KR101260235B1 - Acethylene containing reactive mesogens based on triphenylene core - Google Patents
Acethylene containing reactive mesogens based on triphenylene core Download PDFInfo
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Abstract
본 발명은 액정표시장치의 보상필름용 액정화합물로, 보다 상세하게는 아세틸렌을 포함하는 트리페닐렌계 반응성 메조겐 화합물에 관한 것이다. 본 발명에서 제조한 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물은 복굴절율이 높아 보상필름을 박막으로 제조할 수 있으며 이 보상필름을 채용한 액정장치는 대화면의 광시야각을 구현할 수 있는 장점이 있다. The present invention relates to a liquid crystal compound for a compensation film of a liquid crystal display device, and more particularly, to a triphenylene-based reactive mesogen compound containing acetylene. The acetylene-containing triphenylene-based reactive mesogen compound prepared in the present invention has a high birefringence so that a compensation film can be manufactured in a thin film, and the liquid crystal device employing the compensation film has the advantage of realizing a wide viewing angle of a large screen.
Description
본 발명은 자외선(UV) 조사에 의한 광가교 반응을 통해 필름 형성이 가능한 광반응성기를 함유하고 고복굴절을 위한 아세틸렌을 함유하는 원반상 메조겐(mesogen) 화합물 및 이의 제조방법에 관한 것이다.The present invention relates to a disk-shaped mesogen compound containing a photoreactive group capable of film formation through photocrosslinking reaction by ultraviolet (UV) irradiation and containing acetylene for high birefringence, and a method for preparing the same.
고도의 디지털화, 정보화가 가속화 되면서 많은 IT 기기들이 생활속에서 이용되고 있으며 그를 위한 디스플레이 기술도 많은 발전을 하고 있다. 과거 사용되었던 전자 디스플레이중 가장 대표적인 것은 TV나 컴퓨터 모니터 등에 사용되었던 CRT(cathod ray tube)모니터 이다. 그러나 CRT 모니터는 부피가 크고 중량이 무겁기 때문에 대형화와 휴대화에 어려움이 있고 소비전력이 높으며, 높은 구동전압으로 점차 다른 평판 디스플레이가 그 자리를 대체하고 있다. CRT의 한계를 극복하기 위한 평판 디스플레이로는 LCD, PDP, OLED등이 대표적이며, 이중 현재 가장 보편적인 것이 LCD이다. 액정과 반도체 기술이 접목된 LCD는 얇고 가벼우며 소비전력이 낮은 장점으로 인해 현재 대형 TV, PC 모니터, 각종 측정장치의 표시소자, PMP나 mp3기기, 자동차의 네비게이션 장치, 휴대폰 등에 널리 응용되고 있다. 고품질의 대형 LCD를 구현하기 위해서는 광시야각, 고휘도, 높은 컨트라스트비, 빠른 응답속도가 요구된다.As digitalization and informatization are accelerated, many IT devices are used in daily life, and display technology for them is also developing. The most representative electronic display used in the past is the CRT (cathod ray tube) monitor used in TVs and computer monitors. However, because CRT monitors are bulky and heavy, they are difficult to enlarge and carry, high power consumption, and high driving voltages are gradually replacing other flat panel displays. Representative flat panel displays such as LCD, PDP, and OLED to overcome the limitations of CRT are the most common of these. LCD, which combines liquid crystal and semiconductor technology, is widely applied to large TVs, PC monitors, display devices of various measuring devices, PMP or mp3 devices, car navigation devices, mobile phones, etc. due to its thin, light and low power consumption. To realize high quality large LCD, wide viewing angle, high brightness, high contrast ratio and fast response speed are required.
현재 알려져 있는 LCD 동작 모드 중 실용화 되어 널리 사용되고 있는 것은 TN (twisted nematic), STN (super twisted nematic), VA (Vertical alignment) 그리고 IPS (Inplane switching)이다. 이러한 LCD에서 사용되는 막대형 액정분자는 고분자 배향막 위에 한쪽 방향으로 배향되게 되고 이러한 배향은 각각의 LCD에서 시야각에 따른 액정의 겉보기 Δnd의 변화를 일으켜 LCD에서의 광 시야각을 제한하는 원인이 된다. 전기장의 인가에 의해 액정분자의 배열이 변화하는 경우 진행하는 빛은 다른 각도로 액정분자와 만나게 되고 이에 따라 투과되는 빛의 편광 상태에 차이가 발생하게 된다. 그 결과 투과된 빛이 LCD 표면의 편광판을 통과할 경우 일부의 빛이 누출된다. 이 경우 정면에서와 경사각에서 휘도의 차이가 나거나 콘트라스트의 역전이 일어난다. 이러한 현상을 극복하고 광시야각을 확보하려는 다양한 시도가 있었다. 이러한 시도 중 현재는 보상필름을 이용하는 방법이 비교적 널리 사용되어지고 있다. 보상 필름은 시야각의 증가에 따른 위상차의 변화값을 가지면서 방향이 반대인 필름을 사용하여 보상하는 원리이다. 현재 TN 모드의 LCD에 사용되고 있는 광시야각용 보상 필름은 음의 복굴절율을 갖는 원반상 반응성 액정을 포함하는 혼합물을 필름화한 것으로 상용화되고 있으나 복굴절율값이 낮고 필름의 두께가 두꺼운 단점이 있다.Among the currently known LCD operating modes, TN (twisted nematic), STN (super twisted nematic), VA (Vertical alignment) and IPS (Inplane switching) are widely used. The rod-shaped liquid crystal molecules used in such LCDs are oriented in one direction on the polymer alignment layer, and this orientation causes a change in the apparent Δnd of the liquid crystals with respect to the viewing angle in each LCD, thereby limiting the optical viewing angle in the LCD. When the arrangement of liquid crystal molecules is changed by the application of an electric field, the traveling light meets the liquid crystal molecules at different angles, thereby causing a difference in the polarization state of the transmitted light. As a result, some of the light leaks when the transmitted light passes through the polarizer on the LCD surface. In this case, there is a difference in luminance or an inversion of contrast at the inclination angle from the front. There have been various attempts to overcome this phenomenon and to secure wide viewing angles. Currently, a method using a compensation film is relatively widely used. Compensation film is a principle of compensating using a film having an opposite direction while having a change value of a phase difference with increasing viewing angle. Compensation films for wide viewing angles, which are currently used in LCDs in TN mode, have been commercialized as film-forming mixtures containing discotic reactive liquid crystals having negative birefringence, but have a low birefringence value and a thick film.
이러한 현재의 문제점을 극복하고 고효율의 초박막 보상필름을 구현하기 위해선 높은 복굴절을 갖는 반응성 액정 화합물이 절실히 요구된다. In order to overcome such current problems and to implement a highly efficient ultra thin film compensation film, a reactive liquid crystal compound having a high birefringence is urgently needed.
본 발명은 대화면 광시야각 액정 표시장치에 핵심 소재인 보상필름을 제작할 수 있는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 제공하며 상기 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 포함하여 제조되는 보상필름을 제공한다. The present invention provides an acetylene-containing triphenylene-based reactive mesogen compound capable of producing a compensation film, which is a core material, for a large-screen wide viewing angle liquid crystal display, and provides a compensation film prepared by including the acetylene-containing triphenylene-based reactive mesogen compound. do.
또한, 상기 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 이용하여 제조된 보상필름을 구비하는 전자기기, 특히 액정표시장치를 제공한다.In addition, the present invention provides an electronic device, particularly a liquid crystal display device having a compensation film manufactured using the acetylene-containing triphenylene-based reactive mesogen compound.
본 발명은 광가교에 의해 필름형성이 가능한 광반응성기를 갖고 고복굴절율을 위한 아세틸렌을 포함하는 하기 화학식 1의 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 제공한다.The present invention provides an acetylene-containing triphenylene-based reactive mesogen compound of the general formula (1) having a photoreactive group capable of film formation by photocrosslinking and including acetylene for high birefringence.
[화학식 1][Formula 1]
[상기 화학식 1에서, [In
X 는 O, NH, S중에서 선택되는 어느 하나이며,X Is any one selected from O, NH, S,
L 은 R, C(=O)R, C(=O)ArOR 및 -C(=O)ArNHR 로부터 선택되며, L is selected from R, C (= O) R, C (= O) ArOR, and -C (= O) ArNHR,
Y 는 CH2, Ar, ArO, ArS, ArNH, C(=O), C(=O)O, C(=O)NH, C(=O)Ar, C(=O)ArO, C(=O)ArS, C(=O)ArNH, ArC(=O), ArC(=O)O, ArC(=O)S, ArC(=O)NH로부터 선택되며, Y is CH 2 , Ar, ArO, ArS, ArNH, C (= 0), C (= 0) O, C (= 0) NH, C (= 0) Ar, C (= 0) ArO, C (= O) ArS, C (= 0) ArNH, ArC (= 0), ArC (= 0) O, ArC (= 0) S, ArC (= 0) NH,
Z는 
A는 -R′, C(=O)R′, -R′-Z로부터 선택되는 어느 하나이며, 상기 R은 C1C20 알킬렌이고, Ar는 C6C30 아릴렌이며, R′은 C1C20 알킬이다.]A is any one selected from -R ', C (= O) R', -R'-Z, R is C 1 C 20 alkylene, Ar is C 6 C 30 arylene, and R 'is C 1 C 20 alkyl.]
바람직하게는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물은 하기 화학식 2 또는 화학식 3으로 표시되는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물로 예시될 수 있다.Preferably, the acetylene-containing triphenylene-based reactive mesogen compound may be exemplified by the acetylene-containing triphenylene-based reactive mesogen compound represented by the following formula (2) or (3).
[화학식 2][Formula 2]
[화학식 3](3)
[상기 화학식 2 또는 화학식 3에 있어서, X, Y, L, Z, A의 정의는 상기 화학식 1과 동일하다.][In Formula 2 or Formula 3, the definitions of X, Y, L, Z, and A are the same as in
보다 바람직하게는 상기 R은 직쇄 또는 분지쇄의 C1C12 알킬렌기이고, Ar는 페닐렌, 나프틸렌, 안트라세닐렌, 벤조피레닐렌, 피레닐렌, 페난트릴렌 또는 플루오레닐렌인 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물로 예시될 수 있으나, 이것은 본 반응의 화합물을 제한하는 것은 아니다.More preferably, R is C 1 C 12 of a straight or branched chain An alkylene group, and Ar may be exemplified by an acetylene-containing triphenylene-based reactive mesogen compound which is phenylene, naphthylene, anthracenylene, benzopyrenylene, pyrenylene, phenanthrylene or fluorenylene, It does not limit the compound.
또한 본 발명은 화학식 1로 표시되는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 포함하는 액정 조성물을 포함하며 상기 액정 조성물을 포함하는 보상필름을 제공한다.In another aspect, the present invention provides a compensation film comprising a liquid crystal composition comprising an acetylene-containing triphenylene-based reactive mesogen compound represented by the formula (1).
