KR102311861B1 - Nitrogen heteroaromatic containing azobenzene compound and composition for blue hologram recording comprising thereof - Google Patents

Nitrogen heteroaromatic containing azobenzene compound and composition for blue hologram recording comprising thereof Download PDF

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KR102311861B1
KR102311861B1 KR1020190151521A KR20190151521A KR102311861B1 KR 102311861 B1 KR102311861 B1 KR 102311861B1 KR 1020190151521 A KR1020190151521 A KR 1020190151521A KR 20190151521 A KR20190151521 A KR 20190151521A KR 102311861 B1 KR102311861 B1 KR 102311861B1
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polymer
hologram recording
hologram
mmol
azobenzene
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KR20210063063A (en
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가재원
강혜주
이미혜
강이영
김학린
주경일
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한국화학연구원
경북대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/82—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/2403—Layers; Shape, structure or physical properties thereof
    • G11B7/24035—Recording layers
    • G11B7/24044—Recording layers for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/12—Photopolymer

Abstract

본 발명은 아조벤젠 화합물, 이를 포함하는 홀로그램 기록용 조성물, 홀로그램 기록용 매체, 이를 사용한 홀로그램 기록 재료 및 홀로그램 기록 또는 재기록 방법에 관한 것으로써, 본 발명의 아조벤젠 단량체 화합물은 장파장의 파장에서 광 이성질화가 일어나고, 적은 양의 광조사에 의해서도 굴절율 변화를 크게 할 수 있는 고복굴절율 부분을 포함하고 있어 아조벤젠 단량체 화합물을 포함하는 고분자는 레이저 조사에 의한 홀로그램 기록/재기록 소재로 유용하게 사용될 수 있다.The present invention relates to an azobenzene compound, a hologram recording composition comprising the same, a hologram recording medium, a hologram recording material using the same, and a hologram recording or rewriting method, wherein the azobenzene monomer compound of the present invention undergoes photoisomerization at a long wavelength. Since it contains a high birefringence portion that can increase the refractive index change even with a small amount of light irradiation, a polymer containing an azobenzene monomer compound can be usefully used as a hologram recording/rewriting material by laser irradiation.

Description

함질소 헤테로방향족 포함 아조벤젠 화합물 및 이를 포함하는 청색 홀로그램 기록용 조성물{NITROGEN HETEROAROMATIC CONTAINING AZOBENZENE COMPOUND AND COMPOSITION FOR BLUE HOLOGRAM RECORDING COMPRISING THEREOF}Azobenzene compound containing nitrogen-containing heteroaromatic and composition for blue hologram recording containing the same

본 발명은 피리딘 및 피리미딘과 같은 함질소 헤테로방향족 포함 아조벤젠 화합물, 이를 포함하는 청색 홀로그램 기록용 조성물, 홀로그램 기록용 매체, 이를 사용한 홀로그램 기록 재료 및 홀로그램 기록 또는 재기록 방법에 관한 것이다.The present invention relates to an azobenzene compound containing nitrogen-containing heteroaromatics such as pyridine and pyrimidine, a blue hologram recording composition comprising the same, a hologram recording medium, a hologram recording material using the same, and a hologram recording or rewriting method.

빛이 사물에 맞고 반사되어 나온 파장과 세기, 위상차 정보를 모두 기록하여 사물의 완벽한 3차원 정보를 볼 수 있는 것이 홀로그램이다. 홀로그램 (hologram)의 어원은 그리스어로 holos (전체)와 gramma (정보, 메시지)의 합성어로 풀이하자면 전체의 정보를 기록한 것 이라 할 수 있다.A hologram is a hologram that records all of the wavelength, intensity, and phase difference information that light hits an object and reflects, so that you can see the perfect three-dimensional information of the object. The origin of the hologram (hologram) can be interpreted as a compound word of a gritty holos (whole) and a gramm (information messages) to Greek to as a record of the complete information.

홀로그래피는 1948년 헝가리 태생의 영국 물리학자 데니스 가보르에 의해 발견되고 명명된 기술로 피사체로 부터 반사된 물체파와 피사체 정보가 없는 기준파를 서로 간섭시켜 이때 생성된 간섭무늬를 기록하고 재생하는 방식이다. 가보르에 의해 홀로그래피가 처음 발견되었을 당시에는 레이저가 개발되기 전으로, 선명하지 못한 결과물로 인해 홀로그래피가 많은 주목을 받지 못하다가, 1960년대 이후 코히어런트한 빛을 발생시킬 수 있는 레이저가 개발되면서 비로서 선명한 홀로그램이 가능해 졌으며, 이후 본격적으로 연구되기 시작하였다.Holography is a technique discovered and named by Denis Gabor, a British physicist born in Hungary in 1948, by interfering with an object wave reflected from a subject and a reference wave without subject information to record and reproduce the generated interference pattern. . When holography was first discovered by Gabor, it was before the development of lasers, and holography did not receive much attention due to its unclear results. Clear holograms became possible as a result, and studies began in earnest afterwards.

홀로그램은 그 기록과정이 복잡하고 복제가 쉽지 않다는 점 때문에 보안 및 군사 분야에 많이 활용되고 있다. 우리나라를 비롯 여러 나라에서 고액권 지폐에 위조방지 목적으로 홀로그램을 새겨 넣고 있으며, 여권, 운전면허증과 같은 신분증에도 위변조 방지를 목적으로 사용중이다. 또한, 현재 홀로그램의 가장 큰 시장은 화장품, 주류, 의류 등에 부착되는 정품인증 마크용이다. 최근에는 유물과 보물의 복원, 교육용 컨텐츠 등으로 홀로그램이 활용되고 있다.Holograms are widely used in security and military fields because the recording process is complicated and it is not easy to duplicate. In many countries, including Korea, holograms are engraved on high denomination bills for the purpose of preventing counterfeiting, and they are also being used for the purpose of preventing counterfeiting in identification cards such as passports and driver's licenses. In addition, the largest market for holograms is for authenticity marks attached to cosmetics, alcoholic beverages, and clothing. Recently, holograms are being used for the restoration of relics and treasures, as well as educational contents.

다양한 응용분야에서 이용되는 홀로그램을 기록하는 재료는 빛에 의해 반응하여 굴절률이 변화하는 재료들이다. 현재까지 개발된 홀로그램 기록 재료들은 은염 (silver halide), DCG (dichromated gelatin), 포토레지스트 (photoresist), 광변색 물질 (photochromic), 포토폴리머, 광굴절물질 (photorefractive)등이 있다. 하지만 대부분의 재료가 미국, 러시아, 독일 등에서 개발된 재료로 불공정한 물질이전계약 (MTA) 및 비밀유지계약 (NDA)에 의해서만 공급받을 수 있고, 사용범위도 연구용으로만 제한된다.Materials for recording holograms used in various applications are materials whose refractive index changes in response to light. Hologram recording materials developed so far include silver halide, dichromated gelatin (DCG), photoresist, photochromic, photopolymer, and photorefractive. However, most materials are developed in the United States, Russia, Germany, etc., and can only be supplied under unfair material transfer agreements (MTA) and non-disclosure agreements (NDA), and the scope of use is limited only for research purposes.

앞서 기술한 홀로그램 기록 재료들은 대부분 한번 기록하고 나면 재기록이 되지 않는 단일기록 재료들이다. 실감나는 3차원 입체 영상의 디스플레이를 위해선 홀로그램 영상정보를 ?㎢? 지웠다가 가능한 재기록 재료가 반드시 필요하다. 2008년과 2010년 아리조나대학교의 페이감바리안 교수팀에서는 세계 최초로 업데이터블 홀로그램을 구현하여 보고한바 있다(비특허문헌 1, JOURNAL OF DISPLAY TECHNOLOGY, VOL. 6, NO. 10, OCTOBER 2010, Materials for an Updatable Holographic 3D Display). 이들은 NLO 염료를 사용한 광굴절 조성물을 기록 매질로 사용하였는데, 전기장하에서 레이저를 조사하여 전기광학 (electro-optic)효과에 의해 굴절율 차이를 줄 수 있음에 착안하였다. 당시 이들이 보고한 동영상 구현 수준은 2초에 한번 화면이 바뀌는 수준이었지만, 현재 고출력 레이저 및 광학계 설계 그리고 광굴절 조성물의 최적화를 통해 화면전환 속도를 높이는 연구를 진행중에 있다.Most of the hologram recording materials described above are single recording materials that cannot be rewritten once recorded. In order to display realistic 3D stereoscopic images, holographic image information is converted to ?㎢? Erasable and rewritable material is essential. In 2008 and 2010, Professor Paygambarian's team at the University of Arizona implemented and reported the world's first updateable hologram (Non-Patent Document 1, JOURNAL OF DISPLAY TECHNOLOGY, VOL. 6, NO. 10, OCTOBER 2010, Materials for an Updatable Holographic 3D Display). They used a photorefractive composition using NLO dye as a recording medium, and they paid attention to the fact that a refractive index difference could be given by an electro-optic effect by irradiating a laser under an electric field. At the time, the video implementation level they reported was that the screen changed once every 2 seconds, but research is currently underway to increase the screen conversion speed by designing high-power lasers and optical systems and optimizing the photorefractive composition.

산업 분야에서 다양한 염료로 사용되어온 아조벤젠은 빛에 의해 trans-cis 이성질화가 가능한 분자로 빛에 의해 이성질화 되면 기하학적 모양이 바뀌게 되고 이에 따라 그 구조뿐만 아니라 빛의 흡수 및 발광, 굴절률 등과 같은 광학적 성질이 변화하며 이를 활용한 소자 적용 연구가 많이 되어왔다. 홀로그램 재기록 재료로서 아조벤젠 화합물을 적용한 연구가 많이 되어 왔다. 하지만, 기록 및 재생하는 레이저 파장과의 불일치로 그 회절효율이 낮거나, 기록/재기록시 높은 에너지의 광조사를 필요로 하거나 동적 특성이 현저히 낮았다.Azobenzene, which has been used as a variety of dyes in the industrial field, is a molecule capable of trans-cis isomerization by light. When isomerized by light, the geometric shape changes. There have been many researches on device application utilizing this change. A lot of research has been done on applying an azobenzene compound as a hologram rewritable material. However, the diffraction efficiency was low due to the discrepancy with the laser wavelength for recording and reproducing, or it required high-energy light irradiation during recording/rewriting, or the dynamic characteristics were remarkably low.

이에, 본 발명자들은 홀로그램의 기록 및 재기록이 가능한 고분자 화합물에 대한 연구를 수행하던 중, 본 발명에 따른 아조벤젠 단량체를 포함하는 고분자가 홀로그램 기록 레이저 파장에서 광 이성질화의 등흡수점이 있어, 기록 레이저 조사에 의해 동적특성이 매우 우수하게 홀로그램의 기록 및 재기록이 가능한 것을 알아내어 본 발명을 완성하였다.Accordingly, while the present inventors were conducting research on a polymer compound capable of recording and rewriting holograms, the polymer containing the azobenzene monomer according to the present invention has an isomerization point of photoisomerization at the wavelength of the hologram recording laser, recording laser irradiation The present invention was completed by finding out that recording and rewriting of holograms were possible with very excellent dynamic characteristics.

본 발명의 일 측면에서의 목적은 함질소 헤테로방향족 포함 아조벤젠 단량체를 제공하는데 있다.It is an object of the present invention to provide an azobenzene monomer comprising a nitrogen-containing heteroaromatic.

본 발명의 다른 일 측면에서의 목적은 상기 아조벤젠 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 형성되는 고분자를 제공하는데 있다.Another object of the present invention is to provide a polymer formed by polymerization of the azobenzene monomer and a monomer having a vinyl acryl group.

본 발명의 또 다른 일 측면에서의 목적은 상기 아조벤젠 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 형성되는 고분자를 포함하는 광 굴절율 변조 중합체 조성물을 제공하는데 있다.Another object of the present invention is to provide a light refractive index modulating polymer composition comprising a polymer formed by polymerization of the azobenzene monomer and a monomer having a vinyl acryl group.

본 발명의 다른 일 측면에서의 목적은 상기 아조벤젠 단량체 및 바이닐 아크릴기를 가지는 단량체의 중합에 의해 형성되는 고분자를 포함하는 홀로그램 기록용 조성물을 제공하는데 있다.Another object of the present invention is to provide a hologram recording composition comprising a polymer formed by polymerization of the azobenzene monomer and a monomer having a vinyl acryl group.

본 발명의 또 다른 일 측면에서의 목적은 상기 홀로그램 기록용 조성물로 이루어진 기록층이 기판 위에 형성된 홀로그램 기록 매체를 제공하는데 있다.Another object of the present invention is to provide a hologram recording medium in which a recording layer made of the hologram recording composition is formed on a substrate.

본 발명의 다른 일 측면에서의 목적은 상기 고분자를 사용한 홀로그램 기록 방법을 제공하는데 있다.Another object of the present invention is to provide a hologram recording method using the polymer.

본 발명의 또 다른 일 측면에서의 목적은 상기 홀로그램 기록 매체 상에 홀로그램 재기록 방법을 제공하는데 있다.Another object of the present invention is to provide a hologram re-recording method on the hologram recording medium.

