KR100830561B1 - Multifunctional mesogenic compounds and method of preparing thereof, and image patterns obtained therefrom - Google Patents

Abstract

A multifunctional liquid crystal compound, a method for preparing the compound, and a micropattern obtained from the compound are provided to allow a micropattern of high quality to be prepared by forming conjugated polyacetylene chains. A multifunctional liquid crystal compound is represented by the formula I, wherein m is an integer of 2-4; n is an integer of 3-11; and R is a C1-C5 alkyl group or a nitrile group. The multifunctional liquid crystal compound of the formula I is prepared by adding 4-[4-(6-acryloyloxyhexyloxy)phenyl]benzoic acid and a compound represented by the formula II to an organic solvent; and reacting them under nitrogen.

Description

Multifunctional Mesogenic Compounds and Method of Preparing Sweet, and Image Patterns obtained therefrom}

The present invention relates to a novel multifunctional liquid crystal compound and a method for preparing the same, and more particularly, to a liquid crystal compound containing a diacetylene group and an acryl group, which are different photopolymerization groups, and thermal and photopolymerization characteristics of these compounds.

In general, the liquid crystal compound may align the molecules in one direction by applying an electric field on a substrate such as a glass plate. In the case of polymerizable liquid crystal molecules, a photomask is placed thereon, and the liquid crystal molecules in the portion where the photomask exists by UV irradiation are maintained, and the liquid crystal compound is a liquid crystal state polymerization in the portion where the photomask is not present. The reaction can be used to form an isotropic film.

Polymerizing the arranged monomer molecules has the advantage of being quicker and easier than arranging the polymers, and thermal or mechanical stability is imparted by polymerization in the best way to obtain anisotropic compounds.

In particular, photopolymerizable liquid crystals have received a lot of attention because they have unique characteristics of fluidity and molecular order, and are easy to control order. The liquid crystal compound is arranged macroscopically by rubbing on an electric field, a magnetic field, a shear stress or a substrate, and maintains the arrangement even after polymerization.

 Photopolymerization of oriented polymerizable liquid crystal molecules alters the electronic structure to change optical properties such as refractive index. The present inventors previously published a photopolymerizable liquid crystal compound having a diacetylene or a chalcone group. In the previous study, the image pattern was formed by UV polymerization using a photomask, and the image was formed by 1,4 addition reaction of diacetylene or [2 + 2] addition reaction of chalcone. Korean Patent Registration No. 0487959 (2005.04.27) and the following references:

references:

(1) Hwang, IH; Lee, SJ; Chang, JY J. Polym . Sci ., Polym . Chem . Ed . 2003 , 41 , 188.

(2) Chang, JY; Baik, JH; Lee, CB; Han, MJ; Hong, S.-K. J. Am . Chem . Soc . 1997 , 119 , 3197.

(3) Chang, JY; Yeon, JR; Shin, YS; Han, MJ; Hong, S.-K. Chem . Mater . 2000 , 12 , 1076.

(4) Cho, HJ; Seo, K .; Lee, CJ; Yun, H .; Chang, JY J. Mater . Chem . 2003 , 13 , 986.

(5) Chang, JY; Nam, SW; Hong, CG; Im, J. -H .; Kim, J.-H .; Han, MJ Adv . Mater. 2001 , 13 , 1298.

(6) Nam, SW; Kang, SH; Chang, JY Macromol . Res . 2007 , 15 , 74.

An object of the present invention relates to a novel multifunctional liquid crystal compound, a method for preparing the same, and a micropattern obtained therefrom, and more particularly, to a novel multifunctional liquid crystal compound containing a diacetylene group and an acryl group, which are different photopolymerization groups. will be.

In order to solve this object, the present inventors have conducted a lot of research, and as a result, a novel multifunctional liquid crystal compound having two different photopolymerization groups of acryl and diacetylene was synthesized. Some of the liquid crystal compounds showed a smetic phase at room temperature, and imaging experiments were performed at room temperature where the liquid crystal phase appeared. In addition, the present inventors were able to obtain the fluorescent image pattern shown in FIG. 3 through selective photopolymerization of liquid crystal compounds.

Specifically, in one step, uniaxial shear stress was applied to induce molecular arrangement, and the acrylic group was selectively polymerized using a photoinitiator at a weak 365 nm ultraviolet wavelength. In the second step, polydiacetylene was produced in the region where the ultraviolet rays were irradiated by polymerization by a continuous ultraviolet irradiation method having a wavelength of 254 nm using a photomask. Polyacetylene was fluorescent and was observed directly by fluorescence microscope.

The selective photopolymerization of the novel multifunctional liquid crystal compounds of the present invention can be represented by the following Scheme 1:

Selective photopolymerization of multifunctional liquid crystal compounds

The novel multi-functional liquid crystal compound (6-12) according to the present invention and the compounds (15 - 18), was synthesized by the method shown in the following reaction scheme 2a and 2b:

(Reaction scheme 2a) Synthesis of functional liquid crystal compound: Compound (6-12)

Wherein m is an integer from 2 to 4, n is an integer from 3 to 11, and R is a C ₁ to C ₅ lower alkyl group or a nitrile group.

(Reaction scheme 2b) versatility synthesis of liquid crystal compounds: compound (15 - 18)

The reactions of the present invention will be described in detail as follows.

The multifunctional liquid crystal compound of formula (I) is prepared by adding 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoic acid in an organic solvent with the compound of formula (II) and reacting in a nitrogen atmosphere. can do:

Wherein m is an integer from 2 to 4, n is an integer from 3 to 11, and R is a C ₁ to C ₅ lower alkyl group or a nitrile group.

Preferably m is an integer of 2 or 4, n is an integer of 3, 5, 7 or 11 and R is methyl or nitrile.

The organic solvent is at least one selected from the group consisting of dichloromethane, chloroform and tetrahydrofuran, preferably at least two kinds of mixed solvents selected from the group consisting of these groups.