또한 상기 보상필름을 구비한 액정표시장치를 제공한다.The present invention also provides a liquid crystal display device having the compensation film.
본 발명은 고복굴절율을 위한 아세틸렌과 액정상 온도 조절을 위한 곁가지를 도입하여 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 제공한다. The present invention provides an acetylene-containing triphenylene-based reactive mesogen compound by introducing acetylene for high birefringence and side branches for liquid crystal phase temperature control.
또한, 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 포함하여 제조되는 보상필름으로부터 이를 구비하는 전자기기, 특히 액정표시장치에 효과적으로 사용될 것으로 기대된다.In addition, it is expected to be effectively used in electronic devices including the acetylene-containing triphenylene-based reactive mesogen compound, particularly in electronic devices having the same.
도 1은 실시예 2를 통해 제조한 아세틸렌을 포함하는 트리페닐렌계 반응성 메조겐 화합물의 편광 광학현미경 사진이다.
도 2는 실시예 2를 통해 제조한 아세틸렌을 포함하는 트리페닐렌계 반응성 메조겐 화합물을 배향막 위에서 배향시킨 후 필름화 한 후 관찰한 편광 광학현미경 사진이다.
도 3은 제조예 3의 광경화에 의해 제조된 필름의 복굴절율 측정 장치(PEM) 및 필름 두께에 따른 측정된 복굴절율값을 나타낸 것이다.1 is a polarized light micrograph of a triphenylene-based reactive mesogen compound including acetylene prepared in Example 2.
FIG. 2 is a polarization optical microscope photograph observed after aligning a triphenylene-based reactive mesogen compound including acetylene prepared in Example 2 on an alignment layer and film formation.
Figure 3 shows the measured birefringence value according to the birefringence measuring device (PEM) and the film thickness of the film produced by the photocuring of Preparation Example 3.
본 발명은 액정 표시장치의 핵심 소재인 보상필름을 제작할 수 있는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 제공한다. The present invention provides an acetylene-containing triphenylene-based reactive mesogen compound capable of producing a compensation film, which is a core material of a liquid crystal display.
본 발명의 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물은 트리페닐렌을 중심으로 고복굴절율을 위한 아세틸렌을 포함하고 화합물의 곁가지 말단에 광반응에 의해 가교될 수 있는 아크릴로일기, 메타아크릴로일기, 페닐아크릴로일기(신나모일기) 또는 퓨릴아크릴로일기가 도입되었다. The acetylene-containing triphenylene-based reactive mesogen compound of the present invention comprises acetylene for high birefringence around triphenylene and can be crosslinked by photoreaction at the side branch terminal of the compound, acryloyl group, methacryloyl group, phenyl Acryloyl group (cinnamoyl group) or furyl acryloyl group was introduced.
본 발명의 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물은 하기 화학식 1로 표시되는 것을 특징으로 한다. The acetylene-containing triphenylene-based reactive mesogen compound of the present invention is characterized by the following formula (1).
[화학식 1][Formula 1]
[상기 화학식 1에서, [In
X 는 O, NH, S중에서 선택되는 어느 하나이며,X Is any one selected from O, NH, S,
L 은 R, C(=O)R, C(=O)ArOR 및 -C(=O)ArNHR 로부터 선택되며, L is selected from R, C (= O) R, C (= O) ArOR, and -C (= O) ArNHR,
Y 는 CH2, Ar, ArO, ArS, ArNH, C(=O), Y is CH 2 , Ar, ArO, ArS, ArNH, C (= O),
C(=O)O, C(=O)NH, C(=O)Ar, C(=O)ArO, C (= O) O, C (= O) NH, C (= O) Ar, C (= O) ArO,
C(=O)ArS, C(=O)ArNH, ArC(=O), ArC(=O)O, ArC(=O)S, ArC(=O)NH로부터 선택되며, C (= O) ArS, C (= O) ArNH, ArC (= O) , ArC (= O) O, ArC (= O) S, ArC (= O) NH
Z는 
A는 -R′, C(=O)R′, -R′-Z로부터 선택되는 어느 하나이며, 상기 R은 C1C20 알킬렌이고, Ar는 C6C30 아릴렌이며, R′은 C1C20 알킬이다.]A is any one selected from -R ', C (= O) R', -R'-Z, R is C 1 C 20 alkylene, Ar is C 6 C 30 arylene, and R 'is C 1 C 20 alkyl.]
바람직하게는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물은 하기 화학식 2 또는 화학식 3으로 표시되는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물로 예시될 수 있다.Preferably, the acetylene-containing triphenylene-based reactive mesogen compound may be exemplified by the acetylene-containing triphenylene-based reactive mesogen compound represented by the following formula (2) or (3).
[화학식 2][Formula 2]
[화학식 3](3)
[상기 화학식 2 또는 화학식 3에 있어서, X, Y, L, Z, A의 정의는 상기 화학식 1과 동일하다.][In Formula 2 or Formula 3, the definitions of X, Y, L, Z, and A are the same as in
보다 바람직하게는 상기 R은 직쇄 또는 분지쇄의 C1C12 알킬렌기이고, Ar는 페닐렌, 나프틸렌, 안트라세닐렌, 벤조피레닐렌, 피레닐렌, 페난트릴렌 또는 플루오레닐렌인 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물로 예시될 수 있으나, 이것은 본 반응의 화합물을 제한하는 것은 아니다.More preferably, R is C 1 C 12 of a straight or branched chain An alkylene group, and Ar may be exemplified by an acetylene-containing triphenylene-based reactive mesogen compound which is phenylene, naphthylene, anthracenylene, benzopyrenylene, pyrenylene, phenanthrylene or fluorenylene, It does not limit the compound.
본 발명은 상기 화학식 1로 표시되는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 포함하는 액정 조성물을 제공하며 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 포함하는 액정 조성물은 특별히 한정이 있는 것은 아니나 액정표시 장치의 보상필름, IPS를 포함한 각종 모드에서 액정 매질, 액정형 유기반도체 재료층 등으로 유용하게 사용되어 질 수 있다.The present invention provides a liquid crystal composition comprising an acetylene-containing triphenylene-based reactive mesogen compound represented by Formula 1, and the liquid crystal composition comprising an acetylene-containing triphenylene-based reactive mesogen compound is not particularly limited, but a liquid crystal display device It can be usefully used as a liquid crystal medium, a liquid crystal organic semiconductor material layer, etc. in various modes including a compensation film, IPS.
또한 본 발명은 상기 액정 조성물을 포함하는 보상필름을 제공하며 이러한 보상필름은 복굴절율이 높아 이를 구비한 액정표시장치는 대화면의 광시야각을 구현할 수 있는 장점이 있다. In addition, the present invention provides a compensation film including the liquid crystal composition, and the compensation film has a high birefringence and the liquid crystal display device having the same has an advantage of realizing a wide viewing angle of a large screen.
본 발명의 상기 화학식 1의 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물은 하기 반응식 1~221에 기재된 반응에 의해 제조할 수 있다.The acetylene-containing triphenylene-based reactive mesogen compound of Chemical Formula 1 of the present invention can be produced by the reactions described in
[반응식1][Scheme 1]
[반응식2][Scheme 2]
[반응식3][Reaction Scheme 3]
[반응식4] [Reaction Scheme 4]
[반응식5][Scheme 5]
[반응식6]Scheme 6
[반응식7]Scheme 7
상기 반응식 1~7을 통해 대칭형의 트리할로겐트리페닐렌트리올을 제조할 수 있다.Through the
[반응식8]Scheme 8
[반응식9]Scheme 9
[반응식10][Reaction Scheme 10]
[반응식11][Reaction Scheme 11]
[반응식12][Reaction Scheme 12]
[반응식13][Reaction Scheme 13]
상기 반응식 8~13을 통해 비대칭형의 트리할로겐트리페닐렌트리올을 제조할 수 있다.Through the schemes 8 to 13 can be prepared an asymmetric trihalogentriphenylene triol.
[반응식14]Scheme 14
[반응식15]Scheme 15
[반응식16]Scheme 16
[반응식17]Scheme 17
[반응식18]Scheme 18
[반응식19]Scheme 19
[반응식20]Scheme 20
[반응식21]Scheme 21
[반응식22]Scheme 22
[반응식23]Scheme 23
[반응식24]Scheme 24
[반응식25]Scheme 25
[반응식26]Scheme 26
[반응식27]Scheme 27
[반응식 28][Reaction Scheme 28]
[반응식 29][Reaction Scheme 29]
[반응식 30][Reaction Scheme 30]
[반응식 31][Reaction Scheme 31]
[반응식 32][Reaction Scheme 32]
[반응식 33][Reaction Scheme 33]
[반응식 34][Reaction Scheme 34]
[반응식 35][Reaction Scheme 35]
[반응식 36][Reaction Scheme 36]
[반응식 37][Reaction Scheme 37]
[반응식 38][Reaction Scheme 38]
[반응식 39][Reaction Scheme 39]
[반응식 40][Reaction Scheme 40]
[반응식 41][Reaction Scheme 41]
[반응식 42][Reaction Scheme 42]
[반응식 43][Reaction Scheme 43]
[반응식 44][Reaction Scheme 44]
[반응식 45][Reaction Scheme 45]
[반응식 46][Reaction Scheme 46]
[반응식 47][Reaction Scheme 47]
[반응식 48][Reaction Scheme 48]
[반응식 49][Reaction Scheme 49]
[반응식 50][Reaction Scheme 50]
[반응식 51][Reaction Scheme 51]
[반응식 52][Reaction Scheme 52]
[반응식 53][Reaction Scheme 53]
[반응식 54][Reaction Scheme 54]
[반응식 55][Reaction Scheme 55]
[반응식 56][Reaction Scheme 56]
[반응식 57][Reaction Scheme 57]
[반응식 58][Reaction Scheme 58]
[반응식 59][Reaction Scheme 59]
[반응식 60][Reaction Scheme 60]
[반응식 61]Scheme 61
[반응식 62][Reaction Scheme 62]
[반응식 63][Reaction Scheme 63]
[반응식 64][Reaction Scheme 64]
[반응식 65][Reaction Scheme 65]
[반응식 66][Reaction Scheme 66]
[반응식 67][Reaction Scheme 67]
[반응식 68][Reaction Scheme 68]
[반응식 69][Reaction Scheme 69]
[반응식 70][Reaction Scheme 70]
[반응식 71][Reaction Scheme 71]
[반응식 72][Reaction Scheme 72]
[반응식 73][Reaction Scheme 73]
[반응식 74][Reaction Scheme 74]
[반응식 75][Reaction Scheme 75]
[반응식 76][Reaction Scheme 76]
[반응식 77][Reaction Scheme 77]
[반응식 78][Reaction Scheme 78]
[반응식 79][Reaction Scheme 79]
[반응식 80][Reaction Scheme 80]
[반응식 81][Reaction Scheme 81]
[반응식 82][Reaction Scheme 82]
[반응식 83][Reaction Scheme 83]
[반응식 84][Reaction Scheme 84]
[반응식 85][Reaction Scheme 85]
[반응식 86][Reaction Scheme 86]
[반응식 87]Scheme 87
[반응식 88]Scheme 88
[반응식 89]Scheme 89
[반응식 90]
[반응식 91]Scheme 91
[반응식 92]Scheme 92
[반응식 93]Scheme 93
[반응식 94]Scheme 94
[반응식 95]Scheme 95
[반응식 96]Scheme 96
[반응식 97]Scheme 97
[반응식 98]Scheme 98
[반응식 99]Scheme 99
[반응식 100]
[반응식 101]Scheme 101
[반응식 102]Scheme 102
[반응식 103]Scheme 103
[반응식 104]Scheme 104
[반응식 105]Scheme 105
[반응식 106]Scheme 106
[반응식 107]Scheme 107
[반응식 108]Scheme 108
[반응식 109]Scheme 109
[반응식 110]Scheme 110
[반응식 111]Scheme 111
[반응식 112]Scheme 112
상기 반응식 25~112를 통해 고복굴절율 원반상 메조겐을 위한 아세틸렌 포함 곁가지를 제조할 수 있다.The acetylene-containing side branches for the high birefringence disc-shaped mesogen can be prepared through the reaction schemes 25 to 112.
