrasiloxane (c = 3), undecamethylpentasiloxane (c = 4), tridecamethylhexasiloxane (c = 5), and pentadecamethylheptasiloxane (c = 6). The hydrosilylation reaction of the oxetane compound represented by the formula (8) and the hydrosilane compound represented by the formula (9) is usually carried out in the presence of a hydrosilylation catalyst. Examples of such hydrosilylation catalysts include platinum salts, inorganic complexes, organic complexes, halides, and the like, specifically chloroplatinic acid, acetylacetonate bisbenzonitrile chloride, ethylenediamine dichloride, 1,3-divinyl tetramethyl dichloride. Examples thereof include siloxane. The reaction for introducing the liquid crystal substituent L and the group R as described above into the 3,3-bis (hydroxymethyl) oxetane compound is usually carried out in a suitable solvent such as dimethylformamide at a reaction temperature of −50.
Performed at ~ + 200 ° C. The oxetane compound represented by the formula (1) serves as a raw material for the polyether polymer having the repeating unit represented by the formula (3), and the compound alone or other liquid crystalline low molecular compound and / or Mixing with various side chain type liquid crystalline polymers, liquid crystal display device,
It can be used very suitably for liquid crystal optical devices, recording materials, measurement / sensor materials, and the like.

Polyether Polymer Next, the polyether polymer having a repeating unit represented by the formula (3) of the present invention has a polystyrene reduced weight average molecular weight (hereinafter, referred to as "Mw") of 1. 000-1,0
0,000, preferably 5,000 to 200,000
Is a homopolymer or a copolymer of, and in the case of a copolymer,
It can also have a block structure. In the polyether polymer of the present invention, the content of the repeating unit represented by the formula (3) is usually 10 mol% or more, preferably 50 to 100 mol%, particularly preferably 80 to 100 mol. %. In this case, when the content of the repeating unit represented by the formula (3) is less than 50 mol%, the liquid crystal forming ability of the polymer tends to decrease. Such a polyether-based polymer is obtained by (co) polymerizing an oxetane-based compound represented by the formula (1), alone or in the presence of another cationically polymerizable monomer, using a cationic polymerization catalyst. It can be manufactured by Examples of the cationic polymerization catalyst include protonic acids such as sulfuric acid, perchloric acid, fluorosulfuric acid, and trifluoromethanesulfonic acid; BF ₃ , AlCl ₃ , PF ₅ , and SbCl.
Lewis acid such as ₃ and a system comprising such Lewis acid and a cocatalyst such as ether or an alkyl halide; (C ₂ H ₅ ) ₃ O ⁺
BF ₄ ^- trialkyl oxonium salts such _{as; (C 6 H 5) 3} C + B
Trifluoromethyl sulfonic acid, esters of super strong acid such as fluorosulfonic acid;; ^- F ₄ carbenium salt such as an acid anhydride of the superacid can be exemplified. The amount of these cationic polymerization catalysts used is usually 0.0001-0.
It is about 1 mol%. Other cationically polymerizable monomers copolymerized with the oxetane compound represented by the formula (1) include, for example, cyclic ethers such as tetrahydrofuran, oxetane, methyloxetane, and 3,3′-bischloromethyloxetane. Kinds; 1,3-dioxolane, 1,
3,5-trioxane, 1,3-dioxepane, 1,
Cyclic acetals and macrocyclic acetals such as 3,6-trioxacyclooctane; β-propiolactone and its alkyl-substituted products, lactones such as δ-valerolactone and ε-caprolactone; lactams such as ε-caprolactam. Cyclic siloxanes such as hexamethylcyclotrisiloxane and octamethyltetrasiloxane; aziridine,
Cyclic amines such as 1-t-butylaziridine; cyclic monomers such as 2-oxazoline, and unsaturated monomers such as isobutyl vinyl ether, styrene, α-methylstyrene, and isoprene. The (co) polymerization of the oxetane compound is usually carried out in a suitable solvent such as hydrocarbon or halogenated hydrocarbon, for example, -100 to +.
It is carried out at a temperature of 100 ° C. After completion of the polymerization, a polyether polymer can be precipitated by adding a poor solvent such as ethanol to the reaction system, and the precipitated polymer is separated and recovered from the solvent by a usual method. The oxetane compound represented by the formula (1) is represented by the formula (3) either alone or in the presence of another cationically polymerizable monomer, by selecting a cationic polymerization catalyst and polymerization conditions. A block copolymer is produced by producing a living polymer having a repeating unit, and subjecting the living polymer to sequential addition of another cationically polymerizable monomer or a coupling reaction with a polymer having a reactive terminal group. Can also be manufactured. Furthermore, the polyether polymer having a repeating unit represented by the formula (3) may be chemically modified by introducing various substituents at appropriate positions, if desired, unless the effects of the present invention are impaired. You can also The polyether polymer having a repeating unit represented by the formula (3) has a liquid crystal substituent (that is, a mesogen group) in the side chain, and the liquid crystal transition temperature and the glass transition temperature are designed independently of each other. And a liquid crystal display device, a liquid crystal optical device, a recording material, and a measurement, which polymer has a property of being capable of -It can be used very suitably as a sensor material, etc., and also as a modifier for improving the low-temperature characteristics of various resins including styrene-based resins by making use of its thermal characteristics, as a coating material for various electronic materials. It is useful.

