KR101167234B1 - Polymerisable Liquid Crystal Compounds and Their Polymers - Google Patents

Abstract

The present invention provides a novel polymerizable liquid crystal compound represented by the following formula (1) in which 2,7-diethynyl-fluorene is introduced at the center of a molecule. These novel polymerizable liquid crystal compounds have a wide liquid crystal phase temperature range, excellent solubility, high isotropic transition temperature, high optical anisotropy, high charge mobility, low viscosity, excellent compatibility with other liquid crystals, excellent orientation characteristics, and excellent degree of polymerization. to provide. In addition, the present invention is to easily produce a polymerizable liquid crystal composition that maintains the liquid crystal phase in a wide temperature range including room temperature even with a single component polymerizable liquid crystal compound. Provided are polymers for semiconductors and / or organic light-emitting bodies.
≪ Formula 1 >

Description

Polymerizable Liquid Crystal Compounds and Their Polymers

The present invention relates to a novel polymerizable liquid crystal compound derived from fluorene and a polymerizable liquid crystal composition comprising the same and a polymer prepared therefrom.

Polyfluorene conjugated polymer compounds having a 9,9-dialkylfluorene unit structure and semiconductor properties are very attractive display materials due to their advantages such as efficient blue light emission, high mobility, and process ease (Ullrich Scherf et al., Adv. Mater., 2002, 14 (7), 477-487). On the other hand, skeletal agglomeration occurring in conjugated polymers leads to the disappearance of excimers, so minimizing agglomeration of the polymer skeleton is required to obtain an effective organic light emission efficiency.

The long alkyl chain substituted at the 9,9-position improves the solubility of the polymer to secure solution fairness and is oriented perpendicular to the polymer main chain, thereby solving the aggregation of the polymer chain.

In this regard, Bin Liu et al. Synthesized copolymers containing 9,9-dihexylfluorene and substituted thiophenes or bithiophenes and applied them to OLEDs (Macromolecules, 2000, 33, 8945-8952). The authors investigated the optical, electrochemical and thermal properties of an efficient blue-green light emitting polymer that is useful as a light emitting device by controlling the number of thiophenes, the position of alkyl groups substituted in the thiophene ring, and the connection structure of a plurality of thiophenes. By adjusting, a fluorene-thiophene hybrid polymer having a solubility in solvents, high thermal stability and high glass transition temperature was prepared:

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On the other hand, Mary O'Neil and Stephane, et al. More than one liquid crystal compound was mixed to extend the liquid crystal phase temperature range (US 2005/0146263 A1, Chem. Mater, 2004. 16. 4928-4936):

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Brown, B., et al., Of AVECIA, has described a field effect transistor comprising a fluorene polymer organic semiconductor and a binder and a method of manufacturing the same in WO 02/45184.

H. Sirringhaus et al. Observed a charge mobility of 10 ^-2 cm ² V ^-1 s ^-1 in a field effect transistor made of 9,9-dioctyl-fluorene-co-bithiophene (F8T2) liquid crystal polymer. This is believed to be due to the liquid crystallinity (nematic phase, 275-285 ° C.) of the polymer that controls the morphology of the semiconductor. However, the 9,9-substituted dioctyl groups interfere with the packing of the polymer and interfere with charge transport.

In order to eliminate this problem, Ian Mc Culloch et al. Designed a liquid crystalline polymer compound with no substitution of 9-position of fluorene to enhance packing property and introduced solubility without interrupting packing by introducing thiophene copolymer monomer substituted with alkyl group. Solved. The copolymer obtained thus exhibited liquid crystallinity and resulted in a significantly lower liquid crystal phase temperature (265 ° C. → 150 ° C.) than the polymer obtained from F8T2, thereby lowering the temperature of the field effect transistor manufacturing process.

It is also reported that a polymer having higher order, charge mobility and stability can be obtained from a polymerizable liquid crystal compound having a spacer and one or more polymer groups in a central core including 9-H, H-fluorene and arylene groups. (US 7,126,013 B2). The polymerizable liquid crystal compound described below is useful as a field effect transistor (FET) device material as an organic semiconductor or a charge transport material, and photoelectric properties are known to be applicable to photovoltaic cells, sensors, and organic light emitting device materials.

As described above, the polymerizable liquid crystal reactive compound may have a high degree of orientation control by intrinsic self-assembly and an external magnetic field and / or an alignment film, and may have optical properties inherent to the liquid crystal monomer compound through UV and / or thermal polymerization after coating in solution. It can be converted into a high performance, high performance polymer film that maintains electrical properties, photoelectric properties and at the same time ensures heat resistance and chemical resistance.

Therefore, the present inventors have studied to improve the orientation and polymerization processability while maintaining the optical anisotropy and electrical anisotropy characteristics of the liquid crystal derived from the known fluorene, as a result, by introducing an acetylene conjugated structure to fluorene, a single component liquid crystal compound A novel polymerizable liquid crystal compound which maintains a liquid crystal phase in a wide range of temperatures including room temperature alone, a polymerizable liquid crystal composition comprising a single component thereof or other liquid crystals and / or compounds, and polymers thereof have been developed and completed the present invention.

An object of the present invention is to provide a novel polymerizable liquid crystal compound in which 2,7-diethynyl-fluorene is introduced at the molecular center.