상기 목적을 달성하기 위하여,In order to achieve the above object,

본 발명의 일 측면은,One aspect of the present invention is

하기 화학식 1로 표시되는 아조벤젠 단량체를 제공한다.An azobenzene monomer represented by the following Chemical Formula 1 is provided.

[화학식 1][Formula 1]

Figure 112019120568208-pat00001
Figure 112019120568208-pat00001

상기 화학식 1에서,In Formula 1,

R1은 수소, 또는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬이고, 상기 n은 1 내지 4의 정수이고;R 1 is hydrogen or straight-chain or branched C 1-20 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer from 1 to 4;

R2는 질소를 하나 이상 포함하는 5 내지 10 원자의 헤테로아릴이고;R 2 is 5 to 10 membered heteroaryl containing at least one nitrogen;

L은 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬렌이고; 및 L is straight or branched C 1-20 alkylene unsubstituted or substituted with one or more fluoro; and

Q는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기이다.Q is a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.

본 발명의 다른 일 측면은,Another aspect of the present invention is

상기 화학식 1로 표시되는 아조벤젠 단량체; 및 바이닐 아크릴기를 가지는 단량체;의 중합에 의해 형성되는 고분자를 제공한다.an azobenzene monomer represented by Formula 1; and a monomer having a vinyl acryl group; provides a polymer formed by polymerization.

본 발명의 또 다른 일 측면은,Another aspect of the present invention is

상기 고분자를 포함하는 광 굴절율 변조 중합체 조성물을 제공한다.It provides a light refractive index modulating polymer composition comprising the polymer.

본 발명의 다른 일 측면은, Another aspect of the present invention is

상기 고분자를 포함하는 홀로그램 기록용 조성물을 제공한다.There is provided a hologram recording composition comprising the polymer.

본 발명의 또 다른 일 측면은,Another aspect of the present invention is

상기 홀로그램 기록용 조성물로 이루어진 기록층이 기판 위에 형성된 홀로그램 기록 매체를 제공한다.There is provided a hologram recording medium in which a recording layer made of the hologram recording composition is formed on a substrate.

본 발명의 다른 일 측면은,Another aspect of the present invention is

상기 고분자로 박막을 제조하는 단계(단계 1); 및preparing a thin film from the polymer (step 1); and

상기 단계 1에서 제조한 박막에 레이저 회절무늬를 조사하는 단계(단계 2);를 포함하는 홀로그램 기록 방법을 제공한다.It provides a hologram recording method comprising; irradiating a laser diffraction pattern on the thin film prepared in step 1 (step 2).

본 발명의 또 다른 일 측면은,Another aspect of the present invention is

상기 홀로그램 기록 매체에 홀로그램을 기록할 때 사용된 기준광만을, 상기 홀로그램 기록 매체에 조사하는 단계를 포함하는 홀로그램 재기록 방법을 제공한다.Provided is a hologram re-recording method comprising irradiating only a reference light used when recording a hologram on the hologram recording medium to the hologram recording medium.

본 발명의 아조벤젠 단량체 화합물은 청색 레이저의 파장 (460 nm) 근처에서 광 이성질화의 등흡수점이 존재하고, 광 조사에 의해서 굴절율 변화를 크게 할 수 있는 고복굴절율 부분을 포함하고 있어 아조벤젠 단량체 화합물을 포함하는 고분자는 청색 레이저 조사에 의한 홀로그램 기록/재기록 소재로 유용하게 사용될 수 있다.The azobenzene monomer compound of the present invention has an isomerization point of photoisomerization near the wavelength of the blue laser (460 nm) and contains a high birefringence part capable of increasing the refractive index change by light irradiation, so it contains an azobenzene monomer compound Polymers can be usefully used as hologram recording/rewriting materials by blue laser irradiation.

도 1은 본 발명에 따른 고분자 화합물의 시스-트란스 이성질화 후 자외선-가시광선 흡수 스펙트럼을 나타낸 그래프이다.
도 2는 본 발명에 따른 고분자 화합물의 회절효율을 측정한 결과를 나타낸 그래프이다.
도 3은 본 발명에 따른 아조벤젠 고분자 필름의 청색 레이저로 기록한 홀로그램의 회절효율을 나타낸 그래프이다.
도 4는 Four wave mixing(FWM)의 개념도를 나타낸 그림이다.1 is a graph showing the ultraviolet-visible absorption spectrum after cis-trans isomerization of the polymer compound according to the present invention.
2 is a graph showing the results of measuring the diffraction efficiency of the polymer compound according to the present invention.
3 is a graph showing the diffraction efficiency of a hologram recorded with a blue laser of an azobenzene polymer film according to the present invention.
4 is a diagram showing a conceptual diagram of Four wave mixing (FWM).

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

한편, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. 또한, 본 발명의 실시 형태는 당해 기술분야에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다.On the other hand, the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided in order to more completely explain the present invention to those of ordinary skill in the art.

나아가, 명세서 전체에서 어떤 구성요소를 "포함"한다는 것은 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.Furthermore, "including" a certain component throughout the specification means that other components may be further included, rather than excluding other components, unless otherwise stated.

본 발명의 일 측면은,One aspect of the present invention is

하기 화학식 1로 표시되는 아조벤젠 단량체를 제공한다.An azobenzene monomer represented by the following Chemical Formula 1 is provided.

[화학식 1][Formula 1]

Figure 112019120568208-pat00002
Figure 112019120568208-pat00002

상기 화학식 1에서,In Formula 1,

R1은 수소, 또는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬이고, 상기 n은 1 내지 4의 정수이고;R 1 is hydrogen or straight-chain or branched C 1-20 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer from 1 to 4;

R2는 질소를 하나 이상 포함하는 5 내지 10 원자의 헤테로아릴이고;R 2 is 5 to 10 membered heteroaryl containing at least one nitrogen;

L은 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬렌이고; 및 L is straight or branched C 1-20 alkylene unsubstituted or substituted with one or more fluoro; and

Q는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기이다.Q is a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.

바람직하게는,Preferably,

R1은 수소, 또는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-10알킬이고, 상기 n은 1 내지 3의 정수이고;R 1 is hydrogen or straight or branched C 1-10 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer from 1 to 3;

R2는 질소를 하나 이상 포함하는 6 원자의 헤테로아릴이고;R 2 is 6 membered heteroaryl containing at least one nitrogen;

L은 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-10알킬렌이고; 및 L is straight or branched C 1-10 alkylene unsubstituted or substituted with one or more fluoro; and

Q는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기일 수 있다.Q may be a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.

더욱 바람직하게는,More preferably,

R1은 수소, 또는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-5알킬이고, 상기 n은 1 내지 2의 정수이고;R 1 is hydrogen or straight-chain or branched C 1-5 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer from 1 to 2;

R2는 피리딘, 또는 피리미딘이고;R 2 is pyridine or pyrimidine;

L은 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-6알킬렌이고; 및 L is straight or branched C 1-6 alkylene unsubstituted or substituted with one or more fluoro; and

Q는

Figure 112019120568208-pat00003
,
Figure 112019120568208-pat00004
,
Figure 112019120568208-pat00005
,
Figure 112019120568208-pat00006
,
Figure 112019120568208-pat00007
,
Figure 112019120568208-pat00008
,
Figure 112019120568208-pat00009
,
Figure 112019120568208-pat00010
,
Figure 112019120568208-pat00011
,
Figure 112019120568208-pat00012
또는
Figure 112019120568208-pat00013
일 수 있다.Q is
Figure 112019120568208-pat00003
,
Figure 112019120568208-pat00004
,
Figure 112019120568208-pat00005
,
Figure 112019120568208-pat00006
,
Figure 112019120568208-pat00007
,
Figure 112019120568208-pat00008
,
Figure 112019120568208-pat00009
,
Figure 112019120568208-pat00010
,
Figure 112019120568208-pat00011
,
Figure 112019120568208-pat00012
or
Figure 112019120568208-pat00013
can be

상기 R1은 아조(-N=N-)기에 대하여 메타(meta) 위치에 치환된 것일 수 있다.The R 1 may be substituted at the meta position with respect to the azo (-N=N-) group.

가장 바람직하게는,Most preferably,

상기 화학식 1로 표시되는 아조벤젠 단량체는, 하기 화합물 군으로부터 선택되는 어느 하나의 화합물일 수 있다.The azobenzene monomer represented by Formula 1 may be any one compound selected from the following compound group.

Figure 112019120568208-pat00014
,
Figure 112019120568208-pat00015
,
Figure 112019120568208-pat00016
,
Figure 112019120568208-pat00017
,
Figure 112019120568208-pat00018
,
Figure 112019120568208-pat00019
및
Figure 112019120568208-pat00020
.
Figure 112019120568208-pat00014
,
Figure 112019120568208-pat00015
,
Figure 112019120568208-pat00016
,
Figure 112019120568208-pat00017
,
Figure 112019120568208-pat00018
,
Figure 112019120568208-pat00019
and
Figure 112019120568208-pat00020
.

본 발명에 따른 단량체는 청색 파장 영역인 약 460 nm의 파장에서 등흡수점이 나타남으로써, 청색 색상을 기록하는 홀로그램용 조성물로 유용하게 사용될 수 있다.The monomer according to the present invention can be usefully used as a composition for a hologram that records blue color because the isosorption point appears at a wavelength of about 460 nm, which is a blue wavelength region.

본 발명의 일 측면은,One aspect of the present invention is

상기 화학식 1로 표시되는 아조벤젠 단량체; 및 바이닐 아크릴기를 가지는 단량체;의 중합에 의해 형성되는 고분자를 제공한다. 상기 고분자는 상기 화학식 1로 표시되는 아조벤젠 단량체 내 Q의 이중결합과, 상기 바이닐 아크릴기를 가지는 단량체 내 바이닐기가 중합 반응되어 형성될 수 있다.an azobenzene monomer represented by Formula 1; and a monomer having a vinyl acryl group; provides a polymer formed by polymerization. The polymer may be formed by a polymerization reaction between the double bond of Q in the azobenzene monomer represented by Formula 1 and the vinyl group in the monomer having the vinyl acryl group.

본 발명에 따른 고분자는 상기 화학식 1로 표시되는 아조벤젠 단량체와 바이닐 아크릴기를 가지는 단량체와 공중합체를 형성할 수 있다.The polymer according to the present invention may form a copolymer with the azobenzene monomer represented by Formula 1 and a monomer having a vinyl acryl group.

본 발명에 따른 고분자에 있어서, 상기 바이닐 아크릴기를 가지는 단량체로는, 라디칼 메커니즘에 의하여 중합될 수 있는 불포화 이중결합을 적어도 하나 함유하는 단량체 및 터미날 또는 펜던트 에틸렌성 불포화 결합을 포함하는 단량체를 포함할 수 있다. 구체적으로, 상기 화학식 1로 표시되는 아조벤젠 단량체의 Q인 광가교성 관능기와 광중합을 수행할 수 있는 단량체이면 특히 제한되지 않으나, 바이닐 아크릴기를 가지는 단량체가 바람직하고, 예를 들면, 바이닐아크릴레이트, 바이닐메타크릴레이트, 바이닐에틸아크릴레이트, 바이닐에틸메타크릴레이트, 바이닐옥틸메타크릴레이트, 바이닐헥실메타크릴레이트, 바이닐부틸메타크릴레이트 등을 들 수 있다.In the polymer according to the present invention, the monomer having the vinyl acryl group may include a monomer containing at least one unsaturated double bond that can be polymerized by a radical mechanism and a monomer containing a terminal or pendant ethylenically unsaturated bond. have. Specifically, it is not particularly limited as long as it is a monomer capable of photopolymerization with a photocrosslinkable functional group that is Q of the azobenzene monomer represented by Formula 1, but is preferably a monomer having a vinyl acryl group, for example, vinyl acrylate, vinyl meta A acrylate, vinyl ethyl acrylate, vinyl ethyl methacrylate, vinyl octyl methacrylate, vinyl hexyl methacrylate, vinyl butyl methacrylate, etc. are mentioned.

본 발명에 따른 고분자는 상기 화학식 1로 표시되는 아조벤젠 단량체 A와 바이닐 아크릴기를 가지는 단량체 B의 공중합 배열이 AAAAAA-BBBBBB-와 같은 블록 연쇄를 형성하는 블록 공중합체일 수 있고, ABAABABABBA-와 같은 랜덤 연쇄를 형성하는 랜덤 공중합체 일 수 있다. 상기 단량체의 배열은 목적하는 굴절률의 증가와 물성을 고려하여 적절하게 이용할 수 있다.The polymer according to the present invention may be a block copolymer in which the copolymerization arrangement of the azobenzene monomer A represented by Formula 1 and the monomer B having a vinyl acryl group forms a block chain such as AAAAAA-BBBBBB-, and random chain such as ABAABABABBA- It may be a random copolymer that forms The arrangement of the monomers may be appropriately used in consideration of a desired increase in refractive index and physical properties.