[반응식 113] Scheme 113
[반응식 114] Scheme 114
[반응식 115]Scheme 115
[반응식 116]Scheme 116
[반응식 117]Scheme 117
[반응식 118]Scheme 118
[반응식 119]Scheme 119
[반응식 120]Scheme 120
[반응식 121]Scheme 121
[반응식 122]Scheme 122
[반응식 123]Scheme 123
[반응식 124]Scheme 124
[반응식 125]Scheme 125
[반응식 126]Scheme 126
[반응식 127]Scheme 127
[반응식 128]Scheme 128
[반응식 129]Scheme 129
[반응식 130]Scheme 130
[반응식 131]Scheme 131
[반응식132]Scheme 132
[반응식133]Scheme 133
[반응식134]Scheme 134
[반응식135]Scheme 135
[반응식 136]Scheme 136
[반응식 137]Scheme 137
[반응식 138]Scheme 138
[반응식 139]Scheme 139
[반응식 140]Scheme 140
[반응식 141]Scheme 141
[반응식 142]Scheme 142
[반응식 143]Scheme 143
[반응식 144]Scheme 144
[반응식145]Scheme 145
[반응식146]Scheme 146
[반응식147]Scheme 147
[반응식148]Scheme 148
[반응식149]
[반응식 150]
[반응식 151]Scheme 151
[반응식 152]Scheme 152
[반응식 153]Scheme 153
[반응식 154]Scheme 154
[반응식 155]Scheme 155
[반응식 156]Scheme 156
[반응식 157]Scheme 157
[반응식 158]Scheme 158
[반응식 159]Scheme 159
[반응식 160]Scheme 160
[반응식 161]Scheme 161
[반응식 162]Scheme 162
[반응식 163]Scheme 163
[반응식 164]Scheme 164
[반응식 165]Scheme 165
[반응식 166] Scheme 166
[반응식 167]Scheme 167
[반응식 168]Scheme 168
[반응식 169]Scheme 169
[반응식 170]Scheme 170
[반응식 171]Scheme 171
[반응식 172]Scheme 172
[반응식 173]Scheme 173
[반응식 174]Scheme 174
[반응식 175]Scheme 175
[반응식 176]Scheme 176
[반응식 177]Scheme 177
[반응식 178]Scheme 178
[반응식 179]Scheme 179
[반응식 180]Scheme 180
[반응식 181]Scheme 181
[반응식 182]Scheme 182
[반응식 183]Scheme 183
[반응식 184]Scheme 184
[반응식 185]Scheme 185
[반응식 186]Scheme 186
[반응식 187]Scheme 187
[반응식 188]Scheme 188
[반응식 189]Scheme 189
[반응식 190]Scheme 190
[반응식 191]Scheme 191
[반응식 192]Scheme 192
[반응식 193]Scheme 193
[반응식 194]Scheme 194
[반응식 195]Scheme 195
[반응식 196]Scheme 196
[반응식 197]Scheme 197
[반응식 198] Scheme 198
[반응식 199]Scheme 199
[반응식 200]
[반응식 201]Scheme 201
[반응식 202]Scheme 202
[반응식 203]Scheme 203
[반응식 204]Scheme 204
[반응식 205]Scheme 205
[반응식 206] Scheme 206
[반응식 207]Scheme 207
[반응식 208]Scheme 208
[반응식 209]Scheme 209
[반응식 210]Scheme 210
[반응식 211]Scheme 211
[반응식 212]Scheme 212
[반응식 213]Scheme 213
[반응식 214] Scheme 214
[반응식 215]Scheme 215
[반응식 216]Scheme 216
[반응식 217]Scheme 217
[반응식 218]Scheme 218
[반응식 219]Scheme 219
[반응식 220]Scheme 220
[반응식 221]Scheme 221
상기 반응식 113~221을 통해 대칭형 혹은 비대칭형의 아세틸렌기가 포함된 광가교 가능한 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 제조할 수 있다.Through reaction schemes 113 to 221, a photocrosslinkable acetylene-containing triphenylene-based reactive mesogen compound including a symmetric or asymmetric acetylene group may be prepared.
본 발명의 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물은 대칭형 혹은 비대칭형의 트리페닐렌을 중심과 고복굴절율을 위한 아세틸렌기, 다양한 액정상 온도 조절을 위한 곁가지, 다양한 조건에서 광가교가 가능하도록 화합물의 곁가지 말단에 아크릴로일기, 메타아크릴로일기, 페닐아크릴로일기(신나모일기) 또는 퓨릴아크릴로일기가 도입되었다. The acetylene-containing triphenylene-based reactive mesogen compound of the present invention is a symmetric or asymmetric triphenylene acetylene group for the center and high birefringence, side branches for various liquid crystal phase temperature control, the compound of the crosslinking to enable a variety of conditions The acryloyl group, the methacryloyl group, the phenyl acryloyl group (cinnamoyl group), or the furyl acryloyl group was introduce | transduced by the side of the branch.
본 발명의 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물은 고복굴절률을 갖기 때문에 액정 표시장치의 보상필름을 박막으로 제조할 수 있으며, 이러한 보상필름을 채용한 액정장치는 대화면 광시야각을 구현할 수 있는 장점이 있다. Since the acetylene-containing triphenylene-based reactive mesogen compound of the present invention has a high birefringence, a compensation film of a liquid crystal display device can be manufactured in a thin film, and a liquid crystal device employing such a compensation film has an advantage of realizing a wide viewing angle. have.
이하, 본 발명을 하기의 실시예에 의거하여 좀 더 상세히 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 한정하지는 않는다.
Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.
[실시예1] 아세틸렌 포함 대칭형 원반형 반응성 메조겐 2,6,10트리스(4헥실페닐에티닐)3,7,11트리스(4(6아크릴로일옥시헥실록시)벤조일록시)트리페닐렌(2,6,10tris(4hexylphenylethynyl)3,7,11tris(4(6acryloyloxyhexyloxy)benzoyloxy)triphenylene)의 합성EXAMPLE 1 Symmetric Disk-shaped Reactive Mesogen with Acetylene 2,6,10 Tris (4hexylphenylethynyl) 3,7,11 Tris (4 (6Acryloyloxyhexyloxy) benzoyloxy) triphenylene ( Synthesis of 2,6,10tris (4hexylphenylethynyl) 3,7,11tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene)
삭제delete
1-(헥실록시)-2-메톡시벤젠(1-(Hexyloxy)-2-methoxybenzene)의 합성Synthesis of 1- (hexyloxy) -2-methoxybenzene
2-메톡시페놀(2Methoxyphenol) (20 g, 0.16 mol)을 아세톤 (500 mL)에 녹인 후, K2CO3 (111 g, 0.81 mol)을 첨가하여 30분 동안 교반한다. 1브로모헥산 (25 mL, 0.18 mol)을 적가 한 후 질소 분위기 하에서 24시간 동안 환류한다. 반응 종료 후 아세톤을 제거 한 후 디클로로메탄으로 추출한다. 용매제거 후 관 크로마토그래피 (실리카, hexane/CH2Cl2 = 5 / 1)로 분리하여 1-(헥실록시)-2-메톡시벤젠(1-(Hexyloxy)-2-methoxybenzene) (29 g, 88 %)을 얻었다. 2-Methoxyphenol (20 g, 0.16 mol) is dissolved in acetone (500 mL), and then K 2 CO 3 (111 g, 0.81 mol) is added and stirred for 30 minutes. 1 bromohexane (25 mL, 0.18 mol) is added dropwise and refluxed under nitrogen atmosphere for 24 hours. After completion of the reaction, acetone is removed and extracted with dichloromethane. After solvent removal, the reaction mixture was separated by column chromatography (silica, hexane / CH 2 Cl 2 = 5/1) to obtain 1- (hexyloxy) -2-methoxybenzene (1- (Hexyloxy) -2-methoxybenzene) (29 g , 88%).
1H NMR (CDCl3, 300MHz) δ 6.886.82 (m, 4H, ArH), 3.99 (t, 2H, ArOCH2), 3.80 (s, 3H, OCH3) 1.831.76 (m, 2H, CH2), 1.471.29 (m, 6H, CH2), 0.910.88 (m, 3H, CH3); MS m/z 208 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 6.886.82 (m, 4H, ArH), 3.99 (t, 2H, ArOCH 2 ), 3.80 (s, 3H, OCH 3 ) 1.831.76 (m, 2H, CH 2 ), 1.471.29 (m, 6H, CH 2 ), 0.910.88 (m, 3H, CH 3 ); MS m / z 208 (M + )
2,6,10트리메톡시3,7,11트리스(헥실록시)트리페닐렌(2,6,10Trimethoxy3,7,11tris(hexyloxy)triphenylene)의 합성Synthesis of 2,6,10'trimethoxy'3,7,11'tris (hexyloxy) triphenylene (2,6,10'Trimethoxy'3,7,11'tris (hexyloxy) triphenylene)
1-(헥실록시)-2-메톡시벤젠(1-(Hexyloxy)-2-methoxybenzene) (29 g, 0.14 mol)을 디클로로메탄 (1 L)에 녹인 후 FeCl3 (68 g, 0.42 mol)을 적가한다. 24시간 반응 진행 후 메탄올로 반응을 종료시킨다. 용매 제거 후 관 크로마토그래피 (실리카, hexane/CH2Cl2 = 2/3)로 분리하여 흰색 고체 (5.5 g, Yield 19 %)를 얻었다. 1- (hexyloxy) -2-methoxybenzene (29 g, 0.14 mol) was dissolved in dichloromethane (1 L) and then FeCl 3 (68 g, 0.42 mol) Drop it off. After the reaction proceeds for 24 hours, the reaction is terminated with methanol. After removal of the solvent, separation by column chromatography (silica, hexane / CH 2 Cl 2 = 2/3) afforded a white solid (5.5 g, Yield 19%).