Another object of the present invention is to provide a polymerizable liquid crystal compound composition comprising at least one polymerizable liquid crystal compound.

Furthermore, another object of the present invention is to provide a polymer formed by polymerizing the polymerizable liquid crystal compound.

It is also an object of the present invention to provide a method for producing a polymerizable liquid crystal compound.

Furthermore, another object of the present invention is to provide an organic semiconductor transistor, a charge transporter and a light emitting body using a polymer formed by polymerizing the polymerizable liquid crystal compound.

In order to achieve the above object, the present invention provides a novel polymerizable liquid crystal compound, characterized in that represented by the formula (1) in which 2,7-diethynyl-fluorene is introduced at the molecular center:

≪ Formula 1 >

상기 식에서 R₁ 및 R₂는 각각 수소, 불소, 탄소수가 1-4인 직쇄형 또는 분지형의 알킬이고;
P₁ 및 P₂는 각각 하기의 중합성 반응기 군으로부터 선택되는 1종이고;

L₁ 및 L₂는 각각 -{O-(CH₂)m}-, -{O-(CH₂)m-CO}-, -{COO-(CH₂)m-}- 또는 -{COO-(CH₂)m-CO}- 이고;
상기 m은 1 내지 20의 정수이고;
상기 m개의 -(CH₂)- 중 1 또는 2 이상의 -(CH₂)-는 -O-, -S-, -CF₂-로 치환할 수 있고;
X₁, X₂, X₃ 및 X₄는 각각 하기의 방향족 치환기 군으로부터 선택되는 1종이고;

상기 R₃, R₄, R₅ 및 R₆는 각각 수소, 할로겐, 시아노, 니트로, C₁-C₁₂의 직쇄 또는 측쇄 알킬 또는 C₃-C₇의 시클로알킬기이고;
상기 R₃, R₄, R₅ 또는 R₆가 C₁-C₁₂, C₃-C₇의 알킬기일 경우 상기 알킬기는 비치환되거나 또는 할로겐 또는 시아노기로 치환될 수 있으며;
상기 알칼기 중 1 이상의 ?CH₂?기는 ?O?, ?S?, ?CF₂?로 치환될 수 있다.

Wherein R ₁ and R ₂ are each hydrogen, fluorine or straight or branched alkyl having 1 to 4 carbon atoms;
P ₁ and P ₂ are each one selected from the group of the following polymerizable reactors;

L ₁ and L ₂ are each-{O- (CH ₂ ) m}-,-{O- (CH ₂ ) m-CO}-,-{COO- (CH ₂ ) m-}-or-{COO- (CH ₂ ) m-CO}-;
M is an integer from 1 to 20;
One or two or more of the m — (CH ₂ ) — — (CH ₂ ) — may be substituted with —O—, —S—, —CF ₂ —;
X ₁ , X ₂ , X ₃ and X ₄ are each one selected from the following aromatic substituent groups;

R ₃ , R ₄ , R ₅ and R ₆ are each hydrogen, halogen, cyano, nitro, C ₁ -C ₁₂ straight or branched chain alkyl or C ₃ -C ₇ cycloalkyl group;
When the R ₃ , R ₄ , R ₅ or R ₆ is an alkyl group of C ₁ -C ₁₂ , C ₃ -C _7, the alkyl group may be unsubstituted or substituted with halogen or cyano group;
One or more —CH ₂ — groups in the alkali group may be substituted with —O ?,? S ?, or? CF ₂ ?.

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In addition, the present invention provides a polymerizable liquid crystal compound composition comprising at least one polymerizable liquid crystal compound.

Furthermore, the present invention provides a polymer formed by polymerizing a polymerizable liquid crystal compound.

The present invention also provides a method for producing a polymerizable liquid crystal compound.

Furthermore, the present invention provides an organic semiconductor transistor, a charge transporter, and a light emitting body using a polymer formed by polymerizing the polymerizable liquid crystal compound.

The novel polymerizable liquid crystal compound of the present invention has a wide liquid crystal phase temperature range including room temperature, high isotropic transition temperature, optical anisotropy, high charge mobility, low viscosity, excellent compatibility with other liquid crystals, excellent alignment characteristics, and excellent polymers. Can provide the degree of flower. In addition, the polymerizable liquid crystal compound of the present invention may provide a polymerizable liquid crystal composition by mixing with a single compound or another liquid crystal, and may be used as an organic semiconductor for an OFET, a hole transport material or an organic light emitting material for an OLED, and the like.

In addition, the polymer prepared from the polymerizable liquid crystal composition of the present invention can exhibit excellent functionalities such as heat resistance due to crosslinking, excellent charge mobility, high luminescence properties, low moisture permeability, high gas barrier properties, and excellent dimensional stability against heat. have. Therefore, the polymer prepared from the polymerizable liquid crystal composition of the present invention is useful as a material for an organic electro-optical device including an organic semiconductor device, an organic light emitting device, and the like.