In addition, the multifunctional liquid crystal compound of formula (Ia) may be prepared by adding 4- (6-hydroxyhexyloxy) benzoic acid and a compound of formula (III) in an organic solvent and reacting in nitrogen atmosphere:

delete

Wherein n is an integer from 3 to 9.

Preferably n is an integer of 3, 5, 7 or 9.

The organic solvent is at least one selected from the group consisting of dichloromethane, chloroform and tetrahydrofuran, preferably at least two kinds of mixed solvents selected from the group consisting of these groups.

The selective photopolymerization method of the obtained multifunctional liquid crystal compound may include a step of selectively polymerizing an acrylic group by adding a photoinitiator to the compound of Formula (I) or (Ia) and then irradiating 350 to 380 nm UV;

The polymer film formed in step 1 is characterized in that it comprises two steps of polymerizing an acrylic group and a diacetylene group by irradiating 240 to 270 nm UV through a photomask.

The photoinitiator can be selected from 2,2-dimethoxy-2-phenylacetophenone (DMPA) or 2,6 di-tert-butyl 4-methylphenol.

In the scheme, 4- [4- (6-hydroxyhexyl-oxy) phenyl] benzoic acid compound ( 3 ) is ethyl 4- (4-hydroxyphenyl) benzoate compound ( 1 ) and 6-bromo-1-hexane. The reaction was carried out and then synthesized by successive hydrolysis reactions. Compound ( 4 ) was synthesized by linking an acryl group and compound ( 3 ), and a diacetylene compound represented by formula (II) by reacting 5-hexyn-1-ol or 3-butyn-1-ol with 1-alkyne compound ( 5a - f ) was synthesized. Dimethyl acetylene compound (5) and only the acrylic compound (6 to 12) represented by the general formula (I) by esterification of the molecular compound (4) was synthesized.

The compounds of formula (III) were obtained using the same synthetic method as compound ( 5a ). Compound ( 15-18 ) represented by formula (Ia) was synthesized by esterification of compounds of formula (III) and acrylic monomolecular compound ( 14 ).

All compounds of the structure are ¹ H and ¹³ C NMR, infrared spectroscopy and was confirmed by elemental analysis of the compound (6-12) was observed in the liquid crystal property of the differential scanning calorimetry, polarized light microscopy and X-ray diffraction analyzer. All compounds showed birefringence of focal-conic fan phase in polarized light microscope with bi-directional liquid crystal.

For example, Compound ( 6 ) showed two endothermic peaks at 26.4 ° C and 44.9 ° C when heated and two exothermic peaks at 39.6 ° C and 12.9 ° C when cooled. Focal-conic fan phase appeared at 39.6 ℃ upon cooling and maintained at room temperature. Compound having a butyl between the die and acetylene biphenyl (6-9) and the compound (12) Compound (10 - 11) having an ethyl group showed a liquid crystal property at a lower temperature than the. Transition temperature of the crystal in the liquid crystal was decreased with decreasing the length of the alkyl compound (6-8) showed a crystal phase at room temperature. The thermal properties of the compounds are summarized in Tables 1 and 2 below.

Table 1 Phase transition temperature of compound (6-12) measured by differential scanning calorimeter (raising rate 10 ℃ / min)

sample Temperature ( ^o C) [Δ H , kJ / mol] ^a Heating ( ^o C) Cooling ( ^oC ) 6 K 26.4 [13.4] Sm 44.9 [8.1] I I 39.6 [7.8] Sm 12.9 [12.0] K 7 K 30.4 [16.4] Sm 41.8 [10.4] I I 38.2 [9.0] Sm 17.4 [15.3] K 8 K 34.7 [15.4] Sm 43.1 [8.4] I I 38.5 [8.7] Sm 19.9 [13.7] K 9 K 47.4 [9.8] Sm 55.5 [42.9] I I 43.5 [10.3] Sm 33.9 [32.3] K 10 K 87.7 [9.6] Sm 96.4 [9.4] I I 91.9 [9.6] Sm 83.1 [9.8] K 11 K 13.1 [4.9] K 81.0 [12.3] Sm 88.6 [12.4] I I 87.8 [13.6] Sm 79.1 [13.4] K 21.2 [3.5] K 12 K 35.9 [1.5] Sm 54.5 [14.1] I I 43.4 [6.3] Sm 21.8 [12.1] K

Table 2 Phase transition temperature of compound (15-18) measured by differential scanning calorimeter (raising rate 10 ℃ / min)

sample Temperature ( ^o C) [Δ H , kJ / mol] ^a Heating ( ^o C) Cooling ( ^oC ) 15 K 63.8 [33.1] Sm 83.8 [4.36] N 92.1 [0.77] I I 91.7 [0.60] N 83.3 [2.16] Sm 27.2 [19.5] K 16 K 55.4 [31.5] Sm 79.7 [1.67] N 86.1 [0.38] I I 84.8 [0.76] N 78.4 [1.66] Sm 3.7 [20.6] K 17 K 21.2 [0.8] Sm 81.5 [3.37] N 84.8 [0.95] I I 83.0 [0.89] N 80.0 [1.86] Sm -11.5 [0.6] K 18 K 47.7 [26.3] Sm 82.4 [8.27] I I 80.3 [7.90] Sm -6.6 [20.4] K

^a K = crystal; Sm = smectic; N = nematic; I = melting.

Photopolymerization of compound ( 6 ) in the liquid crystal phase was confirmed by infrared spectroscopy. A mixture of compound ( 6 ) and photoinitiator 2,2-dimethoxy-2-phenylacetophenone (DMPA, 4 wt%) was applied over a KBr window. When irradiated with 365nm UV light (1mW / cm ² ), the absorption peak of acrylic group is 1636 cm ^-1 (C = C stretching mode), 1408 cm ^-1 (vinyl CH ₂ in plane deformation mode), 985cm ^-1 and 810cm ^-1 Peaks in the vinyl CH out of plane deformation mode gradually decreased with the irradiation time, and the peak change of 1636 cm ^-1 was confirmed that after 50 minutes of irradiation, the acrylic group participated in the polymerization.