1H NMR (CDCl3, 500MHz) δ 7.76 (d, 2H, ArH), 4.23 (t, 2H, ArOCH2), 4.07 (s, 3H, OCH3), 1.981.92 (m, 2H, CH2), 1.581.52 (m, 2H, CH2), 1.431.30 (m, 4H, CH2), 0.930.86 (m, 3H, CH3); MS m/z 618 (M+)
1 H NMR (CDCl 3 , 500 MHz) δ 7.76 (d, 2H, ArH), 4.23 (t, 2H, ArOCH 2 ), 4.07 (s, 3H, OCH 3 ), 1.981.92 (m, 2H, CH 2 ) , 1.581.52 (m, 2H, CH 2 ), 1.431.30 (m, 4H, CH 2 ), 0.930.86 (m, 3H, CH 3 ); MS m / z 618 (M + )
2,6,10트리하이드록시3,7,11트리스(헥실록시)트리페닐렌(2,6,10Trihydroxy3,7,11tris(hexyloxy)triphenylene)의 합성Synthesis of 2,6,10trihydroxy3,7,11tris (hexyloxy) triphenylene (2,6,10Trihydroxy3,7,11tris (hexyloxy) triphenylene)
2,6,10트리메톡시3,7,11트리스(헥실록시)트리페닐렌(2,6,10Trimethoxy3,7,11tris(hexyloxy)triphenylene) (0.5 g, 0.8 mmol )을 THF (200 mL)에 녹인 후 질소기체 하에서 0.5M 리튬 다이페닐포스핀 (6.5 mL, 3.2 mmol)을 첨가한다. 12 시간 반응 진행 후 2M 염산 수용액과 디클로로메탄으로 유기층을 추출한다. 관 크로마토그래피 (실리카, hexane/CH2Cl2 = 1/5)로 분리하여 흰색 고체 (434 mg, 94 %)를 얻었다. 2,6,10trimethoxy3,7,11tris (hexyloxy) triphenylene (2,6,10Trimethoxy3,7,11tris (hexyloxy) triphenylene) (0.5 g, 0.8 mmol) in THF (200 mL) After dissolving in, add 0.5M lithium diphenylphosphine (6.5 mL, 3.2 mmol) under nitrogen gas. After the reaction proceeds for 12 hours, the organic layer is extracted with 2M aqueous hydrochloric acid solution and dichloromethane. Separated by column chromatography (silica, hexane / CH 2 Cl 2 = 1/5) to give a white solid (434 mg, 94%).
1H NMR (CDCl3, 300MHz) δ = 7.93 (s, 3H, ArH), 7.65 (s, 3H, ArH), 5.82 (s, 3H, ArOH), 4.25 (t, 6H, ArOCH2), 1.96 (m, 6H, CH2), 1.53 (m, 6H, CH2), 1.411.36 (m, 12H, CH2), 0.96 (t, 9H, CH3); MS m/z 576 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ = 7.93 (s, 3H, ArH), 7.65 (s, 3H, ArH), 5.82 (s, 3H, ArOH), 4.25 (t, 6H, ArOCH 2 ), 1.96 ( m, 6H, CH 2 ), 1.53 (m, 6H, CH 2 ), 1.411.36 (m, 12H, CH 2 ), 0.96 (t, 9H, CH 3 ); MS m / z 576 (M + )
2,6,10트리스(트리플루오로메탄술포닐)3,7,11트리스(헥실록시)트리페닐렌(2,6,10Tris(trifluoromethanesulfonyl)3,7,11tris(hexyloxy)triphenylene)의 합성Of 2,6,10tris (trifluoromethanesulfonyl) 3,7,11tris (hexyloxy) triphenylene (2,6,10tris (trifluoromethanesulfonyl) 3,7,11tris (hexyloxy) triphenylene) synthesis
2,6,10트리하이드록시3,7,11트리스(헥실록시)트리페닐렌(2,6,10Trihydroxy3,7,11tris(hexyloxy)triphenylene) (1.0 g, 1.7 mmol)을 피리딘 (15 mL)에 녹인다. 0 oC에서 trifluoromethanesulfonic anhydride (1.5 mL, 1.7 mmol)을 적가하고 24시간 동안 교반한다. 반응 종료 후 디클로로메탄으로 추출한다. 용매 제거 후 관 크로마토그래피 (실리카, hexane/CHCl3 = 2/1)로 분리하여 노란색 고체 (1.6 g, 92 %)를 얻었다. 2,6,10trihydroxy3,7,11tris (hexyloxy) triphenylene (2,6,10Trihydroxy3,7,11tris (hexyloxy) triphenylene) (1.0 g, 1.7 mmol) pyridine (15 mL) Dissolve in. Trifluoromethanesulfonic anhydride (1.5 mL, 1.7 mmol) is added dropwise at 0 o C and stirred for 24 h. After completion of the reaction, the mixture was extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, hexane / CHCl 3 = 2/1) to give a yellow solid (1.6 g, 92%).
1H NMR (CDCl3, 300MHz) δ 8.30 (s, 1H, ArH), 8.15 (d, 2H, ArH), 7.92 (d, 2H, ArH), 7.85 (s, 1H, ArH), 4.38 (m, 6H, ArOCH2), 1.95 (m, 6H, CH2), 1.53 (m, 6H, CH2), 1.411.34 (m, 12H, CH2), 0.95 (t, 9H, CH3); MS m/z 972 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 8.30 (s, 1H, ArH), 8.15 (d, 2H, ArH), 7.92 (d, 2H, ArH), 7.85 (s, 1H, ArH), 4.38 (m, 6H, ArOCH 2 ), 1.95 (m, 6H, CH 2 ), 1.53 (m, 6H, CH 2 ), 1.411.34 (m, 12H, CH 2 ), 0.95 (t, 9H, CH 3 ); MS m / z 972 (M + )
2,6,10트리스(헥실록시)트리페닐렌(2,6,10Tris(hexyloxy)triphenylene)의 합성Synthesis of 2,6,10'tris (hexyloxy) triphenylene
2,6,10트리스(트리플루오로메탄술포닐)3,7,11트리스(헥실록시)트리페닐렌(2,6,10Tris(trifluoromethanesulfonyl)3,7,11tris(hexyloxy)triphenylene) (0.5 g, 0.52 mmol), palladium(II) acetate (10 mg, 0.046 mmol), triphenylphosphine (30 mg, 0.115 mmol)에 DMF (10 mL), formic acid (0.1 mL, 3.09 mmol)을 넣고 질소분위기 하에서 24시간 동안 60 oC에서 교반한다. 반응 종료 후 디클로로메탄으로 추출한다. 용매 제거 후 관 크로마토그래피 (실리카, hexane/CH2Cl3 =1/5)로 분리하여 노란색 고체 (275 mg, 99 %)를 얻었다. 2,6,10tris (trifluoromethanesulfonyl) 3,7,11tris (hexyloxy) triphenylene (2,6,10Tris (trifluoromethanesulfonyl) 3,7,11tris (hexyloxy) triphenylene) (0.5 g , 0.52 mmol), palladium (II) acetate (10 mg, 0.046 mmol) and triphenylphosphine (30 mg, 0.115 mmol) were added DMF (10 mL) and formic acid (0.1 mL, 3.09 mmol) for 24 hours under nitrogen atmosphere. Stir at 60 o C. After completion of the reaction, the mixture was extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, hexane / CH 2 Cl 3 = 1/5) to give a yellow solid (275 mg, 99%).
1H NMR (CDCl3, 300MHz) δ 8.408.33 (m, 1H, ArH), 7.90 (m, 1H, ArH), 7.257.20 (m, 1H, ArH), 4.15 (t, 2H, ArOCH2), 1.90 (m, 2H, CH2), 1.50 (m, 2H, CH2), 1.411.36 (m, 4H, CH2), 0.93 (t, 3H, CH3); MS m/z 528 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 8.408.33 (m, 1H, ArH), 7.90 (m, 1H, ArH), 7.257.20 (m, 1H, ArH), 4.15 (t, 2H, ArOCH 2 ) , 1.90 (m, 2H, CH 2 ), 1.50 (m, 2H, CH 2 ), 1.411.36 (m, 4H, CH 2 ), 0.93 (t, 3H, CH 3 ); MS m / z 528 (M + )
2,6,10트리브로모3,7,11트리스(헥실록시)트리페닐렌(2,6,10Tribromo3,7,11tris(hexyloxy)triphenylene)의 합성Synthesis of 2,6,10'tribromo'3,7,11'tris (hexyloxy) triphenylene (2,6,10'Tribromo'3,7,11'tris (hexyloxy) triphenylene)
2,6,10트리스(헥실록시)트리페닐렌(2,6,10Tris(hexyloxy)triphenylene) (2.5 g, 4.73 mmol)을 디클로로메탄 (50 mL)에 녹인 후 0 oC에서 브롬 (65 mL, 14.92 mmol)을 적가한다. 2시간 후 sodium thiosulfate 수용액으로 반응 종결 후 디클로메탄으로 추출한다. 용매 제거 후 관 크로마토그래피 (실리카, hexane/CH2Cl2 =1/1)로 분리하여 노란색 고체 (3.6 g, 99%)를 얻었다. Dissolve 2,6,10tris (hexyloxy) triphenylene (2.5 g, 4.73 mmol) in dichloromethane (50 mL) and then bromine at 0 o C (65 mL). 14.92 mmol) is added dropwise. After 2 hours, the reaction was terminated with aqueous sodium thiosulfate solution and extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, hexane / CH 2 Cl 2 = 1/1) to obtain a yellow solid (3.6 g, 99%).