또한, 본 발명에 따른 고분자는 상기 화학식 1로 표시되는 아조벤젠 단량체와 바이닐 아크릴기를 가지는 단량체의 비율은, 고분자에 광 조사 전후에 원하는 굴절률 변화가 얻어지는 범위라면 특히 한정되지 않으나, 상기 화학식 1로 표시되는 아조벤젠 단량체가 단량체 전체의 0.5 내지 20 몰%, 바람직하게는 1 내지 15 몰%, 보다 바람직하게는 1 내지 10 몰%이다. 상기 화학식 1로 표시되는 아조벤젠 단량체가 단량체 전체의 0.5 몰% 미만이면 광에 감응하는 정도가 너무 낮아 홀로그램이 기록되는데 너무 많은 에너지가 필요하게 되고, 20 몰%을 초과하면 홀로그램 재생 시 사용하는 파장의 빛을 흡수하여 효율이 급격히 저하될 수 있다.In addition, in the polymer according to the present invention, the ratio of the azobenzene monomer and the monomer having a vinyl acryl group represented by Formula 1 is not particularly limited as long as a desired refractive index change is obtained before and after light irradiation to the polymer, but is represented by Formula 1 The amount of the azobenzene monomer is 0.5 to 20 mol%, preferably 1 to 15 mol%, more preferably 1 to 10 mol% of the total monomer. If the azobenzene monomer represented by Formula 1 is less than 0.5 mol% of the total monomer, the degree of sensitivity to light is too low, and too much energy is required to record the hologram. Absorbing light can lead to a sharp decrease in efficiency.

나아가, 본 발명에 따른 고분자는 상기 화학식 1로 표시되는 아조벤젠 단량체와 바이닐 아크릴기를 가지는 단량체를 통상의 중합 반응을 통하여 얻을 수 있으나, 아조비스아이소부틸로나이트릴(AIBN)과 같은 라디칼 개시제를 사용하여 라디칼 중합 반응을 통하여 제조하는 것이 바람직하다.Furthermore, the polymer according to the present invention can be obtained through a conventional polymerization reaction of the azobenzene monomer and the monomer having a vinyl acryl group represented by Formula 1, but using a radical initiator such as azobisisobutylonitrile (AIBN) It is preferable to prepare it through a radical polymerization reaction.

본 발명에 따른 고분자는 청색파장의 광이 조사되면 아조벤젠 구조가 시스-트랜스 이성질화하여, 광의 조사 전·후에 굴절율이 변조되는 성질을 갖고 있으며, 이때, 굴절율 변화는 0.01 내지 0.04 을 나타낸다.When the polymer according to the present invention is irradiated with light of a blue wavelength, the azobenzene structure is cis-trans isomerized, and the refractive index is modulated before and after the light is irradiated. In this case, the refractive index change is 0.01 to 0.04.

또한, 본 발명은 아조벤젠 고분자를 포함하는 광 굴절율 변조 중합체 조성물을 제공한다. 본 발명에 따른 광 굴절율 변조 중합체 조성물은, 상술한 바와 같이, 청색파장의 빛을 흡수하여 광 이성질화가 일어나고, 적은 양의 광조사에 의해서도 굴절율 변화를 크게 할 수 있는 고복굴절율 부분을 가지는 아조벤젠 고분자를 포함하며, 필요에 따라, 광 개시제, 증감제 및 연쇄 이동제로부터 선택되는 1종 이상의 첨가제를 포함시킬 수 있다. 이들의 첨가제를 포함시킴으로써, 화학식 1로 표시되는 아조벤젠 단량체의 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기의 빛의 조사에 의한 가교 반응성을 향상시킬 수 있으며, 이에 따라 굴절률의 증가 변조를 보다 바람직하게 발생시킬 수 있다.In addition, the present invention provides a light refractive index modulating polymer composition comprising an azobenzene polymer. As described above, the light refractive index modulating polymer composition according to the present invention is an azobenzene polymer having a high birefringence portion capable of absorbing light of a blue wavelength to cause photoisomerization and increasing the refractive index change even with a small amount of light irradiation. and, if necessary, at least one additive selected from a photoinitiator, a sensitizer, and a chain transfer agent may be included. By including these additives, crosslinking reactivity by irradiation of light of a photocrosslinkable functional group containing at least one radically polymerizable double bond in the molecule of the azobenzene monomer represented by Formula 1 can be improved, and accordingly, increase modulation of the refractive index can be generated more preferably.

나아가, 본 발명은 상술한 광 굴절률 변조 중합체 조성물에 빛을 조사하여 굴절률을 변조하는 단계를 포함하는 굴절률 제어 방법을 제공한다. Further, the present invention provides a refractive index control method comprising the step of modulating the refractive index by irradiating light to the above-described light refractive index modulating polymer composition.

구체적으로, 본 발명의 굴절률 제어 방법은, 상기 광 굴절률 변조 중합체 조성물을 사용하여 적절한 성형 처리를 실시한 후, 빛을 조사할 수 있다. Specifically, the refractive index control method of the present invention may be irradiated with light after performing an appropriate molding treatment using the light refractive index modulating polymer composition.

본 발명에 따른 굴절률 제어 방법에 있어서, 상기 굴절률을 변조하기 위한 빛으로서, 바람직한 광의 파장은 약 460 nm 이며, 광의 강도는 통상적으로 1000 mJ/cm2 내지 100 mJ/cm2 이고, 바람직하게는 50 ~ 300 mJ/cm2 이나 이에 한정되지 않는다.In the method for controlling the refractive index according to the present invention, as the light for modulating the refractive index, the preferred wavelength of light is about 460 nm, and the intensity of light is usually 1000 mJ/cm 2 to 100 mJ/cm 2 , preferably 50 ~ 300 mJ/cm 2 but not limited thereto.

본 발명의 다른 일 측면은,Another aspect of the present invention is

아조벤젠 고분자를 포함하는 홀로그램 기록용 조성물을 제공한다.Provided is a composition for recording a hologram comprising an azobenzene polymer.

본 발명에 따른 홀로그램 기록용 조성물은, 상술한 바와 같이, 청색 파장의 빛을 흡수하여 광 이성질화가 일어나고, 적은 양의 광조사에 의해서도 굴절율 변화를 크게 할 수 있는 고복굴절율 부분을 가지는 아조벤젠 고분자를 포함하며, 이에 의해 고회절 효율, 고투명성 및 재생 파장 재현성이 우수한 부피 위상형 홀로그램을 형성할 수 있다. 또한, 본 발명에 따른 홀로그램 기록용 조성물은 홀로그램 기록 매체의 내후성, 내열성, 화학적 안정성, 보존 안정성 등을 향상시키기 위하여 본 기술분야에서 공지된 가소제, 증점제, 열중합 금지제, 연쇄 이동제 등의 통상적인 첨가제를 포함할 수 있다. 이때, 상기 첨가제는 본 발명에 따른 단량체 또는 고분자와 비반응성으로 본 발명의 효과를 벗어나지 않도록 첨가할 수 있다. 상기 홀로그램 기록용 조성물은 400 내지 600 nm의 파장을 흡수할 수 있다.As described above, the composition for hologram recording according to the present invention comprises an azobenzene polymer having a high birefringence portion that absorbs light of a blue wavelength to cause photoisomerization and can increase the refractive index change even with a small amount of light irradiation. and, thereby, it is possible to form a volume phase hologram excellent in high diffraction efficiency, high transparency, and reproduction wavelength reproducibility. In addition, the composition for hologram recording according to the present invention is a conventional plasticizer, thickener, thermal polymerization inhibitor, chain transfer agent, etc. known in the art in order to improve the weather resistance, heat resistance, chemical stability, storage stability, etc. of the hologram recording medium. Additives may be included. In this case, the additive may be added so as not to deviate from the effects of the present invention because it is non-reactive with the monomer or polymer according to the present invention. The hologram recording composition may absorb a wavelength of 400 to 600 nm.

본 발명의 다른 일 측면은,Another aspect of the present invention is

상기 홀로그램 기록용 조성물로 이루어진 기록층이 기판 위에 형성된 홀로그램 기록 매체를 제공한다.There is provided a hologram recording medium in which a recording layer made of the hologram recording composition is formed on a substrate.

본 발명에 따른 홀로그램 기록 매체에 있어서, 기판은 광학적으로 투명한 재료가 바람직하고, 특히 한정되지 않으나, 예를 들면 유리판, PET 판 또는 필름, 폴리카보네이트 판 또는 필름, 폴리메틸메타크릴레이트판 또는 필름과 같은 플라스틱판 또는 필름일 수 있다. 기판의 두께는 0.01 ~ 10mm 일 수 있고, 기판은 평면인 것이 통상적이나, 필요에 따라서는 굴곡되어 있거나 또는 표면에 요철구조를 가질 수 있다.In the hologram recording medium according to the present invention, the substrate is preferably an optically transparent material, and is not particularly limited, but for example, a glass plate, a PET plate or film, a polycarbonate plate or film, a polymethyl methacrylate plate or a film and It may be the same plastic plate or film. The thickness of the substrate may be 0.01 to 10 mm, and the substrate is usually flat, but if necessary, it may be curved or have an uneven structure on the surface.

본 발명의 다른 일 측면은,Another aspect of the present invention is

상기 고분자로 박막을 제조하는 단계(단계 1); 및preparing a thin film from the polymer (step 1); and

상기 단계 1에서 제조한 박막에 레이저 회절무늬를 조사하는 단계(단계 2);를 포함하는 홀로그램 기록 방법을 제공한다.It provides a hologram recording method comprising; irradiating a laser diffraction pattern on the thin film prepared in step 1 (step 2).

본 발명에 따른 홀로그램 기록 방법에 있어서, 단계 1은 상기 아조벤젠 단량체를 포함하는 고분자를 박막으로 제조하는 단계이다.In the hologram recording method according to the present invention, step 1 is a step of preparing the polymer including the azobenzene monomer into a thin film.

구체적으로, 고분자를 박막으로 제조하는 방법은, 스핀 코팅, 바 코팅, 딥 코팅 등의 고분자를 기판에 코팅하는 방법이라면 특히 제한되지 않는다. 또한, 기판의 한 면에 코팅시켜 제조할 수도 있고, 기판과 기판 사이에 고분자를 샌드위치 형태로 코팅시켜 제조할 수도 있다.Specifically, the method of manufacturing the polymer into a thin film is not particularly limited as long as it is a method of coating a polymer such as spin coating, bar coating, or dip coating on a substrate. In addition, it may be prepared by coating on one side of the substrate, or may be prepared by coating a polymer in a sandwich form between the substrate and the substrate.

본 발명에 따른 홀로그램 기록 방법에 있어서, 단계 2는 상기 단계 1에서 제조된 박막에 레이저 회절무늬를 조사하는 단계이다.In the hologram recording method according to the present invention, step 2 is a step of irradiating a laser diffraction pattern on the thin film prepared in step 1 above.

이때, 상기 회절 무늬는 아날로그 홀로그램을 기록할 경우에는 기준광과 물체광의 간섭에 의한 회절 무늬, 디지털 홀로그램을 기록할 경우에는 컴퓨터로 생성된 회절무늬일 수 있다.In this case, the diffraction pattern may be a diffraction pattern caused by interference between reference light and object light when an analog hologram is recorded, or a computer generated diffraction pattern when recording a digital hologram.

본 발명의 다른 일 측면은,Another aspect of the present invention is

상기 홀로그램 기록 매체에 홀로그램을 기록할 때 사용된 기준광만을, 상기 홀로그램 기록 매체에 조사하는 단계를 포함하는 홀로그램 재기록 방법을 제공한다. 상기 홀로그램은 상기 간섭무늬가 기준광을 회절시킴으로써 재기록될 수 있다. 이러한 홀로그램 재기록 방법은 홀로그램 기록 방법과 함께 본 기술분야에서 잘 알려져 있으므로 상세한 설명은 생략한다.Provided is a hologram re-recording method comprising irradiating only a reference light used when recording a hologram on the hologram recording medium to the hologram recording medium. The hologram may be rewritten by diffracting the reference light by the interference fringe. Since such a hologram rewriting method is well known in the art along with the hologram recording method, a detailed description thereof will be omitted.

본 발명의 아조벤젠 단량체 화합물은 청색 레이저의 파장 (460 nm) 근처에서 광 이성질화의 등흡수점이 존재하고, 광 조사에 의해서 굴절율 변화를 크게 할 수 있는 고복굴절율 부분을 포함하고 있어 아조벤젠 단량체 화합물을 포함하는 고분자는 청색 레이저 조사에 의한 홀로그램 기록/재기록 소재로 유용하게 사용될 수 있으며, 이는 후술하는 실시예, 실험예에 뒷받침된다.The azobenzene monomer compound of the present invention has an isomerization point of photoisomerization near the wavelength of the blue laser (460 nm) and contains a high birefringence part capable of increasing the refractive index change by light irradiation, so it contains an azobenzene monomer compound This polymer can be usefully used as a hologram recording/rewriting material by blue laser irradiation, which is supported by Examples and Experimental Examples to be described later.

이하, 본 발명을 실시예 및 실험예를 통해 상세히 설명한다.Hereinafter, the present invention will be described in detail through Examples and Experimental Examples.

단, 후술하는 실시예 및 실험예는 본 발명을 일 측면에서 구체적으로 예시하는 것일 뿐, 본 발명이 이에 한정되는 것은 아니다.However, the Examples and Experimental Examples to be described below are merely illustrative of the present invention in detail in one aspect, and the present invention is not limited thereto.