1 shows a method for preparing a polymerizable liquid crystal compound,
2 is a polymerizable liquid crystal compound 6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-florene-2,7-diyl) bis (ethyne-2,1 Differential Scanning Calorimetry (DSC) of -Diyl) bis (thiophene-5,2-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate ego,
3 is a polymerizable liquid crystal compound 6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-florene-2,7-diyl) bis (ethyne-2,1 -Diyl) bis (thiophene-5,2-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate and polarization micrograph (POM) (130 ℃ heating, × 300),
4 is a polymerizable liquid crystal compound 6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-florene-2,7-diyl) bis (ethyne-2,1 Oxidation stability of diyl) bis (thiophene-5,2-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate solution (solvent CH2Cl2) Is measured using cyclic voltammetry,
5 is a degree of curing according to the light energy of a polymer film prepared from a polymerizable liquid crystal compound measured using FT-IR,
6 is a pencil hardness of a polymer film prepared from a polymerizable liquid crystal compound measured by IS standard JIS-K-5400 8.4 pencil scratch test method,
7 is a photoluminescence spectrum of the polymer film prepared from the polymerizable liquid crystal compound.

The present invention provides a novel polymerizable liquid crystal compound characterized in that 2,7-diethynyl-fluorene is represented by the following formula (1) in which the molecular center is introduced.

≪ Formula 1 >

상기 식에서 R₁ 및 R₂는 각각 수소, 불소, 탄소수가 1-4인 직쇄형 또는 분지형의 알킬이고;
P₁ 및 P₂는 각각 하기의 중합성 반응기 군으로부터 선택되는 1종이고;

L₁ 및 L₂는 각각 -{O-(CH₂)m}-, -{O-(CH₂)m-CO}-, -{COO-(CH₂)m-}- 또는 -{COO-(CH₂)m-CO}- 이고;
상기 m은 1 내지 20의 정수이고;
상기 m개의 -(CH₂)- 중 1 또는 2 이상의 -(CH₂)-는 -O-, -S-, -CF₂-로 치환할 수 있고;
X₁, X₂, X₃ 및 X₄는 각각 하기의 방향족 치환기 군으로부터 선택되는 1종이고;

상기 R₃, R₄, R₅ 및 R₆는 각각 수소, 할로겐, 시아노, 니트로, C₁-C₁₂의 직쇄 또는 측쇄 알킬 또는 C₃-C₇의 시클로알킬기이고;
상기 R₃, R₄, R₅ 또는 R₆가 C₁-C₁₂, C₃-C₇의 알킬기일 경우 상기 알킬기는 비치환되거나 또는 할로겐 또는 시아노기로 치환될 수 있으며;

Wherein R ₁ and R ₂ are each hydrogen, fluorine or straight or branched alkyl having 1 to 4 carbon atoms;
P ₁ and P ₂ are each one selected from the group of the following polymerizable reactors;

L ₁ and L ₂ are each-{O- (CH ₂ ) m}-,-{O- (CH ₂ ) m-CO}-,-{COO- (CH ₂ ) m-}-or-{COO- (CH ₂ ) m-CO}-;
M is an integer from 1 to 20;
One or two or more of the m — (CH ₂ ) — — (CH ₂ ) — may be substituted with —O—, —S—, —CF ₂ —;
X ₁ , X ₂ , X ₃ and X ₄ are each one selected from the following aromatic substituent groups;

R ₃ , R ₄ , R ₅ and R ₆ are each hydrogen, halogen, cyano, nitro, C ₁ -C ₁₂ straight or branched chain alkyl or C ₃ -C ₇ cycloalkyl group;
When the R ₃ , R ₄ , R ₅ or R ₆ is an alkyl group of C ₁ -C ₁₂ , C ₃ -C _7, the alkyl group may be unsubstituted or substituted with halogen or cyano group;

One or more —CH ₂ — groups in the alkali group may be substituted with —O ?,? S ?, or? CF ₂ ?.

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Preferably the polymerizable liquid crystal compound according to the present invention is 6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-fluorene-2,7) -Diyl) bis (ethyn-2,1-diyl) bis (thiophen-5,2-diyl) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) die It is an acrylate:

<Formula 2>

Hereinafter, the present invention will be described in more detail.

The novel polymerizable liquid crystal compound according to the present invention has a wide liquid crystal phase temperature range including room temperature, high isotropic transition temperature, high charge mobility, low viscosity, excellent compatibility with other liquid crystals, excellent alignment characteristics, optical anisotropy, It also provides good polymerisation. Therefore, even a single component polymerizable liquid crystal compound can easily prepare a polymerizable liquid crystal composition that maintains a liquid crystal phase in a wide temperature range including room temperature, and can be organically prepared through an ultraviolet and / or thermal polymerization process in a wide temperature range including room temperature. Polymers for semiconductors and / or organic light-emitting bodies can be prepared.

In addition, the polymerizable liquid crystal compound provides a polymerizable liquid crystal compound composition by mixing with a single compound or another liquid crystal.

The polymerizable liquid crystal compound composition can be polymerized according to the purpose.

Furthermore, the present invention provides a polymer formed by polymerizing a polymerizable liquid crystal composition.

The polymer includes at least one polymerizable liquid crystal compound of Formula 1, and the polymer may be prepared by UV curing or thermosetting. The single polymer may be prepared from the polymerizable liquid crystal compound represented by Formula 1, and the copolymer may be prepared by mixing with other monomers. Other monomers include both liquid crystals or non-liquid crystal compounds within a range that does not impair the ease of film manufacturing process and film properties.