1H NMR (CDCl3, 300MHz) δ 8.50 (s, 3H, ArH), 7.62(s, 3H, ArH), 4.25 (t, 6H, ArOCH2), 1.96 (t, 6H, CH2), 1.661.60 (m, 6H, CH2), 1.431.39 (m, 12H, CH2), 0.95 (t, 9H, CH3); MS m/z 764 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 8.50 (s, 3H, ArH), 7.62 (s, 3H, ArH), 4.25 (t, 6H, ArOCH 2 ), 1.96 (t, 6H, CH 2 ), 1.661. 60 (m, 6H, CH 2 ), 1.431.39 (m, 12H, CH 2 ), 0.95 (t, 9H, CH 3 ); MS m / z 764 (M + )
2,6,10트리하이드록시3,7,11트리브로모트리페닐렌(2,6,10트리하이드록시3,7,11트리브로모트리페닐렌)(2,6,10Trihydroxy3,7,11tribromotriphenylene(2,6,10Trihydroxy3,7,11tribromotriphenylene))의 합성 2,6,10 trihydroxy-3,7,11-tribromo triphenylene (2,6,10 trihydroxy-3, 7,11-tribromo-triphenylene) (2,6,10Trihydroxy3,7,11tribromotriphenylene Synthesis of (2,6,10Trihydroxy3,7,11tribromotriphenylene))
2,6,10트리브로모3,7,11트리스(헥실록시)트리페닐렌(2,6,10Tribromo3,7,11tris(hexyloxy)triphenylene) (0.5 g 0.65 mmol)을 디클로로메탄 (10 mL)에 녹인다. 질소기체 하 75 oC에서 BBr3 (2.2 mL, 24.1 mmol)를 디클로로메탄 (10 mL)에 묽힌 용액을 적가 한다. 24시간 후 얼음물로 반응을 종결 시킨 후 생성된 고체를 여과하여 흰색 화합물(268 mg, 80 %)을 얻었다. 2,6,10tribromo3,7,11tris (hexyloxy) triphenylene (2,6,10Tribromo3,7,11tris (hexyloxy) triphenylene) (0.5 g 0.65 mmol) in dichloromethane (10 mL) Dissolve in. Dilute a solution of BBr 3 (2.2 mL, 24.1 mmol) in dichloromethane (10 mL) at 75 ° C. under nitrogen gas. After 24 hours, the reaction was terminated with ice water, and the resulting solid was filtered to give a white compound (268 mg, 80%).
1H NMR (CDCl3, 300MHz) δ 11.0 (s, 3H, ArOH), 8.60 (s, 3H, ArH), 7.90 (s, 3H, ArH); MS m/z 512 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 11.0 (s, 3H, ArOH), 8.60 (s, 3H, ArH), 7.90 (s, 3H, ArH); MS m / z 512 (M + )
3,7,11트리브로모2,6,10트리스(4(6아크릴로일옥시헥실록시)벤조일록시)트리페닐렌(3,7,11tribromo2,6,10tris(4(6acryloyloxyhexyloxy)benzoyloxy) triphenylene)의 합성 3,7,11-tribromo-2,6,10-tris (on day hexyl oxy siloxane in 4 (6 acrylic) benzoyl hydroxy) triphenylene (3,7,11tribromo2,6,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene ) Synthesis
4(6(아크릴로일옥시)헥실록시)벤조익산(4(6(Acryloyloxy)hexyloxy)benzoic acid) (0.65 g, 2.21 mmol)을 DME (30 mL)와 트리에칠아민 (0.77 mL, 5.52 mmol)에 묽힌 후 0oC에서 메탄술포닐 클로라이드(methansulfonyl chloride) (0.2 mL, 2.42 mmol)을 질소 분위기 하에서 적가한다. 3시간 후 상온으로 온도를 올려 4디메칠아미노피리딘 (0.28 g, 0.23 mmol)과 2,6,10트리하이드록시3,7,11트리브로모트리페닐렌(2,6,10trihydroxy3,7,11tribromotriphenylene) (0.24 g, 0.46 mmol)을 첨가한다. 24시간 후 디클로로메탄으로 추출한다. 용매 제거 후 관 크로마토그래피 (실리카, CH2Cl2/MeOH = 60/1)로 분리하여 노란색 고체 (319 mg, 58%)를 얻었다. 4 (6 (acryloyloxy) hexyloxy) benzoic acid (4 (6 (Acryloyloxy) hexyloxy) benzoic acid) (0.65 g, 2.21 mmol) was added to DME (30 mL) and triethylamine (0.77 mL, 5.52 mmol) and methanesulfonyl chloride (0.2 mL, 2.42 mmol) is added dropwise under 0 atmosphere at 0 ° C. After 3 hours, the temperature was raised to room temperature, and 4-dimethylaminopyridine (0.28 g, 0.23 mmol) and 2,6,10trihydroxy 3,7,11 tribromotriphenylene (2,6,10trihydroxy3,7,11tribromotriphenylene ) (0.24 g, 0.46 mmol) is added. After 24 hours it is extracted with dichloromethane. After solvent removal, separation by column chromatography (silica, CH 2 Cl 2 / MeOH = 60/1) afforded a yellow solid (319 mg, 58%).
1H NMR (CDCl3, 300MHz) δ 8.62 (s, 3H, ArH), 8.44 (s, 3H, ArH), 8.22 (d, 6H, ArH), H), 6.90 (d, 6H, ArH), 6.456.37 (m, 3H, OAcr), 6.196.10 (m, 3H, OAcr), 5.855.81 (m, 3H, OAcr), 4.20 (t, 6H, ArOCH2), 4.06 (t, 6H, ArOCH2), 1.901.82 (m, 8H, CH2), 1.761.66 (m, 6H, CH2), 1.551.50 (m, 10H, CH2) ; MS m/z 1336 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 8.62 (s, 3H, ArH), 8.44 (s, 3H, ArH), 8.22 (d, 6H, ArH), H), 6.90 (d, 6H, ArH), 6.456 .37 (m, 3H, OAcr), 6.196.10 (m, 3H, OAcr), 5.855.81 (m, 3H, OAcr), 4.20 (t, 6H, ArOCH 2 ), 4.06 (t, 6H, ArOCH 2 ), 1.901.82 (m, 8H, CH 2 ), 1.761.66 (m, 6H, CH 2 ), 1.551.50 (m, 10H, CH 2 ); MS m / z 1336 (M + )
1에티닐4헥실벤젠(1Ethynyl4hexylbenzene)의 합성Synthesis of 1ethynyl4hexylbenzene
1헥실4아이오도벤젠(1Hexyl4iodobenzene) (2 g, 6.94 mmol)을 THF (30 mL)와 트리에칠아민 (30 mL)에 묽힌 후 상온에서 Pd(PPh3)2Cl2 (0.28 g, 0.69 mmol), PPh3 (91 mg, 0.35 mmol), CuI (0.13 g, 0.69 mmol)을 순서대로 첨가한 후 10분 동안 degassing 해준다. 90℃에서 에틴트리메틸실란(ethynyltrimethylsilane) (1.2 mL, 0.83 mmol)을 THF (10 mL)에 묽혀 적가 해준다. 12시간 후 용매 제거 후 관 크로마토그래피 (실리카, hexane)로 분리하여 중간체 노란색 액체 (1.5 g, 85%)를 얻었다. [(4헥실페닐) 에틴]트리메틸실란([(4hexylphenyl)ethynyl]trimethylsilane) (1.5 g, 5.81 mmol) 을 THF (10 mL)와 MeOH (10 mL)에 묽혀 상온에서 K2CO3 (0.88 g, 6.39 mmol)에 첨가한다. 3시간 후 용매 제거 후 디클로로메탄으로 추출한다. 노란색 액체 (1 g, 95 %)를 얻었다. Dilute 1hexyl4iodobenzene (2 g, 6.94 mmol) with THF (30 mL) and triethamine (30 mL), then add Pd (PPh 3 ) 2 Cl 2 (0.28 g, 0.69 mmol) at room temperature. ), PPh 3 (91 mg, 0.35 mmol) and CuI (0.13 g, 0.69 mmol) are added in this order and degassed for 10 minutes. At 90 ° C., ethynyltrimethylsilane (1.2 mL, 0.83 mmol) is added dropwise to THF (10 mL). After 12 hours, the solvent was removed, followed by column chromatography (silica and hexane) to obtain an intermediate yellow liquid (1.5 g, 85%). [(4hexylphenyl) ethynyl] trimethylsilane (1.5 g, 5.81 mmol) was diluted with THF (10 mL) and MeOH (10 mL) at room temperature, K 2 CO 3 (0.88 g, 6.39 mmol). After 3 hours, the solvent was removed and extracted with dichloromethane. A yellow liquid (1 g, 95%) was obtained.
1H NMR (CDCl3, 300MHz) δ 7.397.37 (m, 2H, ArH), 7.117.08 (m, 2H, ArH), 2.95 (s, 1H, C≡C), 2.592.54 (m, 2H, CH2) 1.611.52 (m, 2H, CH2), 1.341.25 (m, 6H, CH2), 0.890.84 (m, 3H, CH3) ; MS m/z 186 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 7.397.37 (m, 2H, ArH), 7.117.08 (m, 2H, ArH), 2.95 (s, 1H, C≡C), 2.592.54 (m, 2H , CH 2 ) 1.611.52 (m, 2H, CH 2 ), 1.341.25 (m, 6H, CH 2 ), 0.890.84 (m, 3H, CH 3 ); MS m / z 186 (M + )
3,7,11트리스(4헥실페닐에티닐)2,6,10트리스(4(6아크릴로일옥시헥실록시)벤조일옥시)트리페닐렌(3,7,11tris(4hexylphenylethynyl)2,6,10tris(4(6acryloyloxyhexyloxy)benzoyloxy)triphenylene)의 합성3,7,11tris (4hexylphenylethynyl) 2,6,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene (3,7,11tris (4hexylphenylethynyl) 2, Synthesis of 6,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene)
3,7,11트리브로모2,6,10트리스(4(6아크릴로일옥시헥실록시)벤조일옥시)트리페닐렌(3,7,11Tribromo2,6,10tris(4(6acryloyloxyhexyloxy)benzoyloxy)triphenylene) (0.90 g, 0.67 mmol)을 THF (25 mL)와 트리에칠아민 (20 mL)에 묽힌 후 상온에서 Pd(PPh3)2Cl2 (165 mg, 0.41 mmol), PPh3 (53 mg, 0.20 mmol), CuI (78 mg, 0.41 mmol)을 순서대로 첨가한 후 30분 동안 degassing 해준다. 90oC에서 1에티닐4헥실벤젠(1ethynyl4hexylbenzene) (447 mg, 2.43 mmol)을 THF (10 mL)에 묽혀 3시간 동안 적가 해준다. 12시간 후 용매 제거 후 관 크로마토그래피 (실리카, hexane/EA = 1/1)로 분리하여 흰색 고체(707 g, 50%)를 얻었다. 3,7,11tribromo2,6,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene (3,7,11Tribromo2,6,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene ) (0.90 g, 0.67 mmol) in THF (25 mL) and triethylamine (20 mL), and then Pd (PPh 3 ) 2 Cl 2 (165 mg, 0.41 mmol), PPh 3 (53 mg, 0.20 mmol), CuI (78 mg, 0.41 mmol) was added sequentially, followed by degassing for 30 minutes. Dilute 1ethynyl4hexylbenzene (447 mg, 2.43 mmol) in THF (10 mL) at 90 o C and add dropwise for 3 hours. After 12 hours, the solvent was removed, followed by column chromatography (silica, hexane / EA = 1/1) to obtain a white solid (707 g, 50%).