[0025]

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Example 1 (a) Synthesis of 3,3-bis (hydroxymethyloxetane) To a three-necked flask equipped with a stirrer and purged with nitrogen, pentaerythritol 69.0 g, diethyl carbonate 89.0 g and metallic sodium 0.20 g were added. , Under stirring 130 ℃
Then, the reaction was carried out for 4 hours while distilling off by-produced ethanol. After distilling off a predetermined amount of ethanol, set the reaction temperature to 1
The temperature was raised to 80 to 200 ° C., and decarboxylation reaction of the intermediate cyclic carbonate was carried out for 30 minutes. After the generation of carbon dioxide gas, the reaction product was isolated by vacuum distillation. The obtained compound had a boiling point of 110-120 ° C./0.3 mmHg and a yield of 66%, and had a ¹ H-NMR spectrum (solvent: CDCl ₃ ).
Gives 3,3-bis (hydroxymethyloxetane)
Was confirmed. (B) Synthesis of 3-allyloxymethyl-3-hydroxymethyloxetane Sodium hydride in a three-necked flask equipped with a stirrer.
After adding 00 g and purging with nitrogen, 40 ml of dehydrated dimethylformamide was added. Then, a solution prepared by dissolving 16.54 g of 3,3-bis (hydroxymethyloxetane) synthesized in (a) above in 20 ml of dimethylformamide was added dropwise to the reaction system over 30 minutes for reaction. Then allyl bromide 8.4
A solution of 9 g dissolved in 20 ml of dimethylformamide was added dropwise over 1 hour, and stirring was continued for 10 hours. Next, dimethylformamide was distilled off under reduced pressure, diethyl ether was added, and the mixture was filtered. Then, the filtrate was concentrated and purified by column chromatography (carrier: silica gel) using a hexane / ethyl acetate mixed solvent (mixing volume ratio 50/50) to obtain a colorless liquid product. The obtained compound has a yield of 35%,
¹ H-NMR spectrum (solvent: CDCl ₃ ) confirmed that it was 3-allyloxymethyl-3-hydroxymethyloxetane. (C) Synthesis of 3-allyloxymethyl-3-[(4-bromobutoxy) methyl] oxetane In a three-necked flask equipped with a stirrer, 30 ml of 50 wt% sodium hydroxide aqueous solution and tetra-n as a phase transfer catalyst were used. -Butyl ammonium bromide 324 mg
Was added to a solution of 20 ml of hexane, and the mixture was stirred for 30 minutes. Then, 3.16 g of 3-allyloxymethyl-3-hydroxymethyloxetane synthesized in (b) above and 13.4-dibromobutane 13.2
1 g was added, and the mixture was stirred at room temperature overnight for reaction, and then refluxed for 30 minutes to complete the reaction. Then, the mixture was allowed to cool to room temperature, water was further added, the reaction product was extracted with hexane, and the extract was dried over magnesium sulfate. Then, the mixture was filtered, hexane was distilled off from the filtrate, and then distilled under reduced pressure to isolate a colorless liquid product.
The obtained compound has a boiling point of 112 ° C./0.4 mmHg, a yield of 64%, and a ¹ H-NMR spectrum (solvent: CDCl