In addition, continuous 254 nm UV (3 mW / cm ^-2 ) irradiation reduced peaks of 2241 and 2142 cm ^-1 (CC triple bond stretching), increasing peaks of 2201 cm ^-1 . This was confirmed as a result of the 1,4 addition reaction of diacetylene.

1 shows the maximum absorption wavelength of 286 nm in the liquid crystal phase by the ultraviolet and fluorescence spectra of the compound ( 6 ), and the maximum absorption peak was found at 296 nm after UV irradiation of 365 nm. Excitation of 458 nm of light to this sample resulted in no fluorescence and no absorption at 458 nm. However, irradiation with 254 nm UV showed a maximum absorption wavelength of 333 nm and increased the absorption region up to 600 nm, because of the presence of short conjugated polydiacetylene chains. Exciting 458 nm of light on this sample showed emission spectrum up to 650 nm.

For photoimaging, a mixture of compound ( 6 ) and photoinitiator 2,2, -dimethoxy-2-phenylacetophenone (DMPA, 4 wt%) was placed on a glass substrate and sheared at room temperature with a cover glass to provide a unidirectional domain. Formed. The sample was selectively irradiated with ultraviolet light of 365 nm (10 minutes, 1 mW / cm ² ) to form a polymer film. A high pressure mercury arc lamp (HPML) was used to irradiate 254 nm ultraviolet (2 hours, 3 mW / cm ² ) through a photomask to polymerize not only the remaining acrylic groups but also the diacetylene groups.

2 is a patterned photograph observed through an optical microscope. Minimal permeability was observed because the molecules were arranged macroscopically when the shear stress direction was horizontal or perpendicular to the orthogonal polarizer. On the other hand, the birefringence pattern was obtained by rotating the sample at a 45 degree angle. Where UV rays (254 nm) were blocked, birefringence was observed under an optical microscope, whereas the UV-irradiated portion showed a crosslinked structure in which molecular arrangement was broken by polymerization of acryl and diacetylene.

In FIG. 2, the angle between the shear stress direction of the sample and the orthogonal polarizer axis is 0 degrees in FIG. 2A and 45 degrees in FIG. 2B. Patterns were obtained by UV irradiation at 365 nm (10 minutes) and 254 nm (HPML, 2 hours) using a photomask (tested at 30 ° C.).

3 is a fluorescence image observed by confocal laser scanning microscope (CLSM). Portions irradiated through HPML showed that diacetylene formed conjugated polydiacetylene to express high fluorescence, while blocked portions did not show fluorescence. Blue fluorescence is 475 nm light emitted by excitation with a 458 nm argon laser.

In the present invention, a multifunctional liquid crystal compound having two different photopolymerization groups, acrylic and diacetylene, was synthesized. Compound (6-8) are held a smectic phase at room temperature. The anisotropic polymer film was obtained by selectively polymerizing the acryl group of compound 6 using 365 nm ultraviolet rays. Photoimaging using a photomask was obtained by continuous photopolymerization of a diacetylene group. Continuous photopolymerization of multifunctional liquid crystal compounds is useful for performing fine micropatterning, and thus can be applied to various fields. In addition, these compounds showed bidirectional liquid crystal characteristics as well as excellent thermal and photopolymerization characteristics.

In the following, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited by these examples.

¹ H and ¹³ C NMR spectral analyzes of the compounds of the present invention were measured using a BRUKER Avance DPX-300 and Avance 500 spectrometer. Fourier transform infrared (FT-IR) spectra were obtained with Perkin Elemer Spectrum GX I using KBr pellets, and elemental analysis was performed using a CE instrument EA 1110 analyzer. Differential scanning calorimetry was measured at a scan rate of 10 ° C./min using TA modulated DSC Q10 and 2090 instruments. Optical microscopy was performed using a Leica DM LP equipped with a Mettler Toledo FP 82HT heating stage and a Mettler Toledo FP 90 central process controller. UV-Vis spectra were obtained using a Sinco 3150 spectrometer, fluorescence spectra were recorded with a Shimadzu RF-5310PC spectrophotometer, and fluorescence images were obtained using a Carl Zeiss-LSM510 confocal laser scanning microscope.

Example 1

Synthesis of ethyl-4- (4-hydroxyphenyl) benzoate ( 1 )

10 g of 4'-hydroxy-4-biphenylcarboxylic acid and a small amount of sulfuric acid were added to 200 ml of ethanol and heated to reflux for about 24 hours. The reaction solution was concentrated and poured into distilled water and neutralized to pH 8. The obtained precipitate was filtered and washed with distilled water and then recrystallized in ethanol to give 11.3 g (yield: 99.8%) of compound ( 1 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.11 (d, J = 8.3 Hz, -OOCAr-, 2H), 7.62 (d, J = 8.3 Hz, Ar, 2H), 7.54 (d, J = 8.5 Hz , Ar, 2H), 6.98 (d, J = 8.0 Hz, Ar, 2H), 5.30 (s, -OH, 1H), 4.44 (t, -COOCH _2- , 2H), 4.05 (t, -OCH ₂ , 2H), 1.44 (t, -CH ₃ , 3H). Elemental Analysis C ₁₅ H ₁₄ O ₃ : C, 74.36; H, 5.82. Found: 74.19; H, 5.86.