1H NMR (CDCl3, 300MHz) δ 8.808.79 (d, 2H, ArH), 8.61 (s, 3H, ArH), 8.45 (s, 3H, ArH), 7.237.16 (m, 6H, ArH), 7.076.93 (d, 16H, ArH), 6.446.39 (m, 3H, OAcr), 6.186.10 (m, 3H, OAcr), 5.855.82 (m, 3H, OAcr), 4.20 (t, 6H, ArOCH2), 4.08 (t, 6H, OCH2), 2.57 (t, 6H, CH2), 1.871.72 (m, 12H, CH2), 1.55 (m, 20H, CH2), 1.291.25 (m, 16H, CH2), 0.87 (t, 9H, CH3) ; MS m/z 1675 (M+Na)
1 H NMR (CDCl 3 , 300 MHz) δ 8.808.79 (d, 2H, ArH), 8.61 (s, 3H, ArH), 8.45 (s, 3H, ArH), 7.237.16 (m, 6H, ArH), 7.076.93 (d, 16H, ArH), 6.446.39 (m, 3H, OAcr), 6.186.10 (m, 3H, OAcr), 5.855.82 (m, 3H, OAcr), 4.20 (t, 6H, ArOCH 2 ), 4.08 (t, 6H, OCH 2 ), 2.57 (t, 6H, CH 2 ), 1.871.72 (m, 12H, CH 2 ), 1.55 (m, 20H, CH 2 ), 1.291.25 ( m, 16H, CH 2 ), 0.87 (t, 9H, CH 3 ); MS m / z 1675 (M + Na)
[ 실시예2] 아세틸렌 포함 비대칭형 원반형 반응성 메조겐 3,6,11트리스(4헥실페닐에티닐)2,7,10트리스(4(6아크릴로일옥시헥실록시)벤조일록시)트리페닐렌(3,6,11tris(4hexylphenylethynyl)2,7,10tris(4(6acryloyloxyhexyloxy)benzoyloxy)triphenylene)의 합성
Example 2 Asymmetric Disk-Type Reactive Mesogen with Acetylene 3,6,11 Tris (4hexylphenylethynyl) 2,7,10 Tris (4 (6Acryloyloxyhexyloxy) benzoyloxy) triphenylene Synthesis of (3,6,11tris (4hexylphenylethynyl) 2,7,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene)
2헥실록시페놀(2Hexyloxyphenol) 의 합성Synthesis of 2hexyloxyphenol
카테콜 (50 g, 0.45 mol)을 아세톤 (1 L)에 녹인 후, K2CO3 (250 g, 1.81 mol)을 첨가하여 30분 동안 교반한다. 1브로모헥산 (95.6 mL, 0.68 mol)을 적가 한 후 질소분위기 하에서 24 시간 동안 환류한다. 반응 종료 후 아세톤을 제거하고 디클로로메탄으로 추출한다. 용매를 제거한 후 관크로마토그래피 (실리카, hexane/CH2Cl2 = 5/1)로 분리하여 무색의 오일 2헥실옥시페놀 (25 g, 수득율 28 %)을 얻었다. Catechol (50 g, 0.45 mol) is dissolved in acetone (1 L), then K 2 CO 3 (250 g, 1.81 mol) is added and stirred for 30 minutes. 1 bromohexane (95.6 mL, 0.68 mol) is added dropwise and refluxed under nitrogen for 24 hours. After completion of the reaction, acetone is removed and extracted with dichloromethane. The solvent was removed and then separated by column chromatography (silica, hexane / CH 2 Cl 2 = 5/1) to give a colorless oil 2hexyloxyphenol (25 g, 28% yield).
1H NMR (CDCl3, 300MHz) δ 6.936.89 (m, 1H, ArH), 6.856.77 (m, 3H, ArH), 5.76 (s, 1H, ArOH) 3.99 (t, 2H, ArOCH2), 1.801.71 (m, 2H, CH2), 1.461.26 (m, 6H, CH2), 0.91 (m, 3H, CH3); MS m/z 194 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 6.936.89 (m, 1H, ArH), 6.856.77 (m, 3H, ArH), 5.76 (s, 1H, ArOH) 3.99 (t, 2H, ArOCH 2 ), 1.801.71 (m, 2H, CH 2 ), 1.461.26 (m, 6H, CH 2 ), 0.91 (m, 3H, CH 3 ); MS m / z 194 (M + )
2,7,10트리하이드록시3,6,11트리스(헥실록시)트리페닐렌(2,7,10Trihydroxy3,6,11tris(hexyloxy)triphenylene)의 합성Synthesis of 2,7,10trihydroxy3,6,11tris (hexyloxy) triphenylene (2,7,10Trihydroxy3,6,11tris (hexyloxy) triphenylene)
2헥실옥시페놀 (2 g, 0.01 mol)을 디클로로메탄 (250 mL)에 녹인 후 FeCl3 (5 g, 0.03 mol)을 첨가한다. 24 시간 반응 진행 후 메탄올로 종료시킨다. 3시간 후 용매 제거 후 관 크로마토그래피 (실리카, hexane/CH2Cl2 = 1/5)로 분리하여 흰색 고체(0.8 g, 수득율 13%)를 얻었다 . Dissolve 2hexyloxyphenol (2 g, 0.01 mol) in dichloromethane (250 mL) and then add FeCl 3 (5 g, 0.03 mol). After the reaction proceeds for 24 hours it is terminated with methanol. After 3 hours, the solvent was removed, followed by column chromatography (silica, hexane / CH 2 Cl 2 = 1/5) to obtain a white solid (0.8 g, yield 13%).
1H NMR (CDCl3, 300MHz) δ = 7.93 (d, 3H, ArH), 7.78 (s, 1H, ArH), 7.73 (d, 2H, ArH), 5.885.85 (m, 3H, ArOH), 4.314.23 (m, 6H, ArOCH2), 1.971.91 (m, 6H, CH2), 1.571.54 (m, 6H, CH2), 1.401.38 (m, 12H, CH2), 0.94 (m, 9H, CH3)(; MS m/z 576 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ = 7.93 (d, 3H, ArH), 7.78 (s, 1H, ArH), 7.73 (d, 2H, ArH), 5.885.85 (m, 3H, ArOH), 4.314 .23 (m, 6H, ArOCH 2 ), 1.971.91 (m, 6H, CH 2 ), 1.571.54 (m, 6H, CH 2 ), 1.401.38 (m, 12H, CH 2 ), 0.94 (m , 9H, CH 3 ) (; MS m / z 576 (M + )
2,7,10트리스(트리플루오로메탄술포닐)3,6,11트리스(헥실록시)트리페닐렌(2,7,10Tris(trifluoromethanesulfonyl)3,6,11tris(hexyloxy)triphenylene)의 합성Of 2,7,10tris (trifluoromethanesulfonyl) 3,6,11tris (hexyloxy) triphenylene (2,7,10tris (trifluoromethanesulfonyl) 3,6,11tris (hexyloxy) triphenylene) synthesis
2,7,10트리하이드록시3,6,11트리스(헥실록시)트리페닐렌(2,7,10Trihydroxy3,6,11tris(hexyloxy)triphenylene) (0.7 g, 0.001 mol)을 피리딘 (10 mL)에 녹인다. 0 oC에서 트리플로오로메탄술포닉 언하이드라이드(trifluoromethanesulfonic anhydride) (1.2 mL, 0.007 mol)을 적가하고 24시간 동안 교반한다. 반응 종료 후 디클로로메탄으로 추출한다. 용매 제거 후 관 크로마토그래피 (실리카, hexane/CHCl3 = 2/1)로 분리하여 노란색 고체 (1.1 g, 94 %)를 얻었다.2,7,10trihydroxy3,6,11tris (hexyloxy) triphenylene (2,7,10Trihydroxy3,6,11tris (hexyloxy) triphenylene) (0.7 g, 0.001 mol) was pyridine (10 mL) Dissolve in. Trifluoromethanesulfonic anhydride (1.2 mL, 0.007 mol) is added dropwise at 0 ° C. and stirred for 24 hours. After completion of the reaction, the mixture was extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, hexane / CHCl 3 = 2/1) to give a yellow solid (1.1 g, 94%).
1H NMR (CDCl3, 300MHz) δ 8.27 (s, 1H, ArH), 8.15 (d, 2H, ArH), 7.91 (d, 2H, ArH), 7.81 (s, 1H, ArH), 4.334.28 (m, 6H, ArOCH2), 2.001.95 (m, 6H, CH2), 1.621.61 (m, 6H, CH2), 1.431.38 (m, 12H, CH2), 0.94 (m, 9H, CH3); MS m/z 972 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 8.27 (s, 1H, ArH), 8.15 (d, 2H, ArH), 7.91 (d, 2H, ArH), 7.81 (s, 1H, ArH), 4.334.28 ( m, 6H, ArOCH 2 ), 2.001.95 (m, 6H, CH 2 ), 1.621.61 (m, 6H, CH 2 ), 1.431.38 (m, 12H, CH 2 ), 0.94 (m, 9H, CH 3 ); MS m / z 972 (M + )
2,7,10트리스(헥실록시)트리페닐렌(2,7,10Tris(hexyloxy)triphenylene)의 합성Synthesis of 2,7,10'tris (hexyloxy) triphenylene
2,7,10트리스(트리플루오로메탄술포닐)3,6,11트리스(헥실록시)트리페닐렌(2,7,10Tris(trifluoromethanesulfonyl)3,6,11tris(hexyloxy)triphenylene) (0.5 g, 0.52 mmol), palladium(II) acetate (10 mg, 0.046 mmol), 트리페닐포스핀(triphenylphosphine) (30 mg, 0.115 mmol)에 DMF (10 mL), formic acid (0.1 mL, 3.09 mmol)을 넣고 질소분위기 하에서 24시간 동안 60 oC에서 교반한다. 반응 종료 후 디클로로메탄으로 추출한다. 용매 제거 후 관 크로마토그래피 (실리카, hexane/CH2Cl3 =1/5)로 분리하여 노란색 고체 (270 mg, 99 %)를 얻었다.2,7,10tris (trifluoromethanesulfonyl) 3,6,11tris (hexyloxy) triphenylene (2,7,10Tris (trifluoromethanesulfonyl) 3,6,11tris (hexyloxy) triphenylene) (0.5 g , 0.52 mmol), palladium (II) acetate (10 mg, 0.046 mmol) and triphenylphosphine (30 mg, 0.115 mmol) were added DMF (10 mL) and formic acid (0.1 mL, 3.09 mmol). Stir at 60 ° C. for 24 h under nitrogen atmosphere. After completion of the reaction, the mixture was extracted with dichloromethane. After removing the solvent was separated by column chromatography (silica, hexane / CH 2 Cl 3 = 1/5) to give a yellow solid (270 mg, 99%).