The single polymer or copolymer, which is a polymer formed by polymerizing the polymerizable liquid crystal compound, has excellent properties such as heat resistance due to crosslinking, excellent charge mobility, high luminescence properties, low moisture permeability, high gas barrier property, and excellent dimensional stability against heat. There is functionality. Therefore, the prepared polymer may be used as an organic semiconductor for OFET or a hole transport material or light emitter for OLED.

The present invention comprises the steps of dialkylating the 9-position of 2,7-dibromofluorine (step 1);

Introducing an acetylene group by coupling a compound prepared in Step 1 with end-alkaine and Sonogashira (Step 2);

상기 R₃, R₄, R₅ 및 R₆는 각각 수소, 할로겐, 시아노, 니트로, C₁-C₁₂의 직쇄 또는 측쇄 알킬 또는 C₃-C₇의 시클로알킬기이고;
상기 R₃, R₄, R₅ 또는 R₆가 C₁-C₁₂, C₃-C₇의 알킬기일 경우 상기 알킬기는 비치환되거나 또는 할로겐 또는 시아노기로 치환될 수 있고;
상기 알칼기 중 1 이상의 ?CH₂?기는 ?O?, ?S?, ?CF₂?로 치환될 수 있고;
상기 화합물 B는 할로겐으로 치환된 하기 화합물 군으로부터 선택되는 어느 1종의 화합물이다;

Removing the protecting group using NaH from the compound produced in step 2 (step 3);
Sonogashira coupling reaction of the compound produced in step 3 with a mixture of the following compound A and compound A '(step 4); And
Method for producing a polymerizable liquid crystal compound comprising the step (step 5) of reacting the compound produced in step 4 with the following compound B in the presence of a tertiary amine base.

Compound A is Hal ₁ -X ₁ -X ₃ -L ₁ -OH;
Compound A 'is Hal ₂ -X ₂ -X ₄ -L ₂ -OH;
Hal ₁ and Hal ₂ are each independently selected from the group of halogen elements;
L ₁ and L ₂ are each independently-{O- (CH ₂ ) m}-,-{O- (CH ₂ ) m-CO}-,-{COO- (CH ₂ ) m-}-or- {COO- (CH ₂ ) m-CO}-;
M is an integer from 1 to 20;
One or two or more -CH ₂ -in the m —CH ₂ — groups may be substituted with —O—, —S—, —CF ₂ —;
X ₁ to X ₄ are each independently one selected from the following aromatic substituent group;

R ₃ , R ₄ , R ₅ and R ₆ are each hydrogen, halogen, cyano, nitro, C ₁ -C ₁₂ straight or branched chain alkyl or C ₃ -C ₇ cycloalkyl group;
When the R ₃ , R ₄ , R ₅ or R ₆ is an alkyl group of C ₁ -C ₁₂ , C ₃ -C _7, the alkyl group may be unsubstituted or substituted with halogen or cyano group;
At least one CH ₂ ? Group in the alkali group may be substituted with? O?,? S?,? CF ₂ ?
The compound B is any one compound selected from the group of the following compounds substituted with halogen;

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1 shows a method of preparing the polymerizable liquid crystal compound. As shown in FIG. 1, after the compound (a) was synthesized through the dimethylation reaction at the 9-position of 2,7-dibromoflorene and the compound (b) was synthesized through the Sonogashira coupling reaction. The protecting group is removed using NaH to convert to the compound (c) in which the acetylene groups are introduced at the 2 and 7 positions, respectively. Subsequently, a bromination reaction is carried out from 2-bromothiophene to Suzuki coupling, dimethylation, alkylation of phenol and thiophene ring to give compound (g) via compound (d) → (e) → (f). After synthesis, compound (h) can be synthesized from Sonogashira coupling reaction with compound (c). Thereafter, to give a polymerizable reactor to compound (h), acryloyl chloride is reacted in the presence of a tertiary amine base to synthesize (i), which is a polymerizable liquid crystal compound.

The present invention also provides an organic semiconductor transistor using a polymer formed by polymerizing the polymerizable liquid crystal compound.

Furthermore, this invention provides the charge transport body using the polymer formed by superposing | polymerizing the said polymeric liquid crystal compound.

In addition, the present invention provides a light-emitting body using a polymer formed by polymerizing the polymerizable liquid crystal compound.

The single polymer or copolymer, which is a polymer formed by polymerizing the polymerizable liquid crystal compound, has excellent properties such as heat resistance due to crosslinking, excellent charge mobility, high luminescence properties, low moisture permeability, high gas barrier property, and excellent dimensional stability against heat. Demonstrate functionality Therefore, a single polymer or copolymer which is a polymer prepared from the polymerizable liquid crystal composition of the present invention is useful as a material for an organic electro-optical device including an organic semiconductor device, an organic light emitting device, and the like.

The organic semiconductor polymer for OFET can be prepared by applying a polymerizable composition comprising Compound 1 to a substrate subjected to an appropriate alignment treatment by spin coating or bar coating, followed by curing. In order to prepare the polymer of the present invention to have the highest performance as an organic semiconductor for OFET, the polymerizable liquid crystal composition should be cured and fixed as soon as possible after being oriented on the liquid crystal phase. Therefore, it is preferable to use UV or electron beams.