<실시예 1> 4-(6-메타아크릴로옥시헥실옥시)-4'-(4-피리딜)에틴일-3'-메틸아조벤젠의 제조<Example 1> Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(4-pyridyl)ethynyl-3'-methylazobenzene

Figure 112019120568208-pat00021
Figure 112019120568208-pat00021

단계 1 : 4-하이드로옥시-4'-아이오도-3'-메틸아조벤젠의 제조Step 1: Preparation of 4-hydrooxy-4'-iodo-3'-methylazobenzene

반응 용기에 4-아이오도-3-메틸아닐린 5 g (21.45 mmol) 을 아세톤 10 mL 에 녹인 후 0 ℃ 이하에서 교반하며 48% HBF4 20 mL 을 천천히 첨가하였다. 고체가 생성되면 아질산나트륨 2.96 g (42.9 mmol) 을 소량의 증류수에 녹여 반응 용기에 천천히 적가하였다. 0 ℃에서 1 시간 동안 교반 하고, 필터하여 고체를 수득하였다. 얻어진 고체 7 g (15.06 mmol) 를 증류수에 0 ℃ 이하에서 녹이고, 페놀 2.98 g (22.6 mmol), 아세트산나트륨 1.73 g (15.06 mmol) 을 소량의 증류수에 녹여 반응 용기에 천천히 적가하고, 상온에서 7시간 동안 교반한 후, 필터하여 목표화합물 (4.38 g, 64%) 을 얻었다.In a reaction vessel, 5 g (21.45 mmol) of 4-iodo-3-methylaniline was dissolved in 10 mL of acetone, and then 20 mL of 48% HBF 4 was slowly added while stirring at 0 °C or lower. When a solid was formed, 2.96 g (42.9 mmol) of sodium nitrite was dissolved in a small amount of distilled water and slowly added dropwise to the reaction vessel. The mixture was stirred at 0 °C for 1 hour and filtered to obtain a solid. 7 g (15.06 mmol) of the obtained solid was dissolved in distilled water at 0° C. or lower, and 2.98 g (22.6 mmol) of phenol and 1.73 g (15.06 mmol) of sodium acetate were dissolved in a small amount of distilled water and slowly added dropwise to a reaction vessel at room temperature for 7 hours. After stirring for a while, it was filtered to obtain the target compound (4.38 g, 64%).

1H NMR (500 MHz, CDCl3) δ 7.94 (d, J = 8.4 Hz, 1H), 7.90 - 7.83 (m, 2H), 7.73 (dd, J = 2.4, 0.8 Hz, 1H), 7.39 (dd, J = 8.5, 2.4 Hz, 1H), 6.94 (d, J = 8.8 Hz, 2H), 5.24 (s, 1H), 2.53 (s, 3H). 1 H NMR (500 MHz, CDCl 3 ) δ 7.94 (d, J = 8.4 Hz, 1H), 7.90 - 7.83 (m, 2H), 7.73 (dd, J = 2.4, 0.8 Hz, 1H), 7.39 (dd, J = 8.5, 2.4 Hz, 1H), 6.94 (d, J = 8.8 Hz, 2H), 5.24 (s, 1H), 2.53 (s, 3H).

단계 2 : 4-(6-하이드로옥시헥실옥시)-4'-아이오도-3'-메틸아조벤젠의 제조Step 2: Preparation of 4-(6-hydrooxyhexyloxy)-4'-iodo-3'-methylazobenzene

반응 용기에 4-하이드로옥시-4'-아이오도-3'-메틸아조벤젠 4.38 g (12.9 mmol), 탄산칼륨 5.38 g (38.7 mmol) 을 DMF 40 mL 에 녹이고, 질소 분위기 하에서 90 ℃에서 18 시간 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물에 과량의 증류수를 부어 반응을 종료하고 초산 에틸로 추출하였다. 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 5:1) 로 분리하여 주황색의 고체 (3.54 g, 63%) 를 수득하였다.In a reaction vessel, 4.38 g (12.9 mmol) of 4-hydrooxy-4'-iodo-3'-methylazobenzene and 5.38 g (38.7 mmol) of potassium carbonate were dissolved in 40 mL of DMF, and under a nitrogen atmosphere at 90° C. for 18 hours. stirred. After cooling to room temperature, excess distilled water was poured into the reaction mixture to complete the reaction, and extraction was performed with ethyl acetate. After evaporating all of the solvent, separation was performed by column chromatography (hexane/ethyl acetate = 5:1) to obtain an orange solid (3.54 g, 63%).

1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.4 Hz, 1H), 7.91 - 7.87 (m, 2H), 7.73 (d, J = 2.4 Hz, 1H), 7.39 (dd, J = 8.4, 2.4 Hz, 1H), 7.03 - 6.96 (m, 2H), 4.05 (t, J = 6.5 Hz, 2H), 3.72 - 3.64 (t, 2H), 2.52 (s, 3H), 1.89 - 1.80 (m, 2H), 1.62 (m, J = 14.3, 6.7 Hz, 2H), 1.53 (m, J = 9.0, 4.5, 3.1 Hz, 2H), 1.50 - 1.43 (m, 2H). 1 H NMR (500 MHz, CDCl 3 ) δ 7.93 (d, J = 8.4 Hz, 1H), 7.91 - 7.87 (m, 2H), 7.73 (d, J = 2.4 Hz, 1H), 7.39 (dd, J = 8.4, 2.4 Hz, 1H), 7.03 - 6.96 (m, 2H), 4.05 (t, J = 6.5 Hz, 2H), 3.72 - 3.64 (t, 2H), 2.52 (s, 3H), 1.89 - 1.80 (m , 2H), 1.62 (m, J = 14.3, 6.7 Hz, 2H), 1.53 (m, J = 9.0, 4.5, 3.1 Hz, 2H), 1.50 - 1.43 (m, 2H).

단계 3 : 4-(6-하이드로옥시헥실옥시)-4'-(4-피리딜)에틴일-3'-메틸아조벤젠의 제조Step 3: Preparation of 4-(6-hydrooxyhexyloxy)-4'-(4-pyridyl)ethynyl-3'-methylazobenzene

반응 용기에 4-(6-하이드로옥시헥실옥시)-4'-아이오도-3'-메틸아조벤젠 5 g (11.4 mmol) 을 테트라하이드로퓨란 20 mL, 트리에틸아민 20 mL 에 녹이고 산소를 제거하며 질소분위기 하에서 트리페닐포스핀 0.3 g (1.14 mmol), 비스(트리페닐포스핀)팔라듐(II) 클로라이드 0.8 g (1.14 mmol), 요오드화구리 0.3256 g (1.71 mmol) 을 순차적으로 첨가한 후, 80 ℃로 온도를 높여주었다. 80 ℃에서 소량의 테트라하이드로퓨란에 녹인 4-에틴일피리딘 1.175 g (11.4 mmol) 을 천천히 적가하고 24시간 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 3:1) 로 분리하여 주황색의 고체 (2.5 g, 53%) 를 수득하였다.In a reaction vessel, 5 g (11.4 mmol) of 4-(6-hydrooxyhexyloxy)-4'-iodo-3'-methylazobenzene was dissolved in 20 mL of tetrahydrofuran and 20 mL of triethylamine, and oxygen was removed. After sequentially adding 0.3 g (1.14 mmol) of triphenylphosphine, 0.8 g (1.14 mmol) of bis(triphenylphosphine) palladium (II) chloride, and 0.3256 g (1.71 mmol) of copper iodide under a nitrogen atmosphere, 80° C. raised the temperature with 1.175 g (11.4 mmol) of 4-ethynylpyridine dissolved in a small amount of tetrahydrofuran at 80° C. was slowly added dropwise and stirred for 24 hours. After cooling to room temperature, the reaction mixture was extracted with methane dichloride and distilled water, and after evaporation of all solvents, the mixture was separated by column chromatography (hexane/ethyl acetate = 3:1) and an orange solid (2.5 g, 53%) was obtained.

1H NMR (400 MHz, CDCl3) δ 8.70 - 8.61 (m, 2H), 7.99 - 7.90 (m, 2H), 7.80 (s, 1H), 7.77 - 7.72 (m, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.47 - 7.40 (m, 2H), 7.07 - 6.99 (m, 2H), 4.09 (t, J = 6.5 Hz, 2H), 3.71 (t, J = 6.5 Hz, 2H), 2.63 (s, 3H), 1.88 (p, J = 6.6 Hz, 2H), 1.71 - 1.62 (m, 2H), 1.56 - 1.43 (m, 4H). 1 H NMR (400 MHz, CDCl 3 ) δ 8.70 - 8.61 (m, 2H), 7.99 - 7.90 (m, 2H), 7.80 (s, 1H), 7.77 - 7.72 (m, 1H), 7.66 (d, J) = 8.2 Hz, 1H), 7.47 - 7.40 (m, 2H), 7.07 - 6.99 (m, 2H), 4.09 (t, J = 6.5 Hz, 2H), 3.71 (t, J = 6.5 Hz, 2H), 2.63 (s, 3H), 1.88 (p, J = 6.6 Hz, 2H), 1.71 - 1.62 (m, 2H), 1.56 - 1.43 (m, 4H).

단계 4 : 4-(6-메타아크릴로옥시헥실옥시)-4'-(4-피리딜)에틴일-3'-메틸아조벤젠의 제조Step 4: Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(4-pyridyl)ethynyl-3'-methylazobenzene

4-(6-하이드로옥시헥실옥시)-4'-(4-피리딜)에틴일-3'-메틸아조벤젠 1 g (2.4 mmol) 을 반응 용기에 넣고 이염화메탄 5 mL, 트리에틸아민 5mL, 4-디메틸아미노피리딘 0.03 g (0.24 mmol) 을 첨가하였다. 산소를 제거하고 질소분위기 하에서 메타크릴로일클로라이드 0.47 mL (4.8 mmol) 을 천천히 적가하고, 상온에서 3시간 이상동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 5:1) 로 분리하여 주황색의 고체 (0.66 g, 57%) 를 수득하였다.1 g (2.4 mmol) of 4-(6-hydrooxyhexyloxy)-4'-(4-pyridyl)ethynyl-3'-methylazobenzene was placed in a reaction vessel, 5 mL of methane dichloride, and 5 mL of triethylamine , 0.03 g (0.24 mmol) of 4-dimethylaminopyridine were added. After removing oxygen, 0.47 mL (4.8 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for at least 3 hours. The reaction mixture was extracted with methane dichloride and distilled water, and all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 5:1) to obtain an orange solid (0.66 g, 57%).

1H NMR (500 MHz, CDCl3) δ 8.66 - 8.60 (m, 2H), 7.95 - 7.88 (m, 2H), 7.77 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.1, 1.9 Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.43 - 7.38 (m, 2H), 7.03 - 6.98 (m, 2H), 6.10 (t, J = 1.3 Hz, 1H), 5.55 (p, J = 1.7 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.05 (t, J = 6.4 Hz, 2H), 2.60 (s, 3H), 1.95 (t, J = 1.2 Hz, 3H), 1.84 (p, J = 6.6 Hz, 2H), 1.73 (p, J = 6.9 Hz, 2H), 1.58 - 1.46 (m, 4H). 1 H NMR (500 MHz, CDCl 3 ) δ 8.66 - 8.60 (m, 2H), 7.95 - 7.88 (m, 2H), 7.77 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.1, 1.9) Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.43 - 7.38 (m, 2H), 7.03 - 6.98 (m, 2H), 6.10 (t, J = 1.3 Hz, 1H), 5.55 (p , J = 1.7 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.05 (t, J = 6.4 Hz, 2H), 2.60 (s, 3H), 1.95 (t, J = 1.2 Hz, 3H) ), 1.84 (p, J = 6.6 Hz, 2H), 1.73 (p, J = 6.9 Hz, 2H), 1.58 - 1.46 (m, 4H).

<실시예 2> 4-(6-메타아크릴로옥시헥실옥시)-4'-(3-피리딜)에틴일-3'-메틸아조벤젠의 제조<Example 2> Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(3-pyridyl)ethynyl-3'-methylazobenzene

Figure 112019120568208-pat00022
Figure 112019120568208-pat00022

단계 1 : 4-(6-하이드로옥시헥실옥시)-4'-(3-피리딜)에틴일-3'-메틸아조벤젠의 제조Step 1: Preparation of 4-(6-hydrooxyhexyloxy)-4'-(3-pyridyl)ethynyl-3'-methylazobenzene

반응 용기에 4-(6-하이드로옥시헥실옥시)-4'-아이오도-3'-메틸아조벤젠 2.1 g (4.8 mmol) 을 테트라하이드로퓨란 15 mL, 트리에틸아민 15 mL 에 녹이고 산소를 제거하며 질소분위기 하에서 트리페닐포스핀 0.1259 g (0.48 mmol), 비스(트리페닐포스핀)팔라듐(II) 클로라이드 0.3369 g (0.48 mmol), 요오드화구리 0.1371 g (0.72 mmol) 을 순차적으로 첨가한 후, 80 ℃로 온도를 높여주었다. 80 ℃에서 소량의 테트라하이드로퓨란에 녹인 3-에틴일피리딘 0.5 g (4.8 mmol) 을 천천히 적가하고 24시간 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 3:1) 로 분리하여 주황색의 고체 (1.54 g, 78%) 를 수득하였다.In a reaction vessel, 2.1 g (4.8 mmol) of 4-(6-hydrooxyhexyloxy)-4'-iodo-3'-methylazobenzene was dissolved in 15 mL of tetrahydrofuran and 15 mL of triethylamine, and oxygen was removed. After sequentially adding 0.1259 g (0.48 mmol) of triphenylphosphine, 0.3369 g (0.48 mmol) of bis(triphenylphosphine) palladium (II) chloride, and 0.1371 g (0.72 mmol) of copper iodide under a nitrogen atmosphere, 80° C. raised the temperature with 0.5 g (4.8 mmol) of 3-ethynylpyridine dissolved in a small amount of tetrahydrofuran at 80° C. was slowly added dropwise and stirred for 24 hours. After cooling to room temperature, the reaction mixture was extracted with methane dichloride and distilled water, and after evaporation of all solvents, the mixture was separated by column chromatography (hexane/ethyl acetate = 3:1), and an orange solid (1.54 g, 78%) was obtained.