1H NMR (CDCl3, 300MHz) δ 8.468.37 (m, 1H, ArH), 7.937.90 (m, 1H, ArH), 7.247.14 (m, 1H, ArH), 4.184.12 (m, 2H, ArOCH2), 1.921.82 (m, 2H, CH2), 1.54 (m, 2H, CH2), 1.411.37 (m, 4H, CH2), 0.950.91 (m, 3H, CH3); MS m/z 528 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 8.468.37 (m, 1H, ArH), 7.937.90 (m, 1H, ArH), 7.247.14 (m, 1H, ArH), 4.184.12 (m, 2H , ArOCH 2 ), 1.921.82 (m, 2H, CH 2 ), 1.54 (m, 2H, CH 2 ), 1.411.37 (m, 4H, CH 2 ), 0.950.91 (m, 3H, CH 3 ) ; MS m / z 528 (M + )
2,7,10트리브로모3,6,11트리스(헥실록시)트리페닐렌(2,7,10Tribromo3,6,11tris(hexyloxy)triphenylene)의 합성Synthesis of 2,7,10'tribromo'3,6,11'tris (hexyloxy) triphenylene (2,7,10'Tribromo'3,6,11'tris (hexyloxy) triphenylene)
2,7,10트리스(헥실록시)트리페닐렌(2,7,10Tris(hexyloxy)triphenylene) (0.24 g, 0.45 mmol)을 디클로로메탄 (10 mL)에 녹인 후 0 oC에서 브롬 (7.7 mL, 1.49 mmol)을 적가한다. 2시간 후 sodium thiosulfate 수용액으로 반응 종결 후 디클로메탄으로 추출한다. 용매 제거 후 관 크로마토그래피 (실리카, hexane/CH2Cl2 =1/1)로 분리하여 노란색 고체 (345 mg, 99%)를 얻었다.Dissolve 2,7,10tris (hexyloxy) triphenylene (0.24 g, 0.45 mmol) in dichloromethane (10 mL) and then bromine (7.7 mL) at 0 o C. , 1.49 mmol) is added dropwise. After 2 hours, the reaction was terminated with aqueous sodium thiosulfate solution and extracted with dichloromethane. After removing the solvent was separated by column chromatography (silica, hexane / CH 2 Cl 2 = 1/1) to give a yellow solid (345 mg, 99%).
1H NMR (CDCl3, 300MHz) δ 8.53 (s, 1H, ArH), 8.49 (d, 2H, ArH), 7.69(d, 2H, ArH), 7.62 (m, 1H, ArH), 4.274.20 (m, 6H, ArOCH2), 1.991.94 (m, 6H, CH2), 1.641.60 (m, 6H, CH2), 1.421.40 (m, 12H, CH2), 0.970.92 (m, 9H, CH3); MS m/z 764 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 8.53 (s, 1H, ArH), 8.49 (d, 2H, ArH), 7.69 (d, 2H, ArH), 7.62 (m, 1H, ArH), 4.274.20 ( m, 6H, ArOCH 2 ), 1.991.94 (m, 6H, CH 2 ), 1.641.60 (m, 6H, CH 2 ), 1.421.40 (m, 12H, CH 2 ), 0.970.92 (m, 9H, CH 3 ); MS m / z 764 (M + )
2,7,10트리하이드록시3,6,11트리브로모트리페닐렌(2,7,10트리하이드록시3,6,11트리브로모트리페닐렌)의 합성 Synthesis of 2,7,10trihydroxy3,6,11tribromotriphenylene (2,7,10trihydroxy 3,6,11tribromotriphenylene)
2,7,10트리브로모3,6,11트리스(헥실록시)트리페닐렌(2,7,10Tribromo3,6,11tris(hexyloxy)triphenylene) (0.62 g 0.81 mmol)을 디클로로메탄 (10 mL)에 녹인다. 질소기체 하 75 oC에서 BBr3 (2.3 mL, 24.3 mmol)를 디클로로메탄 (10 mL)에 묽힌 후 적가 한다. 24시간 후 얼음물로 반응을 종결 시킨 후 생성된 고체를 여과하여 흰색 화합물(297 mg, 72 %)을 얻었다 .2,7,10tribromo3,6,11tris (hexyloxy) triphenylene (2,7,10Tribromo3,6,11tris (hexyloxy) triphenylene) (0.62 g 0.81 mmol) in dichloromethane (10 mL) Dissolve in. Dilute BBr 3 (2.3 mL, 24.3 mmol) in dichloromethane (10 mL) at 75 o C under nitrogen gas and add dropwise. After 24 hours, the reaction was terminated with ice water. The resulting solid was filtered to give a white compound (297 mg, 72%).
1H NMR (CDCl3, 300MHz) δ 10.96 (s, 1H, ArOH), 10.77 (s, 1H, ArOH), 10.50 (s, 1H, ArOH), 8.818.87 (d, 2H, ArH), 8.48 (s, 1H, ArH), 7.937.88 (t, 3H, ArH); MS m/z 512 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 10.96 (s, 1H, ArOH), 10.77 (s, 1H, ArOH), 10.50 (s, 1H, ArOH), 8.818.87 (d, 2H, ArH), 8.48 ( s, 1H, ArH), 7.937.88 (t, 3H, ArH); MS m / z 512 (M + )
3,6,11트리브로모2,7,10트리스(4(6아크릴로일옥시헥실록시)벤조일록시)트리페닐렌(3,6,11tribromo2,7,10tris(4(6acryloyloxyhexyloxy)benzoyloxy)triphenylene)의 합성 3,6,11tribromo2,7,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene (3,6,11tribromo2,7,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene ) Synthesis
4(6(아크릴로일옥시)헥실록시)벤조익산(4(6(Acryloyloxy)hexyloxy)benzoic acid) (0.65 g, 2.21 mmol)을 DME (30 mL)와 트리에칠아민 (0.77 mL, 5.52 mmol)에 묽힌 후 0 oC에서 메탄술포닐 클로라이드(methansulfonyl chloride) (0.2 mL, 2.42 mmol)을 질소 분위기 하에서 적가한다. 3시간 후 상온으로 온도를 올려 4디메칠아미노피리딘 (0.28 g, 0.23 mmol)과 2,7,10트리하이드록시3,6,11트리브로모트리페닐렌(2,7,10trihydroxy3,6,11tribromotriphenylene) (0.24 g, 0.46 mmol)을 첨가한다. 24시간 후 디클로로메탄으로 추출한다. 용매 제거 후 관 크로마토그래피 (실리카, CH2Cl2/MeOH = 60/1)로 분리하여 노란색 고체(0.38 g, 69%)를 얻었다. 4 (6 (acryloyloxy) hexyloxy) benzoic acid (4 (6 (Acryloyloxy) hexyloxy) benzoic acid) (0.65 g, 2.21 mmol) was added to DME (30 mL) and triethylamine (0.77 mL, 5.52 mmol) and methanesulfonyl chloride (0.2 mL, 2.42 mmol) is added dropwise under 0 atmosphere at 0 ° C. After 3 hours, the temperature was raised to room temperature, and 4-dimethylaminopyridine (0.28 g, 0.23 mmol) and 2,7,10trihydroxy 3,6,11 tribromotriphenylene (2,7,10trihydroxy3,6,11tribromotriphenylene ) (0.24 g, 0.46 mmol) is added. After 24 hours it is extracted with dichloromethane. After solvent removal, the residue was separated by column chromatography (silica, CH 2 Cl 2 / MeOH = 60/1) to give a yellow solid (0.38 g, 69%).
1H NMR (CDCl3, 300MHz) δ 8.648.60 (d, 2H, ArH), 8.39 (s, 1H, ArH), 8.288.12 (m, 8H, ArH), 8.03 (s, 1H, ArH), 6.986.88 (m, 6H, ArH), 6.456.37 (m, 3H, OAcr), 6.186.08 (m, 3H, OAcr), 5.855.82 (m, 3H, OAcr), 4.224.16 (m, 6H, ArOCH2), 4.084.02 (m, 6H, ArOCH2), 1.871.83 (m, 8H, CH2), 1.771.70 (m, 6H, CH2), 1.551.51 (m, 10H, CH2) ; MS m/z 1336 (M+) 1 H NMR (CDCl 3 , 300 MHz) δ 8.648.60 (d, 2H, ArH), 8.39 (s, 1H, ArH), 8.288.12 (m, 8H, ArH), 8.03 (s, 1H, ArH), 6.986.88 (m, 6H, ArH), 6.456.37 (m, 3H, OAcr), 6.186.08 (m, 3H, OAcr), 5.855.82 (m, 3H, OAcr), 4.224.16 (m, 6H, ArOCH 2 ), 4.084.02 (m, 6H, ArOCH 2 ), 1.871.83 (m, 8H, CH 2 ), 1.771.70 (m, 6H, CH 2 ), 1.551.51 (m, 10H, CH 2 ); MS m / z 1336 (M + )
3,6,11트리스(4헥실페닐에티닐)2,7,10트리스(4(6아크릴로일옥시헥실록시)벤조일록시)트리페닐렌(3,6,11tris(4hexylphenylethynyl)2,7,10tris(4(6acryloyloxyhexyloxy)benzoyloxy)triphenylene)의 합성3,6,11 tris (4hexylphenylethynyl) 2,7,10 tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene (3,6,11tris (4hexylphenylethynyl) 2, Synthesis of 7,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene)
3,6,11트리브로모2,7,10트리스(4(6아크릴로일옥시헥실록시)벤조일록시)트리페닐렌(3,6,11Tribromo2,7,10tris(4(6acryloyloxyhexyloxy)benzoyloxy)triphenylene) (0.77 g, 0.57 mmol)을 THF (20 mL)와 트리에칠아민 (20 mL)에 묽힌 후 상온에서 Pd(PPh3)2Cl2 (0.14 g, 0.35 mmol), PPh3 (45 mg, 0.17 mmol), CuI (66 mg, 0.35 mmol)을 순서대로 첨가한 후 30분 동안 degassing 해준다. 90oC에서 1-에티닐-4-헥실벤젠(1ethynyl4hexylbenzene)(0.38 g, 2.07 mmol)을 THF (10 mL)에 묽혀 3시간 동안 첨가 해준다. 12시간 후 용매 제거 후 관 크로마토그래피 (실리카, hexane/EA = 1/1)로 분리하여 흰색 고체(0.6 g, 49%)를 얻었다. 3,6,11tribromo2,7,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene (3,6,11Tribromo2,7,10tris (4 (6acryloyloxyhexyloxy) benzoyloxy) triphenylene ) (0.77 g, 0.57 mmol) in THF (20 mL) and triethylamine (20 mL), and then Pd (PPh 3 ) 2 Cl 2 (0.14 g, 0.35 mmol), PPh 3 (45 mg, 0.17 mmol) and CuI (66 mg, 0.35 mmol) are added sequentially, followed by degassing for 30 minutes. At 90 ° C., 1-ethynyl-4-hexylbenzene (0.38 g, 2.07 mmol) is diluted in THF (10 mL) and added for 3 hours. After 12 hours, the solvent was removed, followed by column chromatography (silica, hexane / EA = 1/1) to obtain a white solid (0.6 g, 49%).