Example 2

Synthesis of ethyl 4- [4- (6-hydroxyhexyloxy) phenyl] benzoate ( 2 )

To 50 ml of DMF, a solution of 5.0 g of compound ( 1 ), 3.7 g of potassium carbonate and a small amount of potassium iodide was stirred at 80 ° C. under a nitrogen stream, and 2.0 g of 1-bromo-6-hydroxyhexane was slowly added dropwise thereto. It was reacted for a time. The reaction solution was poured into 250 ml of distilled water to form a precipitate. The resultant was filtered and washed with distilled water and recrystallized in ethanol to obtain 7.0 g (yield: 99.1%) of compound ( 2 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.11 (d, J = 8.3 Hz, -OOCAr-, 2H), 7.62 (dd, superposition, Ar, 4H) 7.00 (d, J = 8.8 Hz -OCH _2- , 2H), 4.44 (t, -COOCH _2- , 2H), 4.05 (t, -OCH ₂ , 2H), 1.87-1.40 (m, -CH _2- , 11H). Elemental Analysis C ₂₁ H ₂₆ O ₄ : C, 73.66; H, 7.65. Found: C, 73.62; H, 7.66.

Example 3

Synthesis of 4- [4- (6-hydroxyhexyloxy) phenyl] benzoic acid ( 3 )

In 30 ml of tetrahydrofuran (THF), 5.0 g of Compound ( 2 ) and 1.6 g of potassium hydroxide dissolved in ethanol / water (5/1, 60 ml) were added, and the mixed solution was refluxed for 12 hours. After the reaction was cooled, tetrahydrofuran (THF) and ethanol were concentrated and poured into distilled water, and the resulting precipitate was filtered and recrystallized in hexane to obtain 4.5 g (yield: 98.6%) of Compound ( 3 ).

¹ H NMR (DMSO- d ₆ , ppm): δ = 7.86 (d, J = 7.9 Hz, -OOCAr-, 2H), 7.59 (d, J = 8.5 Hz, Ar, 2H), 7.47 (d, J = 8.1 Hz, Ar, 2H), 7.00 (d, J = 8.5 Hz -OCH _2- , 2H), 4.36 (s, -OH, 1H), 4.02 (t, -COOCH _2- , 2H), 3.45 (t, -OCH ₂ , 4H), 1.75-1.65 (m, -OCH ₂ CH _2- , 4H), 1.54-1.27 (m, -CH _2- , 4H). Elemental Analysis C ₁₉ H ₂₂ O ₄ : C, 72.59; H, 7.05. Found: C, 72.39; H, 7.10.

Example 4

Synthesis of 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoic acid ( 4 )

A solution of 5.0 g of compound ( 3 ), 2.0 g of N , N -diethylaniline, and a small amount of 2,6-di-tert-butyl phenol in 50 ml of 1,4-dioxane was stirred at room temperature under a nitrogen stream. 2.7 g of acryloyl chloride was slowly added dropwise and reacted for 24 hours. The reaction solution was poured into 250 ml of distilled water to form a precipitate. The resulting product was filtered and washed with distilled water and recrystallized in ethanol to obtain 4.1 g (yield: 70.0%) of compound ( 4 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.17 (d, J = 8.4 Hz, -OOCAr-, 2H), 7.67 (d, J = 8.4 Hz, Ar, 2H), 7.59 (d, J = 8.7 Hz , Ar, 2H), 7.00 (d, J = 8.8 Hz, -OAr-, 2H), 6.44 (d, J = 17.3 Hz, = CH, 1H), 6.17 (dd, J = 10.4, 6.9 Hz, = CH , 1H), 5.84 (d, J = 10.4 Hz, = CH, 1H), 4.21 (t, -OCH 2 -, 2H), 4.04 (t, -ArOCH 2 -, 2H), 1.84-1.70 (m, - OCH ₂ CH _2- , 4H), 1.60-1.47 (m, -CH2-, 4H). Elemental Analysis C ₂₂ H ₂₄ O ₅ : C, 71.72; H, 6.57. Found: C, 71.77; H, 6.72.

Example 5a

Synthesis of dodeca-5,7-diin-1-ol ( 5a )

To 80/80 ml of pyridine / tetrahydrofuran (THF), 3.0 g of 5-hexyn-1-ol, 3.7 g of 1-hexine, and 11.1 g of copper (II) acetate were added and the mixed solution was stirred for 18 hours under a nitrogen stream of 60 degrees. It was refluxed. The resulting solid was removed by filtration and the solvent was concentrated. Then, 2.2 g (yield: 40.4%) of compound ( 5a ) was purified by silica gel column chromatography using ethyl acetate: hexane 1: 3 (v / v) solution as a developing solvent. )

¹ H NMR (CDCl ₃ , ppm): δ = 3.69 (t, -OCH ₂ , 2H), 2.34 (m, ≡CCH ₂ , 4H), 1.70-1.62 (m, -CH _2- , 4H), 1.52- 1.41 (m, -CH _2- , 4H), 0.94 (t, -CH ₃ , 3H). Elemental Analysis C ₁₂ H ₁₈ O: C, 80.85; H, 10.18. Found: C, 80.57; H, 10.32.

Example 5b

Synthesis of tetradeca-5,7-diin-1-ol ( 5b )

2.4 g (yield: 45.7%) of compound ( 5b ) was obtained using the same synthesis method as compound ( 5a ).

¹ H NMR (CDCl ₃ , ppm): δ = 3.69 (t, -OCH ₂ , 2H), 2.34 (m, ≡CCH ₂ , 4H), 1.70-1.26 (m, -CH _2- , 12H), 0.91 ( t, -CH ₃ , 3H). Elemental Analysis C ₁₄ H ₂₂ O: C, 81.50; H, 10.75. Found: C, 81.73; H, 10.75.

Example 5c

Synthesis of hexadeca-5,7-diin-1-ol ( 5c )

2.3 g (yield: 53.6%) of compound ( 5c ) was obtained using the same synthesis method as compound ( 5a ).

¹ H NMR (CDCl ₃ , ppm): δ = 3.69 (t, -OCH ₂ , 2H), 2.34 (m, ≡CCH ₂ , 4H), 1.70-1.24 (m, -CH _2- , 16H), 0.90 ( t, -CH ₃ , 3H). Elemental Analysis C ₁₆ H ₂₆ O: C, 81.99; H, 11.18. Found: C, 82.18; H, 11.04.