1H NMR (500 MHz, CDCl3) δ 8.84 - 8.79 (m, 1H), 8.60 (dd, J = 4.9, 1.7 Hz, 1H), 7.97 - 7.91 (m, 2H), 7.86 (dt, J = 7.9, 1.9 Hz, 1H), 7.80 (d, J = 1.9 Hz, 1H), 7.74 (dd, J = 8.3, 1.9 Hz, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.34 (ddd, J = 7.9, 4.9, 0.9 Hz, 1H), 7.06 - 7.01 (m, 2H), 4.09 (t, J = 6.4 Hz, 2H), 3.71 (t, J = 6.5 Hz, 2H), 2.64 (s, 3H), 1.88 (dt, J = 14.2, 6.6 Hz, 2H), 1.70 - 1.63 (m, 2H), 1.51 - 1.46 (m, 2H), 0.94 - 0.82 (m, 2H). 1 H NMR (500 MHz, CDCl 3 ) δ 8.84 - 8.79 (m, 1H), 8.60 (dd, J = 4.9, 1.7 Hz, 1H), 7.97 - 7.91 (m, 2H), 7.86 (dt, J = 7.9) , 1.9 Hz, 1H), 7.80 (d, J = 1.9 Hz, 1H), 7.74 (dd, J = 8.3, 1.9 Hz, 1H), 7.66 (d, J = 8.2 Hz, 1H), 7.34 (ddd, J) = 7.9, 4.9, 0.9 Hz, 1H), 7.06 - 7.01 (m, 2H), 4.09 (t, J = 6.4 Hz, 2H), 3.71 (t, J = 6.5 Hz, 2H), 2.64 (s, 3H) , 1.88 (dt, J = 14.2, 6.6 Hz, 2H), 1.70 - 1.63 (m, 2H), 1.51 - 1.46 (m, 2H), 0.94 - 0.82 (m, 2H).

단계 2 : 4-(6-메타아크릴로옥시헥실옥시)-4'-(3-피리딜)에틴일-3'-메틸아조벤젠의 제조Step 2: Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(3-pyridyl)ethynyl-3'-methylazobenzene

4-(6-하이드로옥시헥실옥시)-4'-(3-피리딜)에틴일-3'-메틸아조벤젠 1 g (2.4 mmol) 을 반응 용기에 넣고 이염화메탄 5 mL, 트리에틸아민 5mL, 4-디메틸아미노피리딘 0.03 g (0.24 mmol) 을 첨가하였다. 산소를 제거하고 질소분위기 하에서 메타크릴로일클로라이드 0.47 mL (4.8 mmol) 을 천천히 적가하고, 상온에서 3시간 이상동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 6:1) 로 분리하여 주황색의 고체 (0.95 g, 83%) 를 수득하였다.1 g (2.4 mmol) of 4-(6-hydrooxyhexyloxy)-4'-(3-pyridyl)ethynyl-3'-methylazobenzene was placed in a reaction vessel, 5 mL of methane dichloride, and 5 mL of triethylamine , 0.03 g (0.24 mmol) of 4-dimethylaminopyridine were added. After removing oxygen, 0.47 mL (4.8 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for at least 3 hours. The reaction mixture was extracted with methane dichloride and distilled water, and all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 6:1) to obtain an orange solid (0.95 g, 83%).

1H NMR (500 MHz, Chloroform-d) δ 8.80 (dd, J = 2.1, 1.0 Hz, 1H), 8.57 (dd, J = 4.9, 1.7 Hz, 1H), 7.94 - 7.88 (m, 2H), 7.84 (dt, J = 7.8, 1.9 Hz, 1H), 7.77 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.2, 1.9 Hz, 1H), 7.63 (d, J = 8.1 Hz, 1H), 7.31 (ddd, J = 7.9, 4.9, 0.9 Hz, 1H), 7.02 - 6.98 (m, 2H), 6.10 (dq, J = 1.9, 1.0 Hz, 1H), 5.55 (p, J = 1.7 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.05 (t, J = 6.4 Hz, 2H), 2.61 (s, 3H), 1.95 (dd, J = 1.6, 1.0 Hz, 3H), 1.84 (dt, J = 8.3, 6.5 Hz, 2H), 1.76 - 1.70 (m, 2H), 1.57 - 1.47 (m, 4H). 1 H NMR (500 MHz, Chloroform- d ) δ 8.80 (dd, J = 2.1, 1.0 Hz, 1H), 8.57 (dd, J = 4.9, 1.7 Hz, 1H), 7.94 - 7.88 (m, 2H), 7.84 (dt, J = 7.8, 1.9 Hz, 1H), 7.77 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.2, 1.9 Hz, 1H), 7.63 (d, J = 8.1 Hz, 1H) , 7.31 (ddd, J = 7.9, 4.9, 0.9 Hz, 1H), 7.02 - 6.98 (m, 2H), 6.10 (dq, J = 1.9, 1.0 Hz, 1H), 5.55 (p, J = 1.7 Hz, 1H) ), 4.17 (t, J = 6.6 Hz, 2H), 4.05 (t, J = 6.4 Hz, 2H), 2.61 (s, 3H), 1.95 (dd, J = 1.6, 1.0 Hz, 3H), 1.84 (dt) , J = 8.3, 6.5 Hz, 2H), 1.76 - 1.70 (m, 2H), 1.57 - 1.47 (m, 4H).

<실시예 3> 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피리딜)에틴일-3'-메틸아조벤젠의 제조<Example 3> Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyridyl)ethynyl-3'-methylazobenzene

Figure 112019120568208-pat00023
Figure 112019120568208-pat00023

단계 1 : 4-(6-하이드로옥시헥실옥시)-4'-(2-피리딜)에틴일-3'-메틸아조벤젠의 제조Step 1: Preparation of 4-(6-hydrooxyhexyloxy)-4'-(2-pyridyl)ethynyl-3'-methylazobenzene

반응 용기에 4-(6-하이드로옥시헥실옥시)-4'-아이오도-3'-메틸아조벤젠 2.1 g (4.8 mmol) 을 테트라하이드로퓨란 15 mL, 트리에틸아민 15 mL 에 녹이고 산소를 제거하며 질소분위기 하에서 트리페닐포스핀 0.1259 g (0.48 mmol), 비스(트리페닐포스핀)팔라듐(II) 클로라이드 0.3369 g (0.48 mmol), 요오드화구리 0.1371 g (0.72 mmol) 을 순차적으로 첨가한 후, 80 ℃로 온도를 높여주었다. 80 ℃에서 소량의 테트라하이드로퓨란에 녹인 2-에틴일피리딘 4.9 mL (4.8 mmol) 을 천천히 적가하고 24시간 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 3:1) 로 분리하여 주황색의 고체 (1.62 g, 82%) 를 수득하였다.In a reaction vessel, 2.1 g (4.8 mmol) of 4-(6-hydrooxyhexyloxy)-4'-iodo-3'-methylazobenzene was dissolved in 15 mL of tetrahydrofuran and 15 mL of triethylamine, and oxygen was removed. After sequentially adding 0.1259 g (0.48 mmol) of triphenylphosphine, 0.3369 g (0.48 mmol) of bis(triphenylphosphine) palladium (II) chloride, and 0.1371 g (0.72 mmol) of copper iodide under a nitrogen atmosphere, 80° C. raised the temperature with 4.9 mL (4.8 mmol) of 2-ethynylpyridine dissolved in a small amount of tetrahydrofuran at 80° C. was slowly added dropwise, followed by stirring for 24 hours. After cooling to room temperature, the reaction mixture was extracted with methane dichloride and distilled water, and after evaporating all the solvents, the mixture was separated by column chromatography (hexane/ethyl acetate = 3:1) and an orange solid (1.62 g, 82%) was obtained.

1H NMR (500 MHz, CDCl3) δ 8.67 (ddd, J = 4.9, 1.9, 1.0 Hz, 1H), 7.97 - 7.90 (m, 2H), 7.78 (dt, J = 1.7, 0.9 Hz, 1H), 7.73 - 7.72 (m, 2H), 7.58 (dt, J = 8.0, 1.1 Hz, 1H), 7.31 - 7.25 (m, 2H), 7.05 - 7.00 (m, 2H), 4.07 (t, J = 6.5 Hz, 2H), 3.70 (t, J = 6.6 Hz, 2H), 2.67 (s, 3H), 1.91 - 1.83 (m, 2H), 1.67 - 1.63 (m, 2H), 1.57 - 1.47 (m, 4H). 1 H NMR (500 MHz, CDCl 3 ) δ 8.67 (ddd, J = 4.9, 1.9, 1.0 Hz, 1H), 7.97 - 7.90 (m, 2H), 7.78 (dt, J = 1.7, 0.9 Hz, 1H), 7.73 - 7.72 (m, 2H), 7.58 (dt, J = 8.0, 1.1 Hz, 1H), 7.31 - 7.25 (m, 2H), 7.05 - 7.00 (m, 2H), 4.07 (t, J = 6.5 Hz, 2H), 3.70 (t, J = 6.6 Hz, 2H), 2.67 (s, 3H), 1.91 - 1.83 (m, 2H), 1.67 - 1.63 (m, 2H), 1.57 - 1.47 (m, 4H).

단계 2 : 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피리딜)에틴일-3'-메틸아조벤젠의 제조Step 2: Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyridyl)ethynyl-3'-methylazobenzene

4-(6-하이드로옥시헥실옥시)-4'-(2-피리딜)에틴일-3'-메틸아조벤젠 1 g (2.4 mmol) 을 반응 용기에 넣고 이염화메탄 5 mL, 트리에틸아민 5mL, 4-디메틸아미노피리딘 0.03 g (0.24 mmol) 을 첨가하였다. 산소를 제거하고 질소분위기 하에서 메타크릴로일클로라이드 0.47 mL (4.8 mmol) 을 천천히 적가하고, 상온에서 3시간 이상동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 6:1) 로 분리하여 주황색의 고체 (0.9 g, 78%) 를 수득하였다.1 g (2.4 mmol) of 4-(6-hydrooxyhexyloxy)-4'-(2-pyridyl)ethynyl-3'-methylazobenzene was placed in a reaction vessel, 5 mL of methane dichloride, and 5 mL of triethylamine , 0.03 g (0.24 mmol) of 4-dimethylaminopyridine were added. After removing oxygen, 0.47 mL (4.8 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for at least 3 hours. The reaction mixture was extracted with methane dichloride and distilled water, and all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 6:1) to obtain an orange solid (0.9 g, 78%).

1H NMR (500 MHz, CD2Cl2) δ 8.64 (ddd, J = 5.0, 1.8, 1.0 Hz, 1H), 7.94 - 7.89 (m, 2H), 7.85 - 7.77 (m, 2H), 7.72 (d, J = 1.2 Hz, 2H), 7.63 (d, J = 8.0 Hz, 1H), 7.36 (dd, J = 7.9, 4.9 Hz, 1H), 7.05 - 7.00 (m, 2H), 6.07 (dq, J = 2.0, 1.0 Hz, 1H), 5.54 (p, J = 1.6 Hz, 1H), 4.15 (t, J = 6.6 Hz, 2H), 4.07 (t, J = 6.5 Hz, 2H), 2.66 (d, J = 0.7 Hz, 3H), 1.93 (dd, J = 1.6, 1.0 Hz, 3H), 1.88 - 1.81 (m, 2H), 1.76 - 1.69 (m, 2H), 1.56 - 1.46 (m, 4H). 1 H NMR (500 MHz, CD 2 Cl 2 ) δ 8.64 (ddd, J = 5.0, 1.8, 1.0 Hz, 1H), 7.94 - 7.89 (m, 2H), 7.85 - 7.77 (m, 2H), 7.72 (d , J = 1.2 Hz, 2H), 7.63 (d, J = 8.0 Hz, 1H), 7.36 (dd, J = 7.9, 4.9 Hz, 1H), 7.05 - 7.00 (m, 2H), 6.07 (dq, J = 2.0, 1.0 Hz, 1H), 5.54 (p, J = 1.6 Hz, 1H), 4.15 (t, J = 6.6 Hz, 2H), 4.07 (t, J = 6.5 Hz, 2H), 2.66 (d, J = 0.7 Hz, 3H), 1.93 (dd, J = 1.6, 1.0 Hz, 3H), 1.88 - 1.81 (m, 2H), 1.76 - 1.69 (m, 2H), 1.56 - 1.46 (m, 4H).