The photocuring composition includes an initiator for photopolymerization, and examples of the photopolymerization initiator include 2,2'-dimethoxy-phenyl, acetophenone, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, benzyl dimethyl ketal, 2-methyl-1- [4- (methyl seed O) phenyl] -2-morpholinopropene-1,2,4-diethylxanthone (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2,4-diethylxanthone) and p-dimethylaminobenzoate mixture and the like can be used.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are merely to illustrate the present invention, but the content of the present invention is not limited to the following examples.

Example  One: Polymerizable  Preparation of Liquid Crystal Compound

6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-florene-2,7-diyl) bis (ethyne-2,1-diyl) bis (thiophene -5,2-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate (6,6 '-(4,4'-(5, 5 '-(9,9-Dimethyl-9H-fluorene-2,7-diyl) bis (ethyne-2,1-diyl) bis (thophene-5,2-diyl)) bis (4,1-phenylene) Synthesis of bis (oxy) bis (hexane-6,1-diyl) diacrylate

(1) Synthesis of 2,7-Dibromo-9,9-dimethyl-9H-Florene (2,7-dibromo-9,9-dimethyl-9H-fluorene)

500 mL of dimethyl sulfoxide solution containing 10 g (30 mmol) of 2,7-dibromofluorene, 9 g (80 mmol) of potassium tert-butoxide were cooled to 0 ° C. and 5.7 mL of methyliodide ( 91 mmol) was slowly added drop wise and then stirred at room temperature for 2 hours. After the reaction was completed, the reactant was added dropwise into excess distilled water, and the resulting solid was filtered, washed with water, and dried to obtain 9.7 g (92% yield) of the produced compound (see FIG. 1A).

H-NMR was used to identify compound (a):

1 H NMR (300 MHz, CDCl 3, δ) 7.52 (m, 4H), 7.46 (dd, 2H), 1.46 (s, 6H).

(2) 4,4 '-(9,9-dimethyl-9H-fluorene-2,7-diyl) bis (2-methyl-3-butyn) -2-ol (4,4'-(9, Synthesis of 9-dimethyl-9H-fluorene-2,7-diyl) bis (2-methylbut-3-yn) -2-ol)

5 g (1, 14.2 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene was dissolved in 500 mL of THF: TEA (v / v 1: 1) mixed solvent, followed by dichlorobis ( Triphenylphosphine) palladium (II) 0.5 g (0.7 mmol), triphenylphosphine 0.37 g (1.4 mmol), 3-methyl-1-butyn-3-ol 4.6 mL (46.9 mmol), copper iodide 0.3 g (1.4 mmol) was added sequentially, and the temperature was raised to 90 ° C. and stirred for 24 hours. After the reaction mixture was cooled to room temperature, the reaction solution was poured into excess water, extracted with dichloromethane, concentrated under reduced pressure, and separated by chromatography. Yield).

H-NMR was used to identify compound (b):

1 H NMR (300 MHz, CDCl 3 δ) 1.46 (s, 6H), 1.65 (s, 12H), 2.03 (s, 2H), 7.39 (d, J = 7.83 Hz, 2H), 7.48 (m, 2H), 7.61 ( d, J = 8.22 Hz, 2H).

(3) Synthesis of 2,7-diethynyl-9,9-dimethyl-9H-fluorene (2,7-diethynyl-9,9-dimethyl-9H-fluorene)

70 mL of 4,4 '-(9,9-dimethyl-9H-fluorene-2,7-diyl) bis (2-mail-3-butyn-2-ol) 2.5 g (2, 7.0 mmol) toluene After dissolving in water and cooling to 0 ° C., 4.7 g (122 mmol) of NaH dispersed in a 60% content in mineral oil was slowly added thereto, and the temperature was raised to room temperature. After heating to 70 ℃ and stirred for 5 hours to terminate the reaction. After the reaction mixture was cooled to room temperature, excess NaH activity was removed with methanol and water, extracted with methylene dichloride, concentrated, and separated by chromatography to obtain 1.6 g (94%) of the compound (see FIG. 1C). Yield).

H-NMR confirmed the compound (c):

1 H NMR (300 MHz, CDCl 3) δ 1.47 (s, 6H), 3.14 (s, 2H), 7.47 (d, J = 9.24 Hz, 2H), 7.55 (m, 2H), 7.64 (d, J = 7.83 Hz, 2H).

(4) Synthesis of 2- (4-methoxyphenyl) thiophene (2- (4-methoxyphenyl) thiophene)

3 mL (3, 30 mmol) of 2-bromothiophene was dissolved in 250 mL of 1,2-dimethoxyethane, 5.6 g (46 mmol) of 4-methoxyphenylboronic acid, tetrakis (triphenylphosphine) ) 1.6 g (0.9 mmol) and 9.7 g (92 mmol) of Na 2 CO 3 were added and the temperature was raised to about 100 ° C. and stirred for 24 hours. After completion of the reaction, excess water was added at room temperature, and the precipitate was filtered and washed with water to obtain 5.5 g (96% yield) of the compound (see (d) of FIG. 1).

H-NMR confirmed the compound (d):

1 H-NMR (300 MHz, CDCl 3 δ) 3.83 (s, 3H), 6.90 (d, J = 8.82 Hz, 2H), 7.03-7.06 (m, 1H), 7.19-7.22 (m, 2H), 7.52 (d, J = 8.85 Hz, 2H).