_{According to 3} ), it was confirmed to be 3-allyloxymethyl-3-[(4-bromobutoxy) methyl] oxetane. (D) Synthesis of 3-allyloxymethyl-3-{[4- (4-cyanobiphenyl-4′-yloxy) butoxy] methyl} oxetane Sodium hydride was added to a three-necked flask equipped with a stirrer.
After adding 53 g and purging with nitrogen, 20 ml of hexane was added, and after stirring, the supernatant was removed by decantation, and further dried by a vacuum dryer.
Then, after introducing nitrogen gas into the reactor, a solution prepared by dissolving 1.95 g of 4-cyano-4′-hydroxybiphenyl in 7 ml of dimethylformamide was added dropwise to cause a reaction, and thereafter, the compound synthesized in (c) above was used. A solution of 2.93 g of -allyloxymethyl-3-[(4-bromobutoxy) methyl] oxetane dissolved in 10 ml of a dimethylformamide solution was added dropwise, and the mixture was reacted overnight at room temperature. After completion of the reaction, dimethylformamide was distilled off under reduced pressure, 50 ml of water was added, and the reaction solution was extracted with chloroform. After the extract was concentrated, it was purified by column chromatography (carrier: silica gel) using a hexane / chloroform / diethyl ether mixed solvent (mixing volume ratio 2/1/1) to isolate a colorless liquid product. . The obtained compound had a yield of 58% and had a ¹ H-N
MR spectrum (solvent: CDCl ₃₎ with 3-allyloxy-methyl-3 - {[4- (4-cyano-biphenyl-4 '
-Yloxy) butoxy] methyl} oxetane was confirmed. (E) Synthesis of 3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[4- (4-cyanobiphenyl-4′-yloxy) butoxy] methyl} oxetane Stirrer 2.17 g of 3-allyloxymethyl-3-{[4- (4-cyanobiphenyl-4′-yloxy) butoxy] methyl} oxetane synthesized in (d) above was added to a three-necked flask, and the atmosphere was replaced with nitrogen. After that, 5.32 ml of toluene was added under a nitrogen atmosphere. Next, after adding 70 μl of an isopropanol solution of H ₂ PtCl ₆ · H ₂ O (concentration 0.1 mol / l), 2.04 ml of pentamethyldisiloxane was added, and hydrosilylation reaction was carried out at room temperature for 1 hour. It was After completion of the reaction, toluene was distilled off, and a hexane / chloroform / diethyl ether mixed solvent (mixing volume ratio 2/1/1)
The product was purified by column chromatography (carrier: silica gel) using and the white liquid product was isolated. The yield of the obtained compound was 61%. The infrared absorption spectrum of this compound is shown in FIG. 1, and the ¹ H-NMR spectrum (solvent: CDCl ₃ ) is shown in FIGS. 2 (a) to 2 (c). The obtained compound was 3-{[3 having a structure represented by the following formula (10) (provided that n = 4) by attribution of the following ¹ H-NMR spectrum.
It was confirmed to be-(pentamethyldisiloxanyl) propoxy] methyl} -3-{[4- (4-cyanobiphenyl-4'-yloxy) butoxy] methyl} oxetane. Each chemical shift (δ) in the ¹ H-NMR spectrum below corresponds to an underlined hydrogen atom (the same applies hereinafter).