Example 5d

Synthesis of Aikosa-5,7-diin-1-ol ( 5d )

6.5 g (yield: 36.6%) of Compound ( 5d ) was obtained using the same synthesis method as Compound ( 5a ).

¹ H NMR (CDCl ₃ , ppm): δ = 3.68 (t, -OCH ₂ , 2H), 2.34 (m, ≡CCH ₂ , 4H), 1.70-1.24 (m, -CH _2- , 24H), 0.90 ( t, -CH ₃ , 3H). Elemental Analysis C ₂₀ H ₃₄ O: C, 82.69; H, 11.80. Found: C, 82.81; H, 11.68.

Example 5e

Synthesis of deca-3,5-diin-1-ol ( 5e )

3.0 g (yield: 46.7%) of compound ( 5e ) was obtained using the same synthesis method as compound ( 5a ). (Yield 3.0 g (46.7%)).

¹ H NMR (CDCl ₃ , ppm): δ = 3.69 (t, -OCH ₂ , 2H), 2.34 (m, ≡CCH ₂ , 4H), 1.70-1.62 (m, -CH _2- , 4H), 1.52- 1.41 (m, -CH _2- , 4H), 0.94 (t, -CH ₃ , 3H). Elemental Analysis C ₁₀ H ₁₄ O: C, 79.96; H, 9.39. Found: C, 80.10; H, 9.25.

Example 5f

Synthesis of octadeca-3,5-diin-1-ol ( 5f )

7.0 g (yield: 46.2%) of compound ( 5f ) was obtained using the same synthesis method as compound ( 5a ).

¹ H NMR (CDCl ₃ , ppm): δ = 3.69 (t, -OCH ₂ , 2H), 2.34 (m, ≡CCH ₂ , 4H), 1.70-1.41 (m, -CH _2- , 20H), 0.94 ( t, -CH ₃ , 3H). Elemental Analysis C ₁₈ H ₃₀ O: C, 82.38; H, 11.52. Found: C, 82.04; H, 11.63.

Example 5g

12-hydroxydodeca-5,7-diinnitrile ( 5 g )

1.3 g (yield: 43.2%) of compound ( 5 g ) was obtained using the same synthesis method as compound ( 5a ).

¹ H NMR (CDCl ₃ , ppm): δ = 3.74 (t, -OCH ₂ , 2H), 2.53 (t, CH ₂ CN, ≡CCH ₂ , 4H), 2.34 (t, ≡CCH ₂ , 2H), 1.70 -1.63 (m, -CH _2- , 6H), 1.43 (s, -OH, 1H). Elemental Analysis C ₁₂ H ₁₅ NO: C, 76.16; H, 7.99; N: 7.40. Found: C, 76.44; H, 7.73, N: 7.54.

Example 6

Synthesis of dodeca-5,7-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate ( 6 )

A solution of 2.5 g of Compound ( 4 ) and 1.2 g of Compound ( 5a ) in 20/20 ml of dichloromethane / tetrahydrofuran (THF) was stirred at room temperature under a stream of nitrogen, and dicyclohexylcarbodiimide (DCC) 1.7 g and dimethylaminopyridine (DMAP) were added sequentially and reacted for 24 hours. The resulting solid was removed by filtration filter and the solvent was concentrated, ethyl acetate: hexane 1: 3 (v / v) solution of 1.8g (yield: 50.2%) was purified by silica gel column chromatography using a developing solvent of the compound (6 )

¹ H NMR (CDCl ₃ , ppm): δ = 8.10 (d, J = 8.3 Hz, -OOCAr-, 2H), 7.63 (dd, superposition, Ar, 4H), 7.00 (d, J = 8.8 Hz, -OAr -, 2H), 6.44 (d, J = 17.3 Hz, = CH, 1H), 6.17 (dd, J = 10.3, 7.0 Hz, = CH, 1H), 5.84 (d, J = 10.3 Hz, = CH, 1H _{), 4.37 (t, -COOCH 2} -, 2H), 4.20 (t, -OCH 2 -, 2H), 4.04 (t, -ArOCH 2 -, 2H), 2.39 (t, ≡CCH 2 -, 2H), 2.28 (t, ≡CCH _2- , 2H), 1.91-1.83 (m, -OCH ₂ CH _2- , 6H), 1.75-1.70 (m, ≡CCH ₂ CH _2- , 4H), 1.49-1.42 (m, -CH _2- , 6H), 0.93 (t, -CH ₃ , 3H). Elemental Analysis C ₃₄ H ₄₀ O ₅ : C, 77.24; H, 7.63. Found: C, 77.25; H, 7.66.

Example 7

Synthesis of tetradeca-5,7-diynyl4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate ( 7 )

Using the same synthetic method as Compound ( 6 ), 7.0 g (Yield: 46.2%) of Compound ( 7 ) were obtained.

¹ H NMR (CDCl ₃ , ppm): δ = 8.10 (dd, J = 8.3 Hz, -OOCAr-, 2H), 7.63 (dddd, superposition, Ar, 4H), 7.00 (dd, J = 8.8 Hz, -OAr -, 2H), 6.44 (d, J = 17.3 Hz, = CH, 1H), 6.17 (dd, J = 10.3, 7.0 Hz, = CH, 1H), 5.84 (d, J = 10.3 Hz, = CH, 1H _{), 4.37 (t, -COOCH 2} -, 2H), 4.20 (t, -OCH 2 -, 2H), 4.04 (t, -ArOCH 2 -, 2H), 2.39 (t, ≡CCH 2 -, 2H), 2.28 (t, ≡CCH _2- , 2H), 1.91-1.83 (m, -OCH ₂ CH _2- , 6H), 1.75-1.70 (m, ≡CH ₂ CH _2- , 4H), 1.57-1.28 (m, -CH _2- , 10H), 0.91 (t, -CH ₃ , 3H). Elemental Analysis C ₂₁ H ₂₆ O ₄ : C, 77.66; H, 7.97. Found: C, 77.51; H, 8.08.