<실시예 4> 4-(6-메타아크릴로옥시헥실옥시)-4'-(5-피리미딜)에틴일-3'-메틸아조벤젠의 제조<Example 4> Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(5-pyrimidyl)ethynyl-3'-methylazobenzene

Figure 112019120568208-pat00024
Figure 112019120568208-pat00024

단계 1 : 4-(6-하이드로옥시헥실옥시)-4'-(5-피리미딜)에틴일-3'-메틸아조벤젠의 제조Step 1: Preparation of 4-(6-hydrooxyhexyloxy)-4'-(5-pyrimidyl)ethynyl-3'-methylazobenzene

반응 용기에 4-(6-하이드로옥시헥실옥시)-4'-아이오도-3'-메틸아조벤젠 0.5 g (1.14 mmol) 을 테트라하이드로퓨란 10 mL, 트리에틸아민 10 mL 에 녹이고 산소를 제거하며 질소분위기 하에서 트리페닐포스핀 0.03 g (0.114 mmol), 비스(트리페닐포스핀)팔라듐(II) 클로라이드 0.08 g (0.114 mmol), 요오드화구리 0.0326 g (0.171 mmol) 을 순차적으로 첨가한 후, 80 ℃로 온도를 높여주었다. 80 ℃에서 소량의 테트라하이드로퓨란에 녹인 5-에틴일피리미딘 0.1187 g (1.14 mmol) 을 천천히 적가하고 24시간 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 3:1) 로 분리하여 주황색의 고체 (0.3 g, 64%) 를 수득하였다.In a reaction vessel, 0.5 g (1.14 mmol) of 4-(6-hydrooxyhexyloxy)-4'-iodo-3'-methylazobenzene was dissolved in 10 mL of tetrahydrofuran and 10 mL of triethylamine, and oxygen was removed. After sequentially adding 0.03 g (0.114 mmol) of triphenylphosphine, 0.08 g (0.114 mmol) of bis(triphenylphosphine) palladium (II) chloride, and 0.0326 g (0.171 mmol) of copper iodide under a nitrogen atmosphere, 80° C. raised the temperature with 0.1187 g (1.14 mmol) of 5-ethynylpyrimidine dissolved in a small amount of tetrahydrofuran at 80° C. was slowly added dropwise, followed by stirring for 24 hours. After cooling to room temperature, the reaction mixture was extracted with methane dichloride and distilled water, and after evaporating all the solvents, the mixture was separated by column chromatography (hexane/ethyl acetate = 3:1), and an orange solid (0.3 g, 64%) was obtained.

1H NMR (500 MHz, CDCl3) δ 9.19 (s, 1H), 8.91 (s, 2H), 7.99 - 7.90 (m, 2H), 7.81 (d, J = 1.9 Hz, 1H), 7.75 (dd, J = 8.0, 2.0 Hz, 1H), 7.67 (d, J = 8.1 Hz, 1H), 7.07 - 7.00 (m, 2H), 4.09 (t, J = 6.5 Hz, 2H), 3.71 (t, J = 6.5 Hz, 2H), 2.64 (s, 3H), 1.93 - 1.83 (m, 2H), 1.69 - 1.63 (m, 2H), 1.56 - 1.45 (m, 4H). 1 H NMR (500 MHz, CDCl 3 ) δ 9.19 (s, 1H), 8.91 (s, 2H), 7.99 - 7.90 (m, 2H), 7.81 (d, J = 1.9 Hz, 1H), 7.75 (dd, J = 8.0, 2.0 Hz, 1H), 7.67 (d, J = 8.1 Hz, 1H), 7.07 - 7.00 (m, 2H), 4.09 (t, J = 6.5 Hz, 2H), 3.71 (t, J = 6.5) Hz, 2H), 2.64 (s, 3H), 1.93 - 1.83 (m, 2H), 1.69 - 1.63 (m, 2H), 1.56 - 1.45 (m, 4H).

단계 2 : 4-(6-메타아크릴로옥시헥실옥시)-4'-(5-피리미딜)에틴일-3'-메틸아조벤젠의 제조Step 2: Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(5-pyrimidyl)ethynyl-3'-methylazobenzene

4-(6-하이드로옥시헥실옥시)-4'-(5-피리미딜)에틴일-3'-메틸아조벤젠 0.3 g (0.72 mmol) 을 반응 용기에 넣고 이염화메탄 5 mL, 트리에틸아민 5mL, 4-디메틸아미노피리딘 0.01 g (0.072 mmol) 을 첨가하였다. 산소를 제거하고 질소분위기 하에서 메타크릴로일클로라이드 0.14 mL (1.44 mmol) 을 천천히 적가하고, 상온에서 3시간 이상동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 6:1) 로 분리하여 주황색의 고체 (0.21 g, 61%) 를 수득하였다.0.3 g (0.72 mmol) of 4-(6-hydroxyhexyloxy)-4'-(5-pyrimidyl)ethynyl-3'-methylazobenzene was placed in a reaction vessel, 5 mL of methane dichloride, and 5 mL of triethylamine , 0.01 g (0.072 mmol) of 4-dimethylaminopyridine were added. After removing oxygen, 0.14 mL (1.44 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for at least 3 hours. The reaction mixture was extracted with methane dichloride and distilled water, and all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 6:1) to obtain an orange solid (0.21 g, 61%).

1H NMR (500 MHz, CDCl3) δ 9.16 (s, 1H), 8.89 (s, 2H), 7.94 - 7.90 (m, 2H), 7.78 (d, J = 1.9 Hz, 1H), 7.73 (dd, J = 8.1, 2.0 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 7.02 - 6.99 (m, 2H), 6.10 (dq, J = 2.0, 1.0 Hz, 1H), 5.55 (p, J = 1.6 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.06 (t, J = 6.4 Hz, 2H), 2.61 (s, 3H), 1.95 (dd, J = 1.6, 1.0 Hz, 3H), 1.88 - 1.82 (m, 2H), 1.73 (dq, J = 7.8, 6.7 Hz, 2H), 1.57 - 1.46 (m, 4H). 1 H NMR (500 MHz, CDCl 3 ) δ 9.16 (s, 1H), 8.89 (s, 2H), 7.94 - 7.90 (m, 2H), 7.78 (d, J = 1.9 Hz, 1H), 7.73 (dd, J = 8.1, 2.0 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 7.02 - 6.99 (m, 2H), 6.10 (dq, J = 2.0, 1.0 Hz, 1H), 5.55 (p, J = 1.6 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.06 (t, J = 6.4 Hz, 2H), 2.61 (s, 3H), 1.95 (dd, J = 1.6, 1.0 Hz, 3H) ), 1.88 - 1.82 (m, 2H), 1.73 (dq, J = 7.8, 6.7 Hz, 2H), 1.57 - 1.46 (m, 4H).

<실시예 5> 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피리미딜)에틴일-3'-메틸아조벤젠의 제조<Example 5> Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyrimidyl)ethynyl-3'-methylazobenzene

Figure 112019120568208-pat00025
Figure 112019120568208-pat00025

단계 1 : 4-(6-하이드로옥시헥실옥시)-4'-(2-피리미딜)에틴일-3'-메틸아조벤젠의 제조Step 1: Preparation of 4-(6-hydrooxyhexyloxy)-4'-(2-pyrimidyl)ethynyl-3'-methylazobenzene

반응 용기에 4-(6-하이드로옥시헥실옥시)-4'-아이오도-3'-메틸아조벤젠 2.1038 g (4.8 mmol) 을 테트라하이드로퓨란 20 mL, 트리에틸아민 20 mL 에 녹이고 산소를 제거하며 질소분위기 하에서 트리페닐포스핀 0.1259 g (0.48 mmol), 비스(트리페닐포스핀)팔라듐(II) 클로라이드 0.3369 g (0.48 mmol), 요오드화구리 0.1371 g (0.72 mmol) 을 순차적으로 첨가한 후, 80 ℃로 온도를 높여주었다. 80 ℃에서 소량의 테트라하이드로퓨란에 녹인 2-에틴일피리미딘 0.5 g (4.8 mmol) 을 천천히 적가하고 24시간 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 3:1) 로 분리하여 주황색의 고체 (1.2 g, 61%) 를 수득하였다.In a reaction vessel, 2.1038 g (4.8 mmol) of 4-(6-hydrooxyhexyloxy)-4'-iodo-3'-methylazobenzene was dissolved in 20 mL of tetrahydrofuran and 20 mL of triethylamine, and oxygen was removed. After sequentially adding 0.1259 g (0.48 mmol) of triphenylphosphine, 0.3369 g (0.48 mmol) of bis(triphenylphosphine) palladium (II) chloride, and 0.1371 g (0.72 mmol) of copper iodide under a nitrogen atmosphere, 80° C. raised the temperature with 0.5 g (4.8 mmol) of 2-ethynylpyrimidine dissolved in a small amount of tetrahydrofuran at 80° C. was slowly added dropwise, followed by stirring for 24 hours. After cooling to room temperature, the reaction mixture was extracted with methane dichloride and distilled water, and after evaporating all the solvents, the mixture was separated by column chromatography (hexane/ethyl acetate = 3:1) and an orange solid (1.2 g, 61%) was obtained.

1H NMR (500 MHz, CD2Cl2) δ 8.78 (d, J = 4.9 Hz, 2H), 7.96 - 7.88 (m, 2H), 7.80 (dt, J = 1.7, 0.8 Hz, 1H), 7.77 - 7.70 (m, 2H), 7.32 - 7.27 (m, 1H), 7.06 - 6.98 (m, 2H), 4.06 (t, J = 6.5 Hz, 2H), 3.62 (t, J = 6.6 Hz, 2H), 2.66 (s, 3H), 1.88 - 1.79 (m, 2H), 1.59 (tt, J = 8.2, 6.5 Hz, 2H), 1.55 - 1.48 (m, 2H), 1.48 - 1.41 (m, 2H). 1 H NMR (500 MHz, CD 2 Cl 2 ) δ 8.78 (d, J = 4.9 Hz, 2H), 7.96 - 7.88 (m, 2H), 7.80 (dt, J = 1.7, 0.8 Hz, 1H), 7.77 - 7.70 (m, 2H), 7.32 - 7.27 (m, 1H), 7.06 - 6.98 (m, 2H), 4.06 (t, J = 6.5 Hz, 2H), 3.62 (t, J = 6.6 Hz, 2H), 2.66 (s, 3H), 1.88 - 1.79 (m, 2H), 1.59 (tt, J = 8.2, 6.5 Hz, 2H), 1.55 - 1.48 (m, 2H), 1.48 - 1.41 (m, 2H).

단계 2 : 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피리미딜)에틴일-3'-메틸아조벤젠의 제조Step 2: Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyrimidyl)ethynyl-3'-methylazobenzene

4-(6-하이드로옥시헥실옥시)-4'-(2-피리미딜)에틴일-3'-메틸아조벤젠 1 g (2.4 mmol) 을 반응 용기에 넣고 이염화메탄 5 mL, 트리에틸아민 5mL, 4-디메틸아미노피리딘 0.03 g (0.24 mmol) 을 첨가하였다. 산소를 제거하고 질소분위기 하에서 메타크릴로일클로라이드 0.47 mL (4.8 mmol) 을 천천히 적가하고, 상온에서 3시간 이상동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 5:1) 로 분리하여 주황색의 고체 (1.05 g, 90%) 를 수득하였다.1 g (2.4 mmol) of 4-(6-hydrooxyhexyloxy)-4'-(2-pyrimidyl)ethynyl-3'-methylazobenzene was placed in a reaction vessel, 5 mL of methane dichloride, and 5 mL of triethylamine , 0.03 g (0.24 mmol) of 4-dimethylaminopyridine were added. After removing oxygen, 0.47 mL (4.8 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for at least 3 hours. The reaction mixture was extracted with methane dichloride and distilled water, and all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 5:1) to obtain an orange solid (1.05 g, 90%).

1H NMR (500 MHz, DMSO-d 6) δ 8.88 (d, J = 4.9 Hz, 2H), 7.93 - 7.88 (m, 2H), 7.83 (d, J = 2.0 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.73 (dd, J = 8.2, 2.0 Hz, 1H), 7.55 (t, J = 4.9 Hz, 1H), 7.15 - 7.11 (m, 2H), 6.02 (dd, J = 1.8, 1.1 Hz, 1H), 5.66 (p, J = 1.5 Hz, 1H), 4.10 (dt, J = 8.2, 6.4 Hz, 4H), 2.60 (s, 3H), 1.87 (t, J = 1.3 Hz, 3H), 1.76 (p, J = 6.7 Hz, 2H), 1.65 (p, J = 6.8 Hz, 2H), 1.45 (dt, J = 22.8, 7.6 Hz, 4H). 1 H NMR (500 MHz, DMSO- d 6 ) δ 8.88 (d, J = 4.9 Hz, 2H), 7.93 - 7.88 (m, 2H), 7.83 (d, J = 2.0 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.73 (dd, J = 8.2, 2.0 Hz, 1H), 7.55 (t, J = 4.9 Hz, 1H), 7.15 - 7.11 (m, 2H), 6.02 (dd, J = 1.8) , 1.1 Hz, 1H), 5.66 (p, J = 1.5 Hz, 1H), 4.10 (dt, J = 8.2, 6.4 Hz, 4H), 2.60 (s, 3H), 1.87 (t, J = 1.3 Hz, 3H) ), 1.76 (p, J = 6.7 Hz, 2H), 1.65 (p, J = 6.8 Hz, 2H), 1.45 (dt, J = 22.8, 7.6 Hz, 4H).