[0026]

[Chemical 10]

[0027]

[Chemical 11]

Example 2 (a) Synthesis of 3-allyloxymethyl-3-[(5-bromopentyloxy) methyl] oxetane 1,4-dibromobutane used in Example 1 (c) 13.
Instead of 21 g, 1,5-dibromopentane 13.6
A colorless liquid product was obtained by the same procedure as in Examples 1 (a) to (c) except that 5 g was used. The resulting compound, boiling point of 132 ° C. / 0.5 mmHg, yield a is 57%, ¹ H-NMR spectrum (solvent: CDCl ₃₎ with 3-
It was confirmed to be allyloxymethyl-3-[(5-bromopentyloxy) methyl] oxetane. (B) 3-allyloxymethyl-3-{[5- (4-cyanobiphenyl-4'-yloxy) pentyloxy]
Synthesis of methyl} oxetane 3-allyloxymethyl-3-used in Example 1 (d)
[(4-Bromobutyloxy) methyl] oxetane 2.
Example 1 except that 3.13 g of 3-allyloxymethyl-3-[(5-bromopentyloxy) methyl] oxetane synthesized in (a) above was used instead of 93 g.
Treatment as in (d) gave a colorless liquid product. The yield of the obtained compound was 81%, and it was confirmed by ¹ H-NMR spectrum (solvent: CDCl ₃ ) that 3-allyloxymethyl-3-{[5- (4-cyanobiphenyl-4′-yloxy) was used. It was confirmed to be pentyloxy] methyl} oxetane. (C) Synthesis of 3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[5- (4-cyanobiphenyl-4′-yloxy) pentyloxy] methyl} oxetane Example 1 3-Allyloxymethyl-3-used in (e)
{[4- (4-cyanobiphenyl-4'-yloxy)
Butoxy] methyl} oxetane instead of 2.17 g,
3-allyloxymethyl-3-synthesized in (b) above
{[5- (4-cyanobiphenyl-4'-yloxy)
A white liquid product was obtained in the same manner as in Example 1 (e) except that 2.25 g of pentyloxy] methyl} oxetane was used. The obtained compound has a yield of 58% and has a structure represented by the above formula (10) (where n = 5) according to the assignment of the following ¹ H-NMR spectrum (solvent: CDCl ₃ ).
3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[5- (4-cyanobiphenyl-4′-yloxy) pentyloxy] methyl} oxetane .

[0029]

[Chemical 12]

Example 3 (a) Synthesis of 3-allyloxymethyl-3-[(6-bromohexyloxy) methyl] oxetane 1,4-dibromobutane used in Example 1 (c) 13.
Instead of 21 g, 1,6-dibromohexane 19.5
A colorless liquid product was obtained in the same manner as in Examples 1 (a) to (c) except that 2 g was used. The obtained compound had a boiling point of 130 ° C./0.4 mmHg and a yield of 82%, and it was confirmed by ¹ H-NMR spectrum (solvent: CDCl ₃ ) to give 3-
It was confirmed to be allyloxymethyl-3-[(6-bromohexyloxy) methyl] oxetane. (B) 3-allyloxymethyl-3-{[6- (4-cyanobiphenyl-4'-yloxy) hexyloxy]
Synthesis of methyl} oxetane 3-allyloxymethyl-3-used in Example 1 (d)
[(4-Bromobutoxy) methyl] oxetane 2.93
3-allyloxymethyl-3-[(6-bromohexyloxy) methyl] synthesized in (a) above instead of g.
Example 1 (d) except that 3.21 g of oxetane was used.
Worked as above to give a pale yellow liquid product. The yield of the obtained compound was 78%, and 3-allyloxymethyl-3 was found by ¹ H-NMR spectrum (solvent: CDCl ₃ ).
It was confirmed to be-{[6- (4-cyanobiphenyl-4'-yloxy) hexyloxy] methyl} oxetane. (C) Synthesis of 3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[6- (4-cyanobiphenyl-4′-yloxy) hexyloxy] methyl} oxetane Example 1 3-Allyloxymethyl-3-used in (e)
{[4- (4-cyanobiphenyl-4'-yloxy)
Butoxy] methyl} oxetane instead of 2.17 g,
3-allyloxymethyl-3-synthesized in (b) above
{[6- (4-cyanobiphenyl-4′-yloxy)
A colorless liquid product was obtained in the same manner as in Example 1 (e) except that 2.31 g of hexyloxy] methyl} oxetane was used. The obtained compound had a yield of 62%, and the structure represented by the above formula (10) (where n = 6) was assigned by the following ¹ H-NMR spectrum (solvent: CDCl ₃ ).
3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[6- (4-cyanobiphenyl-4′-yloxy) hexyloxy] methyl} oxetane .