Example 8

Synthesis of hexadeca-5,7-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate ( 8 )

1.3 g (yield: 54.0%) of compound ( 8 ) was obtained using the same synthesis method as compound ( 6 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.10 (dd, J = 8.3 Hz, -OOCAr-, 2H), 7.63 (dddd, superposition, Ar, 4H), 7.00 (dd, J = 8.8 Hz, -OAr -, 2H), 6.44 (d, J = 17.3 Hz, = CH, 1H), 6.17 (dd, J = 10.3, 7.0 Hz, = CH, 1H), 5.84 (d, J = 10.3 Hz, = CH, 1H _{), 4.37 (t, -COOCH 2} -, 2H), 4.20 (t, -OCH 2 -, 2H), 4.04 (t, -ArOCH 2 -, 2H), 2.39 (t, ≡CCH 2 -, 2H), 2.28 (t, ≡CCH _2- , 2H), 1.91-1.83 (m, -OCH ₂ CH _2- , 6H), 1.75-1.70 (m, ≡CCH ₂ CH _2- , 4H), 1.57-1.28 (m, -CH _2- , 14H), 0.90 (t, -CH ₃ , 3H). Elemental Analysis C ₃₈ H ₄₈ O ₅ : C, 78.05; H, 8. 27. Found: C, 78.06; H, 8.40.

Example 9

Synthesis of aikosa-5,7-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate ( 9 )

2.2 g (yield: 41.1%) of compound ( 9 ) was obtained using the same synthesis method as compound ( 6 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.10 (dd, J = 8.3 Hz, -OOCAr-, 2H), 7.63 (dddd, superposition, Ar, 4H), 7.00 (dd, J = 8.8 Hz, -OAr -, 2H), 6.44 (d, J = 17.3 Hz, = CH, 1H), 6.17 (dd, J = 10.3, 7.0 Hz, = CH, 1H), 5.84 (d, J = 10.3 Hz, = CH, 1H _{), 4.37 (t, -COOCH 2} -, 2H), 4.20 (t, -OCH 2 -, 2H), 4.04 (t, -ArOCH 2 -, 2H), 2.39 (t, ≡CCH 2 -, 2H), 2.28 (t, ≡CCH _2- , 2H), 1.91-1.83 (m, -OCH ₂ CH _2- , 6H), 1.75-1.70 (m, ≡CCH ₂ CH _2- , 4H), 1.57-1.25 (m, -CH _2- , 22H), 0.90 (t, -CH ₃ , 3H). Elemental Analysis C ₄₂ H ₅₆ O ₅ : C, 78.71; H, 8.81. Found: C, 78.48; H, 8.87.

Example 10

Synthesis of deca-3,5-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate ( 10 )

0.7 g (yield: 51.5%) of compound ( 10 ) was obtained using the same synthesis method as compound ( 6 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.10 (d, J = 8.3 Hz, -OOCAr-, 2H), 7.63 (dd, superposition, Ar, 4H), 7.00 (d, J = 8.8 Hz, -OAr -, 2H), 6.44 (d, J = 17.3 Hz, = CH, 1H), 6.17 (dd, J = 10.3, 7.0 Hz, = CH, 1H), 5.84 (d, J = 10.3 Hz, = CH, 1H _{), 4.43 (t, -COOCH 2} -, 2H), 4.20 (t, -OCH 2 -, 2H), 4.00 (t, -ArOCH 2 -, 2H), 2.77 (t, ≡CCH 2 -, 2H), 2.28 (t, ≡CCH _2- , 2H), 1.83-1.70 (m, -OCH ₂ CH _2- , 4H), 1.53-1.42 (m, -CH _2- , 8H), 0.93 (t, -CH ₃ , 3H). Elemental Analysis C ₃₂ H ₃₆ O ₅ : C, 76.77; H, 7.25. Found: C, 76.74; H, 7.29.

Example 11

Synthesis of octadeca-3,5-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate ( 11 )

1.2 g (yield: 59.3%) of compound ( 11 ) was obtained using the same synthesis method as compound ( 6 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.10 (d, J = 8.3 Hz, -OOCAr-, 2H), 7.63 (dd, superposition, Ar, 4H), 7.00 (d, J = 8.8 Hz, -OAr -, 2H), 6.44 (d, J = 17.3 Hz, = CH, 1H), 6.17 (dd, J = 10.3, 7.0 Hz, = CH, 1H), 5.84 (d, J = 10.3 Hz, = CH, 1H _{), 4.43 (t, -COOCH 2} -, 2H), 4.20 (t, -OCH 2 -, 2H), 4.00 (t, -ArOCH 2 -, 2H), 2.77 (t, ≡CCH 2 -, 2H), 2.28 (t, ≡CCH _2- , 2H), 1.83-1.70 (m, -OCH ₂ CH _2- , 4H), 1.53-1.25 (m, -CH _2- , 24H), 0.93 (t, -CH ₃ , 3H). Elemental Analysis C ₄₀ H ₅₂ O ₅ : C, 78.39; H, 8.55. Found: C, 78.15; H, 8.62.

Example 12

Synthesis of 11-cyanoounde-5,7-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate ( 12 )

1.2 g (yield: 42.0%) of compound ( 12) was obtained using the same synthesis method as for compound ( 6 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.09 (d, J = 8.3 Hz, -OOCAr-, 2H), 7.64 (dd, superposition, Ar, 4H), 7.00 (d, J = 8.8 Hz, -OAr -, 2H), 6.44 (d, J = 17.3 Hz, = CH, 1H), 6.17 (dd, J = 10.3, 7.0 Hz, = CH, 1H), 5.84 (d, J = 10.3 Hz, = CH, 1H ), 4.38 (t, J = 6.6Hz, -COOCH 2 -, 2H), 4.20 (t, J = 6.6Hz, -OCH 2 -, 2H), 4.04 (t, J = 6.6Hz, -ArOCH 2 -, 2H), 2.53 (t, J = 7.0 Hz, -CH ₂ CN, -CCH _2- , 4H), 2.37 (t, -CCH _2- , 2H), 1.93-1.83 (m, -OCH ₂ CH _2- , 8H), 1.75-1.50 (m, -CH _2- , 6H). Elemental Analysis C ₃₄ H ₃₇ NO ₅ : C, 75.67; H, 6.91; N, 2.60. Found: C, 75.46; H, 7.00; N, 2.59.