(5) Synthesis of 4- (thiophen-2-yl) phenol (4- (thiophen-2-yl) phenol)

5 g (4, 26.3 mmol) of 2- (4-methoxyphenyl) thiophene was dissolved in 300 mL of dichloromethane and cooled to 0 ° C. 53 mL (53 mmol) of 1.0 M BBr3 was added dropwise, followed by stirring at room temperature for 5 hours. The reaction mixture was diluted with water, extracted with dichloromethane, concentrated under reduced pressure, separated by chromatography, and then obtained 4 g (86% yield) of a compound (see FIG. 1E).

H-NMR was used to identify compound (e):

1 H-NMR (300 MHz, DMSO-d 6 δ) 6.79 (d, J = 4.44 Hz, 2H), 7.05-7.08 (m, 1H), 7.29-7.30 (m, 1H), 7.39-7.41 (m, 1H), 7.45 (d, J = 4.44 Hz, 2H), 9.63 (s, 1H).

(6) Synthesis of 6- (4- (thiophen-2-yl) phenoxy) hexan-1-ol (6- (4- (thiophen-2-yl) phenoxy) hexan-1-ol)

Dissolve 6.5 g (5, 37 mmol) of 4- (thiophen-2-yl) phenol in 500 mL DMF, add 7.2 mL (55 mmol) of 1-bromo-6-hexanol, and K2CO3 g. After the reaction was stirred for 24 hours. After cooling, the precipitate was added to excess water, and the precipitated precipitate was filtered and washed with water to obtain 10 g (98% yield) of the compound (see FIG. 1 (f)).

(7) 6- (4- (5-bromothiophen-2-yl) phenoxy) pexane-1-ol (6- (4- (5-bromothiophen-2-yl) phenoxy) hexan-1-ol) Synthesis of

10 g (6, 36 mmol) of 6- (4- (thiophen-2-yl) phenoxy) hexane-1-ol was dissolved, cooled to -78 ° C and 6.4 g (36 mmol of N-bromosuccinimide. ) Was added slowly and the mixture was raised to room temperature and stirred for about 1 hour. The reaction mixture was diluted with excess water, extracted with dichloromethane, concentrated under reduced pressure and separated by chromatography to obtain 7.1 g (56% yield) of the compound (see FIG. 1 (g)).

H-NMR was used to identify compound (g):

1 H-NMR (300 MHz, DMSO-d6 δ) 1.33-1.46 (m, 6H), 1.69? 1.73 (m, 2H), 3.42 (t, J = 6.1 Hz), 4.00 (t, J = 6.5 Hz, 4H), 4.37 (t, J = 5.1 Hz, 1H) 6.98 (d, J = 8.8 Hz, 2H ), 7.21 (m, 2H), 7.53 (d, J = 8.8 Hz, 2H).

(8) 6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-fluorene-2,7-diyl) bis (ethyne-2,1-diyl) bis (Thiophene-5,2-diyl)) bis (4,1-phenylene)) bis (oxy) dihexane-1-ol (6,6 '-(4,4'-(5,5 '-( 9,9-dimethyl-9H-fluorene-2,7-diyl) bis (ethyne-2,1-diyl) bis (thiophene-5,2-diyl)) bis (4,1-phenylene)) bis (oxy) Synthesis of dihexan-1-ol)

2.6 g (3, 10.6 mmol) of 2,7-diethinyl-9,9-dimethyl-9H-fluorene were dissolved in 500 mL of THF: TEA (v / v 1: 1) mixed solvent and dichlorobis ( Triphenylphosphine) palladium (II) 0.2 g (0.3 mmol), triphenylphosphine 0.2 g (0.6 mmol), (6- (4- (5-bromothiophen-2-yl) phenoxy) hexyloxy 11.3 g (7, 31.8 mmol) of hexane-1-ol and 0.1 g (0.6 mmol) of copper iodide were added sequentially, and the temperature was raised to 90 ° C. and stirred for 24 hours. The reaction mixture was cooled to room temperature and the reaction solution was poured into excess water and extracted with dichloromethane. After treatment with MgSO 4, concentration and separation by chromatography gave 2.3 g (28% yield) of the compound (see FIG. 1H).

(9) 6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-fluorene-2,7-diyl) bis (ethyne-2,1-diyl) bis (Thiophene-5,2-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate 6,6 '-(4,4'-( 5,5 '-(9,9-dimethyl-9H-fluorene-2,7-diyl) bis (ethyne-2,1-diyl) bis (thiophene-5,2-diyl)) bis (4,1-phenylene Synthesis of bis (oxy) bis (hexane-6,1-diyl) diacrylate

6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-florene-2,7-diyl) bis (ethyne-2,1-diyl) bis (thiophene 1.2 g (8, 1.5 mmol) of -5,2-diyl)) bis (4,1-phenylene)) bis (oxy) dihexane-1-ol was dissolved in 30 mL of dichloromethane and cooled to 0 ° C. 4.2 mL (30.3 mL) of triethylamine and 0.4 mL (5.3 mmol) of acyl oil chloride were added sequentially. Thereafter, the mixture was stirred at room temperature for about 3 hours to complete the reaction. The reaction mixture was diluted with excess water, extracted with dichloromethane, treated with MgSO 4, concentrated and separated by column chromatography to obtain 0.8 g (60% yield) of the compound (see FIG. 1 (i)).