[0031]

[Chemical 13]

Example 4 (a) Synthesis of 3-allyloxymethyl-3-[(7-bromoheptyloxy) methyl] oxetane 1,4-dibromobutane used in Example 1 (c) 13.
Instead of 21 g, 1,7-dibromoheptane 20.9
A colorless liquid product was obtained in the same manner as in Examples 1 (a) to (c) except that 4 g was used. The obtained compound had a boiling point of 135 ° C./0.2 mmHg and a yield of 74%, and it was confirmed by ¹ H-NMR spectrum (solvent: CDCl ₃ ) to give 3-
It was confirmed to be allyloxymethyl-3-[(7-bromoheptyloxy) methyl] oxetane. (B) 3-allyloxymethyl-3-{[7- (4-cyanobiphenyl-4'-yloxy) heptyloxy]
Synthesis of methyl} oxetane 3-allyloxymethyl-3-used in Example 1 (d)
[(4-Bromobutoxy) methyl] oxetane 2.93
3-allyloxymethyl-3-[(7-bromoheptyloxy) methyl] synthesized in (a) above instead of g.
Example 1 (d) except that 3.36 g of oxetane was used.
Work-up as above, to give a yellow liquid product. The yield of the obtained compound was 60%, and it was confirmed by ¹ H-NMR spectrum (solvent: CDCl ₃ ) that 3-allyloxymethyl-3-
{[7- (4-cyanobiphenyl-4′-yloxy)
It was confirmed to be heptyloxy] methyl} oxetane. (C) Synthesis of 3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[7- (4-cyanobiphenyl-4′-yloxy) heptyloxy] methyl} oxetane Example 1 3-Allyloxymethyl-3-used in (e)
{[4- (4-cyanobiphenyl-4'-yloxy)
Butoxy] methyl} oxetane instead of 2.17 g,
3-allyloxymethyl-3-synthesized in (b) above
{[7- (4-cyanobiphenyl-4′-yloxy)
A light yellow liquid product was obtained by the same treatment as in Example 1 (e) except that 2.34 g of heptyloxy] methyl} oxetane was used. The yield of the obtained compound was 47%, and the structure represented by the above formula (10) (where n = nH was determined by assignment of the following ¹ H-NMR spectrum (solvent: CDCl ₃ )).
7) 3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[7- (4-cyanobiphenyl-4'-yloxy) heptyloxy] methyl} oxetane Was done.