1H NMR (CDCl3, 300MHz) δ 8.808.79 (d, 2H, ArH), 8.64 (m, 1H, ArH), 8.47 (m, 1H, ArH), 8.38 (m, 1H, ArH), 8.338.23 (m, 7H, ArH), 7.237.16 (m, 6H, ArH), 7.076.93 (m, 12H, ArH), 6.456.38 (m, 3H, OAcr), 6.186.08 (m, 3H, OAcr), 5.855.81 (m, 3H, OAcr), 4.234.17 (m, 6H, ArOCH2), 4.104.01 (m, 6H, OCH2),2.592.51 (m, 6H, CH2), 1.871.72 (m, 12H, CH2), 1.55 (m, 20H, CH2), 1.291.25 (m, 16H, CH2), 0.880.86 (m, 9H, CH3) ; MS m/z 1675 (M+Na)
1 H NMR (CDCl 3 , 300 MHz) δ 8.808.79 (d, 2H, ArH), 8.64 (m, 1H, ArH), 8.47 (m, 1H, ArH), 8.38 (m, 1H, ArH), 8.338. 23 (m, 7H, ArH), 7.237.16 (m, 6H, ArH), 7.076.93 (m, 12H, ArH), 6.456.38 (m, 3H, OAcr), 6.186.08 (m, 3H, OAcr), 5.855.81 (m, 3H, OAcr), 4.234.17 (m, 6H, ArOCH 2 ), 4.104.01 (m, 6H, OCH 2 ), 2.592.51 (m, 6H, CH 2 ), 1.871.72 (m, 12H, CH 2 ), 1.55 (m, 20H, CH 2 ), 1.291.25 (m, 16H, CH 2 ), 0.880.86 (m, 9H, CH 3 ); MS m / z 1675 (M + Na)
[실시예3] 실시예 2를 통해 제조한 아세틸렌 함유 트리페닐렌계 반응성 메조겐을 포함하는 필름 제조[Example 3] Film preparation containing acetylene-containing triphenylene-based reactive mesogen prepared in Example 2
ITO유리기판, 유리기판 혹은 고분자 필름 기판에 배향막을 코팅하고 1회 러빙을 하였다. 러빙된 배향막 위에 실시예 2를 통해 제조한 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물을 사용하여 1000 nm 두께 필름 제조시 아니솔(anisole)에 실시예 2 화합물 24wt%, 250 nm 두께 필름 제조시 anisole에 실시예 2 화합물 7wt% 를 녹인 액정 용액을 제조하였다. 이 액정 용액에 광개시제로서 3{4[2,4비스(트리클로로메틸)s트리아진6일]페닐티오}프로피온산(3{4[2,4bis(trichloromethyl)striazine6yl]phenylthio}propionic acid) (아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물에 대해 3wt%)을 첨가한 혼합액을 스핀코팅(1500 rpm, 30 초)한 후, 140 ℃ 온도에서 10분 동안 유지하였다. 이후, 365 nm의 파장에서 0.01~2 J/cm2의 자외선을 조사하여 광경화시켜 필름을 제조하였다.
An alignment film was coated on an ITO glass substrate, a glass substrate, or a polymer film substrate and rubbed once. Anisole when preparing 1000 nm thick film using acetylene-containing triphenylene-based reactive mesogen compound prepared in Example 2 on rubbed alignment layer, and anisole when preparing 24 wt% compound and 250 nm thick film Example 2 A liquid crystal solution in which 7 wt% of a compound was dissolved was prepared. 3 {4 [2,4bis (trichloromethyl) striazine6 yl] phenylthio} propionic acid (3 {4 [2,4bis (trichloromethyl) striazine6yl] phenylthio} propionic acid) (acetylene-containing in this liquid crystal solution as a photoinitiator 3 wt% of the triphenylene-based reactive mesogen compound was added to the mixed solution after spin coating (1500 rpm, 30 seconds), and then maintained at 140 ° C. for 10 minutes. Then, the film was prepared by irradiating with ultraviolet light of 0.01 ~ 2 J / cm 2 at a wavelength of 365 nm.
[비교예] 아세틸렌이 포함되어 있지 않은 트리페닐렌계 반응성 메조겐을 포함하는 필름 제조[Comparative Example] Film preparation containing triphenylene-based reactive mesogen not containing acetylene
제조예 2의 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물 대신 아세틸렌이 포함되어 있지 않은 트리페닐렌계 반응성 메조겐(2,3,6,7,10,11-헥사키스[4-(6-아크릴로일옥시헥실옥시)벤조일록시]트리페닐렌, 2,3,6,7,10,11-hexakis[4-(6-acryloyloxyhexyloxy)benzoyloxy]triphenylene)을 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 필름을 제조하였다.
Triphenylene-based reactive mesogen (2,3,6,7,10,11-hexakis [4- (6-acryloyl) containing no acetylene in place of the acetylene-containing triphenylene-based reactive mesogen compound of Preparation Example 2 Oxyhexyloxy) benzoyloxy] triphenylene, 2,3,6,7,10,11-hexakis [4- (6-acryloyloxyhexyloxy) benzoyloxy] triphenylene) in the same manner as in Example 3 A film was prepared.
실시예 2를 통해 합성한 배향 전 액정 화합물은 도 1에 보는 바와 같이 편광 광학현미경하에서 액정이 갖는 상을 확인 할 수 있으며, 배향 후 실시예 3과 같이 필름화를 하면 도 2의 편광 광학현미경 사진과 같이, 필름이 편광자 사이에 0도와 45도로 위치할 때 각각 검정색과 흰색의 단일상을 보임을 확인 할 수 있었다.As shown in FIG. 1, the liquid crystal compound before alignment synthesized in Example 2 may identify an image of the liquid crystal under a polarization optical microscope, and when the film is formed as in Example 3 after the alignment, the polarization optical micrograph of FIG. 2. As such, when the film is positioned between 0 degrees and 45 degrees between the polarizers, it was confirmed that the black and white single phases were shown.
실시예 3으로부터 얻어진 보상필름의 위상차를 측정하기 위해 도 3과 같이 PEM 장비를 이용하였다. 90o 직교된 편광자와 분석자 사이에 액정의 배향 방향이 편광자와 분석자의 편광축에 각각 45o가 되도록 고정시킨 다음, 평면상에서 360o 회전시켜 빛의 투과도를 전압 변화량으로 측정하였다. 이 실험을 5회 반복하였다.PEM equipment was used as shown in FIG. 3 to measure the phase difference of the compensation film obtained in Example 3. The orientation of the liquid crystal was fixed to the polarizing axis of the polarizer and the analyzer between the 90 ° orthogonal polarizer and the analyzer so as to be 45 ° , and then rotated 360 ° on the plane to measure the transmittance of light as a voltage change amount. This experiment was repeated five times.
그리고 이것을 도 3과 같이 위상차로 환산하여 액정의 두께로 나누어 복굴절율을 계산하였으며, 실시예 2에 의해 합성된 아세틸렌 함유 반응성 메조겐을 이용하여 실시예 3에 의해 제조된 필름의 복굴절율값은 0.15 ~ 0.18의 고 복굴절률 값을 나타내었다. 이 값은 비교예의 아세틸렌을 함유하지 않는 트리페닐렌계 반응성 메조겐을 이용한 필름의 복굴절율인 0.10보다 큰 값이다. And the birefringence was calculated by dividing this by the phase difference as shown in Figure 3 by the thickness of the liquid crystal, the birefringence value of the film prepared in Example 3 using the acetylene-containing reactive mesogen synthesized in Example 2 is 0.15 A high birefringence value of ˜0.18 is shown. This value is larger than 0.10 which is the birefringence of the film using the triphenylene-based reactive mesogen containing no acetylene of the comparative example.
이와 같은 결과에 근거하여, 리타데이션값(retardation = 복굴절율 x 필름의 두께)으로 비교하여 보면 일정한 리타데이션값을 갖는다면 비교예보다 본 발명에 따른 보상필름의 복굴절율이 높기 때문에 상대적으로 필름의 두께를 얇게 할 수 있는 장점이 있어 필름을 박막으로 제조할 수 있는 장점이 있다. Based on these results, when compared with the retardation value (retardation = birefringence x film thickness), if the retardation value has a constant retardation value of the compensation film according to the present invention than the comparative example is relatively relatively There is an advantage in that the thickness can be thin, there is an advantage in that the film can be made into a thin film.
Claims (6)
[화학식 1]
[상기 화학식 1에서,
X 는 O, NH, S중에서 선택되는 어느 하나이며,
L 은 R, C(=O)R, C(=O)ArOR 및 -C(=O)ArNHR 로부터 선택되며,
Y 는 CH2, Ar, ArO, ArS, ArNH, C(=O), C(=O)O, C(=O)NH, C(=O)Ar, C(=O)ArO, C(=O)ArS, C(=O)ArNH, ArC(=O), ArC(=O)O, ArC(=O)S, ArC(=O)NH로부터 선택되며,
Z는
A는 -R′, C(=O)R′, -R-Z로부터 선택되는 어느 하나이며, 상기 R은 C1C20 알킬렌이고, Ar는 C6C30 아릴렌이며, R′은 C1C20 알킬이다.]An acetylene-containing triphenylene-based reactive mesogen compound represented by the following formula (1).
[Formula 1]
[In the above formula (1)
X Is any one selected from O, NH, S,
L is selected from R, C (= 0) R, C (= 0) ArOR and -C (= 0) ArNHR,
Y is CH 2 , Ar, ArO, ArS, ArNH, C (= 0), C (= 0) O, C (= 0) NH, C (= 0) Ar, C (= 0) ArO, C (= O) ArS, C (= 0) ArNH, ArC (= 0), ArC (= 0) O, ArC (= 0) S, ArC (= 0) NH,
Z is
A is any one selected from -R ', C (= 0) R', and -RZ, wherein R is C 1 C 20 alkylene, Ar is C 6 C 30 arylene, and R 'is C 1 C 20 alkyl.]
화학식 2 또는 화학식 3으로 표시되는 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물.
[화학식 2]
[화학식 3]
[상기 화학식 2 또는 화학식 3에 있어서, X, Y, L, Z, A의 정의는 상기 화학식 1과 동일하다.]The method of claim 1,
An acetylene-containing triphenylene-based reactive mesogen compound represented by the formula (2) or (3).
(2)
(3)
[In Formula 2 or Formula 3, the definitions of X, Y, L, Z and A are the same as in Formula 1 above.]
상기 R은 직쇄 또는 분지쇄의 C1C12 알킬렌기이고, Ar는 페닐렌, 나프틸렌, 안트라세닐렌, 벤조피레닐렌, 피레닐렌, 페난트릴렌 또는 플루오레닐렌인 아세틸렌 함유 트리페닐렌계 반응성 메조겐 화합물.The method of claim 1,
R is straight or branched C 1 C 12 An acetylene-containing triphenylene-based reactive mesogen compound wherein the alkylene group is Ar and phenylene, naphthylene, anthracenylene, benzopyrenylene, pyrenylene, phenanthrylene or fluorenylene.
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