H-NMR confirmed the compound (i):

1 H NMR (300 MHz, CDCl 3) δ 1.42-1.51 (m, 8H), 1.68? 1.86 (m, 8H), 3.97 (t, J = 6.42 Hz, 4H), 4.16 (t, J = 6.66 Hz, 4H), 5.80-5.84 (m, 2H), 6.08-6.17 (m, 2H), 6.37 -6.44 (m, 2H), 6.90-6.92 (m, 4H), 7.10-7.11 (m, 2H), 7.23-7.24 (m, 4H) 7.50-7.53 (m, 6H), 7.59 (m, 2H), 7.67-7.70 (m, 2 H).

Example  2: Polymerizable  Liquid crystal composition preparation and Film

3 wt% of the polymerizable liquid crystal compound of Example 1- (9) (see FIG. 1 (i)) was dissolved in a mixed solvent prepared by mixing cyclohexanone and chloroform at 8: 2, and 2,2 'was used as a photocuring agent. 3 wt% of the dimethoxy-phenyl acetophenone and the benzophenone (1: 1) mixture was added to compound 1- (9) to prepare a polymerizable liquid crystal composition.

The polymerizable liquid crystal composition was applied to an ITO glass substrate (2 × 2) using a spin coater in order of 5 seconds at 500 rpm, 3 seconds at 1000 rpm, 2 seconds at 1500 rpm, 30 seconds at 3300 rpm, and 2 seconds at 1500 rpm. After applying for 3 seconds at 1000 rpm at a speed of 500 rpm for 5 seconds, the plate was prebaked at 90 ° C. for 10 minutes, and cured by irradiating UV at 90 ° C. using Black-lay UV. After maintaining the vacuum oven for 90 minutes at 90 ℃ to remove the residual solvent to prepare a polymer film to a thickness of 100 nm.

UV irradiation energy used is summarized in Table 1.

Example
Prebaking
(10 minutes, 90 ° C) UV dosage
(365 nm) Post Baking
(40 minutes, vacuum, 90 ° C) Film thickness
(Nm) Film weight
(Μg) 2-1 ○

1 J ○

100
90 2-2
○

2 J ○
100
90 2-3
○

3 J ○
100
90

Experimental Example  One: Polymerizable  Analysis of Liquid Crystal Compounds

The compound of Example 1- (9) was measured by Differential Scanning Calorimeter (DSC) and Polarized Optical Microscopes (POM) and found to be C 0 ° C <N 205 ° C I (FIGS. 2 and 3). Reference).

C is a melting point, N is a nematic phase, I is an isotropic liquid transition temperature and the unit of temperature is ° C.

Therefore, since the present compound is a nematic liquid crystal phase at room temperature and exhibits a nematic liquid crystal phase at a wide temperature range of 200 ° C. or higher, it is possible to produce a polymerizable liquid crystal composition having a liquid crystal phase temperature range of 200 ° C. or higher alone. Moreover, it has the characteristic useful as a polymerizable liquid crystal composition component which is easy to mix with another reactive or non-reactive liquid crystal compound, and the polymerization processability whose liquid crystal phase temperature was controlled.

Example 1- (9) Oxidation stability of the compound was measured using cyclic voltammetry. The results are shown in FIG. 4. As shown in FIG. 4, the ionization potential (HOMO) calculated as -5.4 eV is used to prepare a polymerizable liquid crystal composition for polymer organic semiconductors for channels of organic field effect transistors using the present compound.

Experimental Example  2: Polymerizable  Analysis of the degree of cure of the polymer film containing a liquid crystal compound 1

The degree of cure of the polymer film including the liquid crystal compound prepared in Example 2 was measured. Measurement by FT-IR showed a degree of cure of 76% (see Fig. 5). In order to measure the film hardness, the UV irradiation amount was further irradiated with 0.5 J and 1.5 J in addition to Example 2, and measured by the JIS standard JIS-K-5400 8.4 pencil scratch test method, and the pencil hardness was 4H or more (see FIG. 6). ).

From this, the polymer film prepared from the polymerizable liquid crystal composition of the present invention can be confirmed that the coated polymerizable liquid crystal compound forms a very solid polymer network by crosslinking by UV photocuring.

Experimental Example  3: Polymerizable  Curing Degree and Luminescent Properties of Polymer Film Containing Liquid Crystal Compound

(1) Extraction-HPLC method of polymer film containing liquid crystal compound (2) GAL analysis to measure MALDI-TOF MS (3) polymer molecular weight which detects by desorption of monomer by irradiating high energy such as laser to thin film The results of monomer, oligomer and polymer analysis using the method are shown in Table 2. For control, additional experiments were performed by spin coating and prebaking only without UV irradiation and postbaking.

Example HPLC
-
UV
Quantitative Results (a)
(%) MALDI
-TOF-
MS
Detection result GPC
(DMF @ 80 ℃)
Detection result Control group 100 Detected None 2-1 To 0 Not detected Not detected 2-2 To 0 Not detected Not detected 2-3 To 0 Not detected Not detected (a) 0J analysis results are considered 100%

After the UV curing, the monomer residue was analyzed by HPLC-UV method. As a result, when the monomer was set to 100 before curing, a trace amount of monomer was detected at the level of several tens of ppm. In addition, MALDI-TOF-MS also confirmed that almost no unreacted monomers, DMF solution was analyzed by GPC, there was no polymer detected.