[0033]

Embedded image

Example 5 (a) Synthesis of 4-cyano-4 '-(3-bromopropoxy) biphenyl Sodium hydride was added to a three-necked flask equipped with a stirrer.
After adding 00 g and purging with nitrogen, 20 ml of hexane was added and washed, and then dried with a vacuum pump. Then, after injecting nitrogen gas, 60 ml of dimethylformamide was added, and 45 ml of a solution in which 3.90 g of 4-cyano-4′-hydroxybiphenyl was dissolved in dimethylformamide was added dropwise and reacted for 30 minutes. Then 1,3-dibromopropane 20.89
15 ml of a solution of g in dimethylformamide was added dropwise over 1 hour, and the reaction was continued overnight at room temperature. Then, dimethylformamide and unreacted 1,3-dibromopropane were distilled off under reduced pressure, and then water 3
0 ml was added, and the organic phase was separated and extracted with chloroform. The extract was washed with water, dried over magnesium sulfate, and the filtrate was concentrated to give a crude product.
Then, it was recrystallized from ethanol to obtain a pale yellow solid product. The obtained compound had a yield of 39% and ¹ H
-NMR spectrum (solvent: CDCl ₃₎ with 4-cyano-4 '- it was confirmed that the (3-bromopropoxy) biphenyl. (B) Synthesis of 3-allyloxymethyl-3-{[3- (4-cyanobiphenyl-4'-yloxy) propoxy] methyl} oxetane In a three-necked flask equipped with a stirrer, a 50% by weight aqueous sodium hydroxide solution was added. After adding a mixed solvent of 50 ml and 10 ml of tetrahydrofuran, 324 mg of tetra-n-butylammonium bromide was added as a phase transfer catalyst, and the mixture was stirred at room temperature for 30 minutes. Then, 7 ml of a solution prepared by dissolving 0.89 g of 3-allyloxymethyl-3-hydroxymethyloxetane synthesized in Example 1 (b) in tetrahydrofuran was added dropwise.
Furthermore, 4-cyano-4 '-(3- synthesized in (a) above
2.21 g of bromopropoxy) biphenyl was added dropwise,
After continuing the reaction overnight, the mixture was refluxed for 2 hours to complete the reaction. Then, the mixture was allowed to cool to room temperature, the tetrahydrofuran was distilled off, and the aqueous phase was extracted with chloroform.
Next, the extract was washed with a 1 wt% hydrochloric acid aqueous solution and water, and then dried over magnesium sulfate. Then, after filtering and distilling chloroform off from the filtrate, hexane /
Purification by column chromatography (carrier: silicagel) using a chloroform / diethyl ether mixed solvent (mixing volume ratio 2/1/1) gave a pale yellow liquid product. The compound obtained had a yield of 37% and had a ¹ H-NM
According to R spectrum (solvent: CDCl ₃ ), 3-allyloxymethyl-3-{[3- (4-cyanobiphenyl-4′-
It was confirmed to be yloxy) propoxy] methyl} oxetane. (C) Synthesis of 3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[3- (4-cyanobiphenyl-4′-yloxy) propoxy] methyl} oxetane A stirrer was provided. In a three-necked flask, 3-allyloxymethyl-3-{[4- (4-cyanobiphenyl-4'-yloxy) butoxy] methyl} used in Example 1 (e) was used.
Instead of 2.17 g of oxetane, 3-allyloxymethyl-3-{[3- (4-cyanobiphenyl-4′-yloxy) propoxy] methyl} synthesized in (b) above.
Example 1 (e) except that 2.20 g of oxetane was used.
Worked as above to give a pale yellow liquid product. The yield of the obtained compound was 57%, and ₃ -H of the structure represented by the above formula (10) (provided that n = 3) was assigned by the following ¹ H-NMR spectrum (solvent: CDCl ₃ ). {[3- (Pentamethyldisiloxanyl) propoxy] methyl} -3-
{[3- (4-cyanobiphenyl-4'-yloxy)
It was confirmed to be propoxy] methyl} oxetane.