Example 13

Synthesis of 4- (6-hydroxyhexyloxy) benzoic acid ( 13 )

A solution of 10.0 g of 4-hydroxybenzoic acid, 10.8 g of potassium hydroxide, and a small amount of potassium iodide was stirred at room temperature under nitrogen stream in 30/20 ml of ethanol / water, and 9.0 g of 1-chloro-6-hydroxyhexane was slowly added dropwise. After refluxing for 48 hours. The reaction solution was concentrated and the remaining product was dissolved in distilled water and extracted with diethyl ether (x3). The aqueous layer was separated, hydrochloric acid was added and acidified to pH 2, and the obtained precipitate was filtered and washed with distilled water and recrystallized in ethanol to obtain 12.1 g (yield: 54.0%) of compound ( 13 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.08, 6.95 (dd, aromatic moiety, 4H), 4.20 (s, -OH, 1H), 4.05 (t, -OCH ₂ , 2H), 1.87-1.48 (m , Alkyl chain proton, 8H).

Example 14

Synthesis of 4- (6-hydroxyhexyloxy) benzoic acid ( 14 )

To 60 ml of toluene was added a solution of 5.0 g of compound ( 13 ), 1.4 g of p -toluene sulfonic acid and a small amount of hydroquinone, and 5.7 ml of acrylic acid was slowly added dropwise, followed by 12 hours using a Dean-stark trap. Reflux for a while. The reaction solution was concentrated, and the remaining product was dissolved in diethyl ether and extracted with distilled water (x3) to remove acrylic acid. Water was removed over magnesium sulfate, and the obtained solution was concentrated and recrystallized in isopropanol to obtain 3.0 g (yield: 48.1%) of compound ( 14 ).

¹ H NMR (CDCl ₃ , ppm): δ = 8.08, 6.95 (dd, aromatic moiety, 4H), 6.45, 6.19, 5.86 (m, vinyl proton, 3H), 4.22, 4.07 (t, -OCH ₂ , 4H) , 1.87-1.48 (m, alkyl chain protons, 8H).

Example 15

Synthesis of 1- (4-hydroxyphenyl) -4-butyldiyne Formula (III) (n = 3)

 Using 4-ethynylphenol and 1-hexine, the compound was obtained in a yield of 52% using the same synthesis method as for compound (5a).

¹ H NMR (CDCl ₃ , ppm): δ = 7.38, 6.77 (dd, aromatic protons, 4H), 5.07 (s, -OH, 3H), 2.34 (t, CCH ₂ , 2H), 1.58-0.85 (m, Alkyl chain protons, 9H).

Example 16

Synthesis of 1- (4-hydroxyphenyl) -4-hexyldiyne Formula (III) (n = 5)

 Using the same synthesis method as in Example 15, a compound having a yield of 56% was obtained.

¹ H NMR (CDCl ₃ , ppm): δ = 7.38, 6.77 (dd, aromatic protons, 4H), 5.07 (s, -OH, 3H), 2.34 (t, CCH ₂ , 2H), 1.58-0.85 (m, Alkyl chain protons, 9H).

Example 17

Synthesis of 1- (4-hydroxyphenyl) -4-octyldiyne Formula (III) (n = 7)

 Using the same synthesis method as in Example 15, a compound having a yield of 66% was obtained.

¹ H NMR (CDCl ₃ , ppm): δ = 7.38, 6.77 (dd, aromatic protons, 4H), 5.07 (s, -OH, 3H), 2.34 (t, CCH ₂ , 2H), 1.58-0.85 (m, Alkyl chain protons, 9H).

Example 18

Synthesis of 1- (4-hydroxyphenyl) -4-decyldiyne Formula (III) (n = 9)

 Using the same synthesis method as in Example 15, a compound having a yield of 40% was obtained.

¹ H NMR (CDCl ₃ , ppm): δ = 7.38, 6.77 (dd, aromatic protons, 4H), 5.07 (s, -OH, 3H), 2.34 (t, CCH ₂ , 2H), 1.58-0.85 (m, Alkyl chain protons, 9H).

Example 19

Synthesis of compound 15 ( 15 )

In 50 ml of dichloromethane, 1.8 g of compound ( 14 ), 2.8 g of thionyl chloride, 0.4 g of an initiator (2,6 di-tert-butyl 4-methylphenol) and a small amount (2 drops) of dimethylformamide (DMF) were added thereto. The mixture was stirred at room temperature under a nitrogen stream. After 40 minutes, excess thionyl chloride was removed under reduced pressure, and the remaining product was dissolved in 8 ml of chloroform, and slowly added dropwise to a solution containing 1.1 g of compound (III) having n = 3, 0.54 g of triethylamine, and 15 ml of chloroform ( 0 ° C.), and the reaction was performed at room temperature for 16 hours. The obtained product was dissolved in 100 ml of chloroform, extracted with distilled water (x1), 2 N sodium hydroxide (x3) and distilled water (x2), and the organic layer was removed with magnesium sulfate, and then ethyl acetate: hexane 1: 4 (v / v). ) Was used as a developing solvent, and the silica gel column chromatography yielded 53% of a compound ( 15 ).