On the other hand, in order to test the solvent resistance to DMF, a 100 nm thick polymer film coated ITO substrate was immersed in 1 mL of DMF solution and tested for solubility at 80 ° C.

From this, the polymer film prepared from the polymerizable liquid crystal composition of the present invention can be confirmed that the coated polymerizable liquid crystal compound forms a very solid polymer network by crosslinking by UV photocuring. This has strong mechanical strength and solvent resistance to process solvents, which are essential conditions for the application of a polymer organic semiconductor for an organic field effect transistor or a polymer light emitting layer for an organic light emitting device.

In addition, the photoluminescence spectrophotometer of the polymer film prepared from the polymerizable liquid crystal composition showed a useful property as an orange light emitter (580 nm) as shown in FIG. 7 (see FIG. 7).

Claims (8)

A novel polymerizable liquid crystal compound characterized in that 2,7-diethynyl-fluorene is introduced at the center of the molecule:
&Lt; Formula 1 >

Wherein R ₁ and R ₂ are each hydrogen, fluorine or straight or branched alkyl having 1 to 4 carbon atoms;
P ₁ and P ₂ are each one selected from the group of the following polymerizable reactors;

L ₁ and L ₂ are each-{O- (CH ₂ ) m}-,-{O- (CH ₂ ) m-CO}-,-{COO- (CH ₂ ) m-}-or-{COO- (CH ₂ ) m-CO}-;
M is an integer from 1 to 20;
One or two or more of the m — (CH ₂ ) — — (CH ₂ ) — may be substituted with —O—, —S—, —CF ₂ —;
X ₁ , X ₂ , X ₃ and X ₄ are each one selected from the following aromatic substituent groups;

R ₃ , R ₄ , R ₅ and R ₆ are each hydrogen, halogen, cyano, nitro, C ₁ -C ₁₂ straight or branched chain alkyl or C ₃ -C ₇ cycloalkyl group;
When the R ₃ , R ₄ , R ₅ or R ₆ is an alkyl group of C ₁ -C ₁₂ , C ₃ -C _7, the alkyl group may be unsubstituted or substituted with halogen or cyano group;
One or more —CH ₂ — groups in the alkali group may be substituted with —O ?,? S ?, or? CF ₂ ?.
The method of claim 1, wherein the polymerizable liquid crystal compound is 6,6 '-(4,4'-(5,5 '-(9,9-dimethyl-9H-fluorene-2,7-diyl) ) Bis (ethyn-2,1-diyl) bis (thiophen-5,2-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate The novel polymerizable liquid crystal compound, characterized in that:
(2)

. A polymerizable liquid crystal compound composition comprising at least one polymerizable liquid crystal compound according to claim 1.
A polymer formed by polymerizing the polymerizable liquid crystal compound of claim 1.

Dealkylating the 9-position of 2,7-dibromofluorene (step 1);
Introducing an acetylene group by coupling a compound prepared in Step 1 with end-alkaine and Sonogashira (Step 2);
Removing the protecting group using NaH from the compound produced in step 2 (step 3);
Sonogashira coupling reaction of the compound produced in step 3 with a mixture of the following compound A and compound A '(step 4); And
Method for producing a polymerizable liquid crystal compound comprising the step (step 5) of reacting the compound produced in step 4 with the following compound B in the presence of a tertiary amine base.

Compound A is Hal ₁ -X ₁ -X ₃ -L ₁ -OH;
Compound A 'is Hal ₂ -X ₂ -X ₄ -L ₂ -OH;
Hal ₁ and Hal ₂ are each independently selected from the group of halogen elements;
L ₁ and L ₂ are each independently-{O- (CH ₂ ) m}-,-{O- (CH ₂ ) m-CO}-,-{COO- (CH ₂ ) m-}-or- {COO- (CH ₂ ) m-CO}-;
M is an integer from 1 to 20;
One or two or more -CH ₂ -in the m —CH ₂ — groups may be substituted with —O—, —S—, —CF ₂ —;
X ₁ to X ₄ are each independently one selected from the following aromatic substituent group;

R ₃ , R ₄ , R ₅ and R ₆ are each hydrogen, halogen, cyano, nitro, C ₁ -C ₁₂ straight or branched chain alkyl or C ₃ -C ₇ cycloalkyl group;
When the R ₃ , R ₄ , R ₅ or R ₆ is an alkyl group of C ₁ -C ₁₂ , C ₃ -C _7, the alkyl group may be unsubstituted or substituted with halogen or cyano group;
At least one CH ₂ ? Group in the alkali group may be substituted with? O?,? S?,? CF ₂ ?
The compound B is any one compound selected from the group of the following compounds substituted with halogen;

.
An organic semiconductor transistor using a polymer formed by polymerizing the polymerizable liquid crystal compound of claim 1.
A charge transporter using a polymer formed by polymerizing the polymerizable liquid crystal compound of claim 1.
A light emitter using a polymer formed by polymerizing the polymerizable liquid crystal compound of claim 1.

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