<실시예 6> 4-(6-메타아크릴로옥시헥실옥시)-4'-(4-피리미딜)에틴일-3'-메틸아조벤젠의 제조<Example 6> Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(4-pyrimidyl)ethynyl-3'-methylazobenzene

Figure 112019120568208-pat00026
Figure 112019120568208-pat00026

단계 1 : 4-(6-하이드로옥시헥실옥시)-4'-(4-피리미딜)에틴일-3'-메틸아조벤젠의 제조Step 1: Preparation of 4-(6-hydrooxyhexyloxy)-4'-(4-pyrimidyl)ethynyl-3'-methylazobenzene

반응 용기에 4-(6-하이드로옥시헥실옥시)-4'-아이오도-3'-메틸아조벤젠 2.1038 g (4.8 mmol) 을 테트라하이드로퓨란 20 mL, 트리에틸아민 20 mL 에 녹이고 산소를 제거하며 질소분위기 하에서 트리페닐포스핀 0.1259 g (0.48 mmol), 비스(트리페닐포스핀)팔라듐(II) 클로라이드 0.3369 g (0.48 mmol), 요오드화구리 0.1371 g (0.72 mmol) 을 순차적으로 첨가한 후, 80 ℃로 온도를 높여주었다. 80 ℃에서 소량의 테트라하이드로퓨란에 녹인 4-에틴일피리미딘 0.5 g (4.8 mmol) 을 천천히 적가하고 24시간 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 3:1) 로 분리하여 주황색의 고체 (1.2 g, 61%) 를 수득하였다.In a reaction vessel, 2.1038 g (4.8 mmol) of 4-(6-hydrooxyhexyloxy)-4'-iodo-3'-methylazobenzene was dissolved in 20 mL of tetrahydrofuran and 20 mL of triethylamine, and oxygen was removed. After sequentially adding 0.1259 g (0.48 mmol) of triphenylphosphine, 0.3369 g (0.48 mmol) of bis(triphenylphosphine) palladium (II) chloride, and 0.1371 g (0.72 mmol) of copper iodide under a nitrogen atmosphere, 80° C. raised the temperature with 0.5 g (4.8 mmol) of 4-ethynylpyrimidine dissolved in a small amount of tetrahydrofuran at 80° C. was slowly added dropwise, followed by stirring for 24 hours. After cooling to room temperature, the reaction mixture was extracted with methane dichloride and distilled water, and after evaporating all the solvents, the mixture was separated by column chromatography (hexane/ethyl acetate = 3:1) and an orange solid (1.2 g, 61%) was obtained.

1H NMR (500 MHz, CDCl3) δ 8.78 (d, J = 4.9 Hz, 2H), 7.96 - 7.88 (m, 2H), 7.80 (dt, J = 1.7, 0.8 Hz, 1H), 7.77 - 7.70 (m, 2H), 7.32 - 7.27 (m, 1H), 7.06 - 6.98 (m, 2H), 4.06 (t, J = 6.5 Hz, 2H), 3.62 (t, J = 6.6 Hz, 2H), 2.66 (s, 3H), 1.88 - 1.79 (m, 2H), 1.59 (tt, J = 8.2, 6.5 Hz, 2H), 1.55 - 1.48 (m, 2H), 1.48 - 1.41 (m, 2H). 1 H NMR (500 MHz, CDCl 3 ) δ 8.78 (d, J = 4.9 Hz, 2H), 7.96 - 7.88 (m, 2H), 7.80 (dt, J = 1.7, 0.8 Hz, 1H), 7.77 - 7.70 ( m, 2H), 7.32 - 7.27 (m, 1H), 7.06 - 6.98 (m, 2H), 4.06 (t, J = 6.5 Hz, 2H), 3.62 (t, J = 6.6 Hz, 2H), 2.66 (s) , 3H), 1.88 - 1.79 (m, 2H), 1.59 (tt, J = 8.2, 6.5 Hz, 2H), 1.55 - 1.48 (m, 2H), 1.48 - 1.41 (m, 2H).

단계 2 : 4-(6-메타아크릴로옥시헥실옥시)-4'-(4-피리미딜)에틴일-3'-메틸아조벤젠의 제조Step 2: Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(4-pyrimidyl)ethynyl-3'-methylazobenzene

4-(6-하이드로옥시헥실옥시)-4'-(4-피리미딜)에틴일-3'-메틸아조벤젠 1 g (2.4 mmol) 을 반응 용기에 넣고 이염화메탄 5 mL, 트리에틸아민 5mL, 4-디메틸아미노피리딘 0.03 g (0.24 mmol) 을 첨가하였다. 산소를 제거하고 질소분위기 하에서 메타크릴로일클로라이드 0.47 mL (4.8 mmol) 을 천천히 적가하고, 상온에서 3시간 이상동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 5:1) 로 분리하여 주황색의 고체 (0.66 g, 57%) 를 수득하였다.1 g (2.4 mmol) of 4-(6-hydrooxyhexyloxy)-4'-(4-pyrimidyl)ethynyl-3'-methylazobenzene was placed in a reaction vessel, 5 mL of methane dichloride, and 5 mL of triethylamine , 0.03 g (0.24 mmol) of 4-dimethylaminopyridine were added. After removing oxygen, 0.47 mL (4.8 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for at least 3 hours. The reaction mixture was extracted with methane dichloride and distilled water, and all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 5:1) to obtain an orange solid (0.66 g, 57%).

1H NMR (500 MHz, CDCl3) δ 8.66 - 8.60 (m, 2H), 7.95 - 7.88 (m, 2H), 7.77 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.1, 1.9 Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.43 - 7.38 (m, 2H), 7.03 - 6.98 (m, 2H), 6.10 (t, J = 1.3 Hz, 1H), 5.55 (p, J = 1.7 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.05 (t, J = 6.4 Hz, 2H), 2.60 (s, 3H), 1.95 (t, J = 1.2 Hz, 3H), 1.84 (p, J = 6.6 Hz, 2H), 1.73 (p, J = 6.9 Hz, 2H), 1.58 - 1.46 (m, 4H). 1 H NMR (500 MHz, CDCl 3 ) δ 8.66 - 8.60 (m, 2H), 7.95 - 7.88 (m, 2H), 7.77 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.1, 1.9) Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.43 - 7.38 (m, 2H), 7.03 - 6.98 (m, 2H), 6.10 (t, J = 1.3 Hz, 1H), 5.55 (p , J = 1.7 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.05 (t, J = 6.4 Hz, 2H), 2.60 (s, 3H), 1.95 (t, J = 1.2 Hz, 3H) ), 1.84 (p, J = 6.6 Hz, 2H), 1.73 (p, J = 6.9 Hz, 2H), 1.58 - 1.46 (m, 4H).

<실시예 7> 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피라진일)에틴일-3'-메틸아조벤젠의 제조<Example 7> Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyrazinyl)ethynyl-3'-methylazobenzene

Figure 112019120568208-pat00027
Figure 112019120568208-pat00027

단계 1 : 4-(6-하이드로옥시헥실옥시)-4'-(2-피라진일)에틴일-3'-메틸아조벤젠의 제조Step 1: Preparation of 4-(6-hydrooxyhexyloxy)-4'-(2-pyrazinyl)ethynyl-3'-methylazobenzene

반응 용기에 4-(6-하이드로옥시헥실옥시)-4'-아이오도-3'-메틸아조벤젠 2.1038 g (4.8 mmol) 을 테트라하이드로퓨란 20 mL, 트리에틸아민 20 mL 에 녹이고 산소를 제거하며 질소분위기 하에서 트리페닐포스핀 0.1259 g (0.48 mmol), 비스(트리페닐포스핀)팔라듐(II) 클로라이드 0.3369 g (0.48 mmol), 요오드화구리 0.1371 g (0.72 mmol) 을 순차적으로 첨가한 후, 80 ℃로 온도를 높여주었다. 80 ℃에서 소량의 테트라하이드로퓨란에 녹인 2-에틴일피라진일 0.5 g (4.8 mmol) 을 천천히 적가하고 24시간 동안 교반하였다. 상온으로 냉각 후, 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 3:1) 로 분리하여 주황색의 고체 (1.2 g, 61%) 를 수득하였다.In a reaction vessel, 2.1038 g (4.8 mmol) of 4-(6-hydrooxyhexyloxy)-4'-iodo-3'-methylazobenzene was dissolved in 20 mL of tetrahydrofuran and 20 mL of triethylamine, and oxygen was removed. After sequentially adding 0.1259 g (0.48 mmol) of triphenylphosphine, 0.3369 g (0.48 mmol) of bis(triphenylphosphine) palladium (II) chloride, and 0.1371 g (0.72 mmol) of copper iodide under a nitrogen atmosphere, 80° C. raised the temperature with 0.5 g (4.8 mmol) of 2-ethynylpyrazinyl dissolved in a small amount of tetrahydrofuran at 80° C. was slowly added dropwise, followed by stirring for 24 hours. After cooling to room temperature, the reaction mixture was extracted with methane dichloride and distilled water, and after evaporating all the solvents, the mixture was separated by column chromatography (hexane/ethyl acetate = 3:1) and an orange solid (1.2 g, 61%) was obtained.

1H NMR (500 MHz, CDCl3) δ 8.78 (d, J = 4.9 Hz, 2H), 7.96 - 7.88 (m, 2H), 7.80 (dt, J = 1.7, 0.8 Hz, 1H), 7.77 - 7.70 (m, 2H), 7.32 - 7.27 (m, 1H), 7.06 - 6.98 (m, 2H), 4.06 (t, J = 6.5 Hz, 2H), 3.62 (t, J = 6.6 Hz, 2H), 2.66 (s, 3H), 1.88 - 1.79 (m, 2H), 1.59 (tt, J = 8.2, 6.5 Hz, 2H), 1.55 - 1.48 (m, 2H), 1.48 - 1.41 (m, 2H). 1 H NMR (500 MHz, CDCl 3 ) δ 8.78 (d, J = 4.9 Hz, 2H), 7.96 - 7.88 (m, 2H), 7.80 (dt, J = 1.7, 0.8 Hz, 1H), 7.77 - 7.70 ( m, 2H), 7.32 - 7.27 (m, 1H), 7.06 - 6.98 (m, 2H), 4.06 (t, J = 6.5 Hz, 2H), 3.62 (t, J = 6.6 Hz, 2H), 2.66 (s) , 3H), 1.88 - 1.79 (m, 2H), 1.59 (tt, J = 8.2, 6.5 Hz, 2H), 1.55 - 1.48 (m, 2H), 1.48 - 1.41 (m, 2H).

단계 2 : 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피라진일)에틴일-3'-메틸아조벤젠의 제조Step 2: Preparation of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyrazinyl)ethynyl-3'-methylazobenzene

4-(6-하이드로옥시헥실옥시)-4'-(2-피라진일)에틴일-3'-메틸아조벤젠 1 g (2.4 mmol) 을 반응 용기에 넣고 이염화메탄 5 mL, 트리에틸아민 5mL, 4-디메틸아미노피리딘 0.03 g (0.24 mmol) 을 첨가하였다. 산소를 제거하고 질소분위기 하에서 메타크릴로일클로라이드 0.47 mL (4.8 mmol) 을 천천히 적가하고, 상온에서 3시간 이상동안 교반하였다. 반응 혼합물을 이염화메탄과 증류수로 추출하고, 용매를 모두 증발시킨 후, 컬럼 크로마토그래피 (헥산/초산에틸 = 5:1) 로 분리하여 주황색의 고체 (0.66 g, 57%) 를 수득하였다.1 g (2.4 mmol) of 4-(6-hydrooxyhexyloxy)-4'-(2-pyrazinyl)ethynyl-3'-methylazobenzene was placed in a reaction vessel, 5 mL of methane dichloride, and 5 mL of triethylamine , 0.03 g (0.24 mmol) of 4-dimethylaminopyridine were added. After removing oxygen, 0.47 mL (4.8 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen atmosphere, and the mixture was stirred at room temperature for at least 3 hours. The reaction mixture was extracted with methane dichloride and distilled water, and all solvents were evaporated, and then separated by column chromatography (hexane/ethyl acetate = 5:1) to obtain an orange solid (0.66 g, 57%).