[0035]

[Chemical 15]

Example 6 A three-necked flask equipped with a stirrer was prepared as in Example 1,
Dehydrated and purified 3-{[3- (pentamethyldisiloxanyl) propoxy] methyl} -3-{[4- (4-cyanobiphenyl-4′-yloxy) butoxy] methyl} oxetane (monomer) 0 .850 mmol (0.472
g) and 0.85 ml of dehydrated and purified methylene chloride were added to dissolve the monomer, and then cooled to 0 ° C. Next, 0.169 ml of a methylene chloride solution of BF ₃ .O (C ₂ H ₅ ) ₂ purified by distillation was added, and the mixture was added at 0 ° C. for 24 hours and then at room temperature for 12 hours.
Polymerized for hours. Then, the reaction solution was poured into excess ethanol to precipitate the polymer, and then reprecipitation with chloroform and ethanol was repeated to purify the polymer.
The obtained polymer had a yield of 10% and had the following ¹ H-NM
By the assignment of R spectrum (solvent: CDCl ₃ ), the following formula (1
1) (however, n = 4) was confirmed to consist of the repeating unit. The ¹ H-NMR spectrum of the polymer is shown in FIG. In FIG. 3, the spectrum (D) is an enlarged view of the spectrum region (d). The properties of the obtained polymer were measured as follows. The characteristic values are shown in Table 1. Molecular weight: Gel permeation chromatography (G
Mw and Mn (polystyrene-equivalent number average molecular weight) were measured by PC). Glass transition temperature and liquid crystal transition temperature: Measured by a differential scanning calorimeter (DSC). Liquid crystal texture: observed with a polarizing microscope.

[0037]

Embedded image

[0038]

[Chemical 17]

Examples 7-9 Instead of 0.850 mmol of the monomer used in Example 6, a series of 3-{[(
3-pentamethyldisiloxanyl) propoxy] methyl} -3-{[ω- (4-cyanobiphenyl-4′-yloxy) alkyloxy] methyl} oxetane 0.8
Example 6 was repeated except that 50 mmol was used.
A polymer was produced. The ¹ H-NMR spectrum (solvent: CDCl ₃ ) of the obtained polymer showed the same chemical shift as that of the polymer produced in Example 6, and the formula (11) (where n = 5) was used.
(Example 7), 6 (Example 8) or 7 (Example 9))
It was confirmed that it was composed of a repeating unit represented by Table 1 shows the characteristic values of the obtained polymers.

[0040]

[Table 1]

[0041]

The oxetane compound of the present invention is itself a liquid crystal display device, a liquid crystal optical device, a recording material, and
It can be used very suitably as a functional material in sensor materials, etc. In particular, since it can form a side chain type liquid crystalline polymer that can independently control the liquid crystal transition temperature and the glass transition temperature, it has a degree of freedom in molecular design. Is high. Further, the polyether polymer of the present invention suppresses the change in the glass transition temperature by changing the spacer length between the liquid crystal substituent and the polymer skeleton (that is, n in the formula (11)). The liquid crystal transition temperature can be greatly changed.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of an oxetane compound produced in Example 1.

FIG. 2 ¹ H-of the oxetane-based compound produced in Example 1
It is a figure which shows a NMR spectrum.

FIG. 3 ¹ H of the polyether-based polymer produced in Example 6
-A diagram showing an NMR spectrum.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 65/22 C08G 65/22 C09K 19/40 9279-4H C09K 19/40

Claims (2)

[Claims] 1. An oxetane compound represented by the following formula (1): Embedded image [In the formula (1), R is a monovalent hydrocarbon group, a halogenated hydrocarbon group or the following formula (2) (where, b is 2 to 20).
, And c is an integer from 0 to 20. ) Is a silicon-containing group, a is an integer of 1 to 20, and L is a liquid crystal substituent. Embedded image ] 2. A polystyrene-converted weight average molecular weight having a repeating unit represented by the following formula (3) is 1,000 to
1,000,000 polyether polymer. Embedded image [In the formula (3), R is a monovalent hydrocarbon group, a halogenated hydrocarbon group or the following formula (2) (where b is 2 to 2).
0 is an integer and c is an integer of 0 to 20. ) Is a silicon-containing group, a is an integer of 1 to 20, and L is a liquid crystal substituent. [Chemical formula 2]