_{^{1 H NMR (DMSO- d 6,}} ppm): δ = 8.07, 7.64, 7.33, 7.12 (dddd, aromatic protons, 8H), 6.32, 6.20, 5.88 (m, vinyl protons, 3H), 4.11 (m, -OCH ₂ , 4H), 2.43 (t, ≡2, 2H), 1.51-1.38 (m, alkyl chain protons, 12H), 0.92 (t, -CH ₃ , 3H). Elemental Analysis C ₃₀ H ₃₂ O ₅ : C, 76.25; H, 6.83. Found: C, 75.94; H, 6.82.

Example 20

Synthesis of compound 16 ( 16 )

Compound ( 16 ) was obtained in yield 41% using the same synthesis method as compound ( 15 ).

_{^{1 H NMR (DMSO- d 6,}} ppm): δ2, 4H), 2.46 (t, ≡CCH 2, 2H), 1.62 - 1.22 (m, alkyl chain protons, 16H), 0.89 (t, -CH 3, 3H ). Elemental Analysis C ₃₂ H ₃₆ O ₅ : C, 76.77; H, 7.25. Found: C, 76.75; H, 7.32.

Example 21

Synthesis of compound 17 ( 17 )

Using the same synthetic method as Compound ( 15 ), Compound ( 17 ) was obtained in a yield of 48.0%.

_{^{1 H NMR (DMSO- d 6,}} ppm): δ = 7.96, 7.53, 7.22, 7.02 (dddd, aromatic protons, 8H), 6.19, 6.11, 5.85 (m, vinyl protons, 3H), 4.03 (m, -OCH ₂ , 4H), 2.34 (t, ≡CCH ₂ , 2H), 1.64-1.15 (m, alkyl chain protons, 20H), 0.76 (t, -CH ₃ , 3H). IR (KBr, cm ⁻¹ ): 2931, 2854, 2243, 2145, 1737, 1723, 1635, 1606, 1408, 1000, 985, 875, 844, 811. Elemental Analysis C ₃₄ H ₄₀ O ₅ : C, 77.24; H, 7.63. Found: C, 77.25; H, 7.66.

Example 22

Synthesis of compound 18 ( 18 )

Using the same synthesis method as Compound ( 15 ), Compound ( 18 ) was obtained in a yield of 47.0%.

_{^{1 H NMR (DMSO- d 6,}} ppm): δ = 8.07, 7.64, 7.32, 7.12 (dddd, aromatic protons, 8H), 6.30, 6.21, 5.95 (m, vinyl protons, 3H), 4.13 (m, -OCH ₂ , 4H), 2.44 (t, ≡CCH ₂ , 2H), 1.75-1.33 (m, alkyl chain protons, 24H), 0.88 (t, -CH ₃ , 3H). Elemental Analysis C ₃₆ H ₄₄ O ₅ : C, 77.66; H, 7.97. Found: C, 77.77; H, 8.00.

In the present invention, a multifunctional liquid crystal compound having two different photopolymerization groups, acrylic and diacetylene, was synthesized. Compound (6-8) are held a smectic phase at room temperature. The anisotropic polymer film was obtained by selectively polymerizing the acryl group of compound ( 6 ) using 365 nm ultraviolet-ray. Photoimaging using a photomask was obtained by continuous photopolymerization of a diacetylene group. Therefore, continuous photopolymerization of multifunctional liquid crystal compounds is very useful for performing fine micropatterning, and thus it is applicable to various fields.

1 shows (a) ultraviolet and (b) photoluminescence spectra of compound 6

Figure 2 is a patterned image photograph observed through an optical microscope

Figure 3 is a fluorescence image using a confocal laser scanning microscope of compound 6

Claims (10)

Multifunctional liquid crystal compound represented by the following formula (I):

Wherein m is an integer from 2 to 4, n is an integer from 3 to 11, and R is a C ₁ to C ₅ lower alkyl group or a nitrile group. The multifunctional liquid crystal compound according to claim 1, wherein the compound of formula (I) is the following compound: Dodeca-5,7-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate Tetradeca-5,7-diynyl4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate Hexadeca-5,7-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate Aicosa-5,7-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate Deca-3,5-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate Octadeca-3,5-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate and 11-cyanoounde-5,7-diynyl 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoate In the organic solvent, 4- [4- (6-acryloyloxyhexyloxy) phenyl] benzoic acid is added to the compound of formula (II), and the reaction is carried out in nitrogen atmosphere. Method for preparing a multifunctional liquid crystal compound:

Wherein m is an integer from 2 to 4, n is an integer from 3 to 11, and R is a C ₁ to C ₅ lower alkyl group or a nitrile group. The method of claim 3, wherein the organic solvent is at least one selected from the group consisting of dichloromethane, chloroform and tetrahydrofuran. Multifunctional liquid crystal compound represented by the following formula (Ia):

Wherein n is an integer from 3 to 9. 4- (6-hydroxyhexyloxy) benzoic acid and a compound of formula (III) are added to the organic solvent, A multifunctional liquid crystal compound of formula (Ia) characterized by comprising reacting in a nitrogen atmosphere Manufacturing Method:

Wherein n is an integer from 3 to 9. The method of claim 6, wherein the organic solvent is at least one selected from the group consisting of dichloromethane, chloroform, and tetrahydrofuran. A step of adding a photoinitiator to a compound of formula (I) or (Ia) and then selectively polymerizing acrylic groups by irradiating 350 to 380 nm UV; Selective photopolymerization method of a multi-functional liquid crystal compound comprising the step of polymerizing a vinyl group and diacetylene groups by irradiating 240 to 270 nm UV through a photomask to the polymer film formed in the first step:

Wherein n is an integer from 3 to 11 and R is a C ₁ to C ₅ lower alkyl group or a nitrile group. 10. The selective photopolymerization of the multifunctional liquid crystal compound according to claim 8, wherein the photoinitiator is 2,2-dimethoxy-2-phenylacetophenone (DMPA) or 2,6 di-tert-butyl 4-methylphenol. Way. Fine pattern obtained by the method of Claim 8 or 9.

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