1H NMR (500 MHz, CDCl3) δ 8.66 - 8.60 (m, 2H), 7.95 - 7.88 (m, 2H), 7.77 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.1, 1.9 Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.43 - 7.38 (m, 2H), 7.03 - 6.98 (m, 2H), 6.10 (t, J = 1.3 Hz, 1H), 5.55 (p, J = 1.7 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.05 (t, J = 6.4 Hz, 2H), 2.60 (s, 3H), 1.95 (t, J = 1.2 Hz, 3H), 1.84 (p, J = 6.6 Hz, 2H), 1.73 (p, J = 6.9 Hz, 2H), 1.58 - 1.46 (m, 4H). 1 H NMR (500 MHz, CDCl 3 ) δ 8.66 - 8.60 (m, 2H), 7.95 - 7.88 (m, 2H), 7.77 (d, J = 1.9 Hz, 1H), 7.72 (dd, J = 8.1, 1.9) Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.43 - 7.38 (m, 2H), 7.03 - 6.98 (m, 2H), 6.10 (t, J = 1.3 Hz, 1H), 5.55 (p , J = 1.7 Hz, 1H), 4.17 (t, J = 6.6 Hz, 2H), 4.05 (t, J = 6.4 Hz, 2H), 2.60 (s, 3H), 1.95 (t, J = 1.2 Hz, 3H) ), 1.84 (p, J = 6.6 Hz, 2H), 1.73 (p, J = 6.9 Hz, 2H), 1.58 - 1.46 (m, 4H).

상기 실시예 1 내지 7에서 제조한 아조벤젠 단량체 화합물의 구조를 정리하여 하기 표 1에 나타내었다.The structures of the azobenzene monomer compounds prepared in Examples 1 to 7 are summarized and shown in Table 1 below.

실시예Example 구조structure 실시예Example 구조structure 1One

Figure 112019120568208-pat00028
Figure 112019120568208-pat00028
55
Figure 112019120568208-pat00029
Figure 112019120568208-pat00029
 22
Figure 112019120568208-pat00030
Figure 112019120568208-pat00030
 66
Figure 112019120568208-pat00031
Figure 112019120568208-pat00031
 33
Figure 112019120568208-pat00032
Figure 112019120568208-pat00032
 77
Figure 112019120568208-pat00033
Figure 112019120568208-pat00033
 44
Figure 112019120568208-pat00034
Figure 112019120568208-pat00034

<실시예 8> 홀로그램 기록용 고분자 제조 1<Example 8> Preparation of polymer for hologram recording 1

Figure 112019120568208-pat00035
Figure 112019120568208-pat00035

반응 용기에 상기 실시예 1 에서 제조한 4-(6-메타아크릴로옥시헥실옥시)-4'-(4-피리딜)에틴일-3'-메틸아조벤젠 0.5 g (1.038 mmol), 아조비스아이소부틸로나이트릴 0.0421 g (0.8 wt%), 메틸메타아크릴레이트 2.1 mL (19.722 mmol) 을 N-메틸-2-피롤리돈에 녹인 후 질소 분위기 하에서 80 ℃에서 48 시간 동안 교반하였다. 반응 혼합물을 과량의 메탄올에 침전시켜 반응을 종료하고 필터 후, 소량의 N-메틸-2-피롤리돈에 녹인 후 과량의 메탄올에 재침전 후 필터하였다. 3회 이상 과량의 메탄올을 이용해서 세척하여 주황색의 고체 고분자 (1.9 g, 77%) 를 얻었다.In a reaction vessel, 0.5 g (1.038 mmol) of 4-(6-methacrylooxyhexyloxy)-4'-(4-pyridyl)ethynyl-3'-methylazobenzene prepared in Example 1, azobis 0.0421 g (0.8 wt%) of isobutylonitrile and 2.1 mL (19.722 mmol) of methyl methacrylate were dissolved in N-methyl-2-pyrrolidone, followed by stirring at 80° C. under a nitrogen atmosphere for 48 hours. The reaction mixture was precipitated in an excess of methanol to complete the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, reprecipitated in an excess of methanol, and then filtered. It was washed three or more times with an excess of methanol to obtain an orange solid polymer (1.9 g, 77%).

GPC Mn 13,848, Mw 21,669, PDI 1.56GPC Mn 13,848, Mw 21,669, PDI 1.56

<실시예 9> 홀로그램 기록용 고분자 제조 2<Example 9> Preparation of polymer for hologram recording 2

Figure 112019120568208-pat00036
Figure 112019120568208-pat00036

반응 용기에 상기 실시예 2 에서 제조한 4-(6-메타아크릴로옥시헥실옥시)-4'-(3-피리딜)에틴일-3'-메틸아조벤젠 0.5 g (1.038 mmol), 아조비스아이소부틸로나이트릴 0.0421 g (0.8 wt%), 메틸메타아크릴레이트 2.1 mL (19.722 mmol) 을 N-메틸-2-피롤리돈에 녹인 후 질소 분위기 하에서 80 ℃에서 48 시간 동안 교반하였다. 반응 혼합물을 과량의 메탄올에 침전시켜 반응을 종료하고 필터 후, 소량의 N-메틸-2-피롤리돈에 녹인 후 과량의 메탄올에 재침전 후 필터하였다. 3회 이상 과량의 메탄올을 이용해서 세척하여 주황색의 고체 고분자 (1.93g, 78) 를 얻었다.In a reaction vessel, 0.5 g (1.038 mmol) of 4-(6-methacrylooxyhexyloxy)-4'-(3-pyridyl)ethynyl-3'-methylazobenzene prepared in Example 2, azobis 0.0421 g (0.8 wt%) of isobutylonitrile and 2.1 mL (19.722 mmol) of methyl methacrylate were dissolved in N-methyl-2-pyrrolidone, followed by stirring at 80° C. under a nitrogen atmosphere for 48 hours. The reaction mixture was precipitated in an excess of methanol to complete the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, reprecipitated in an excess of methanol, and then filtered. It was washed three or more times with an excess of methanol to obtain an orange solid polymer (1.93 g, 78).

GPC Mn 29,586, Mw 69,678, PDI 2.35GPC Mn 29,586, Mw 69,678, PDI 2.35

<실시예 10> 홀로그램 기록용 고분자 제조 3<Example 10> Preparation of polymer for hologram recording 3

Figure 112019120568208-pat00037
Figure 112019120568208-pat00037

반응 용기에 상기 실시예 3 에서 제조한 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피리딜)에틴일-3'-메틸아조벤젠 0.5 g (1.038 mmol), 아조비스아이소부틸로나이트릴 0.0421 g (0.8 wt%), 메틸메타아크릴레이트 2.1 mL (19.722 mmol) 을 N-메틸-2-피롤리돈에 녹인 후 질소 분위기 하에서 80 ℃에서 48 시간 동안 교반하였다. 반응 혼합물을 과량의 메탄올에 침전시켜 반응을 종료하고 필터 후, 소량의 N-메틸-2-피롤리돈에 녹인 후 과량의 메탄올에 재침전 후 필터하였다. 3회 이상 과량의 메탄올을 이용해서 세척하여 주황색의 고체 고분자 (1.8g, 72%) 를 얻었다.In a reaction vessel, 0.5 g (1.038 mmol) of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyridyl)ethynyl-3'-methylazobenzene prepared in Example 3, azobis 0.0421 g (0.8 wt%) of isobutylonitrile and 2.1 mL (19.722 mmol) of methyl methacrylate were dissolved in N-methyl-2-pyrrolidone, followed by stirring at 80° C. under a nitrogen atmosphere for 48 hours. The reaction mixture was precipitated in an excess of methanol to complete the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, reprecipitated in an excess of methanol, and then filtered. It was washed three or more times with an excess of methanol to obtain an orange solid polymer (1.8 g, 72%).

GPC Mn 34,065, Mw 90,335, PDI 2.65GPC Mn 34,065, Mw 90,335, PDI 2.65

<실시예 11> 홀로그램 기록용 고분자 제조 4<Example 11> Preparation of polymer for hologram recording 4

Figure 112019120568208-pat00038
Figure 112019120568208-pat00038

반응 용기에 상기 실시예 4 에서 제조한 4-(6-메타아크릴로옥시헥실옥시)-4'-(5-피리미딜)에틴일-3'-메틸아조벤젠 0.5 g (1.036 mmol), 아조비스아이소부틸로나이트릴 0.042 g (0.8 wt%), 메틸메타아크릴레이트 2.1 mL (19.685 mmol) 을 N-메틸-2-피롤리돈에 녹인 후 질소 분위기 하에서 80 ℃에서 48 시간 동안 교반하였다. 반응 혼합물을 과량의 메탄올에 침전시켜 반응을 종료하고 필터 후, 소량의 N-메틸-2-피롤리돈에 녹인 후 과량의 메탄올에 재침전 후 필터하였다. 3회 이상 과량의 메탄올을 이용해서 세척하여 주황색의 고체 고분자 (1.9 g, 77%) 를 얻었다.In a reaction vessel, 0.5 g (1.036 mmol) of 4-(6-methacrylooxyhexyloxy)-4'-(5-pyrimidyl)ethynyl-3'-methylazobenzene prepared in Example 4, azobis 0.042 g (0.8 wt%) of isobutylonitrile and 2.1 mL (19.685 mmol) of methyl methacrylate were dissolved in N-methyl-2-pyrrolidone, followed by stirring at 80° C. under a nitrogen atmosphere for 48 hours. The reaction mixture was precipitated in an excess of methanol to complete the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, reprecipitated in an excess of methanol, and then filtered. It was washed three or more times with an excess of methanol to obtain an orange solid polymer (1.9 g, 77%).

GPC Mn 13,848, Mw 21,669, PDI 1.56GPC Mn 13,848, Mw 21,669, PDI 1.56

<실시예 12> 홀로그램 기록용 고분자 제조 5<Example 12> Preparation of polymer for hologram recording 5

Figure 112019120568208-pat00039
Figure 112019120568208-pat00039

반응 용기에 상기 실시예 5 에서 제조한 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피리미딜)에틴일-3'-메틸아조벤젠 0.5 g (1.036 mmol), 아조비스아이소부틸로나이트릴 0.0421 g (0.8 wt%), 메틸메타아크릴레이트 2.1 mL (19.685 mmol) 을 N-메틸-2-피롤리돈에 녹인 후 질소 분위기 하에서 80 ℃에서 48 시간 동안 교반하였다. 반응 혼합물을 과량의 메탄올에 침전시켜 반응을 종료하고 필터 후, 소량의 N-메틸-2-피롤리돈에 녹인 후 과량의 메탄올에 재침전 후 필터하였다. 3회 이상 과량의 메탄올을 이용해서 세척하여 주황색의 고체 고분자 (1.9 g, 77%) 를 얻었다.In a reaction vessel, 0.5 g (1.036 mmol) of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyrimidyl)ethynyl-3'-methylazobenzene prepared in Example 5, azobis 0.0421 g (0.8 wt%) of isobutylonitrile and 2.1 mL (19.685 mmol) of methyl methacrylate were dissolved in N-methyl-2-pyrrolidone, followed by stirring at 80° C. under a nitrogen atmosphere for 48 hours. The reaction mixture was precipitated in an excess of methanol to complete the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, reprecipitated in an excess of methanol, and then filtered. It was washed three or more times with an excess of methanol to obtain an orange solid polymer (1.9 g, 77%).

GPC Mn 13,848, Mw 21,669, PDI 1.56GPC Mn 13,848, Mw 21,669, PDI 1.56

<실시예 13> 홀로그램 기록용 고분자 제조 6<Example 13> Preparation of polymer for hologram recording 6

Figure 112019120568208-pat00040
Figure 112019120568208-pat00040

반응 용기에 상기 실시예 6 에서 제조한 4-(6-메타아크릴로옥시헥실옥시)-4'-(4-피리미딜)에틴일-3'-메틸아조벤젠 0.5 g (1.038 mmol), 아조비스아이소부틸로나이트릴 0.0421 g (0.8 wt%), 메틸메타아크릴레이트 2.1 mL (19.722 mmol) 을 N-메틸-2-피롤리돈에 녹인 후 질소 분위기 하에서 80 ℃에서 48 시간 동안 교반하였다. 반응 혼합물을 과량의 메탄올에 침전시켜 반응을 종료하고 필터 후, 소량의 N-메틸-2-피롤리돈에 녹인 후 과량의 메탄올에 재침전 후 필터하였다. 3회 이상 과량의 메탄올을 이용해서 세척하여 주황색의 고체 고분자 (1.9 g, 77%) 를 얻었다.In a reaction vessel, 0.5 g (1.038 mmol) of 4-(6-methacrylooxyhexyloxy)-4'-(4-pyrimidyl)ethynyl-3'-methylazobenzene prepared in Example 6, azobis 0.0421 g (0.8 wt%) of isobutylonitrile and 2.1 mL (19.722 mmol) of methyl methacrylate were dissolved in N-methyl-2-pyrrolidone, followed by stirring at 80° C. under a nitrogen atmosphere for 48 hours. The reaction mixture was precipitated in an excess of methanol to complete the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, reprecipitated in an excess of methanol, and then filtered. It was washed three or more times with an excess of methanol to obtain an orange solid polymer (1.9 g, 77%).

GPC Mn 13,848, Mw 21,669, PDI 1.56GPC Mn 13,848, Mw 21,669, PDI 1.56

<실시예 14> 홀로그램 기록용 고분자 제조 7<Example 14> Preparation of polymer for hologram recording 7

Figure 112019120568208-pat00041
Figure 112019120568208-pat00041

반응 용기에 상기 실시예 7 에서 제조한 4-(6-메타아크릴로옥시헥실옥시)-4'-(2-피라진일)에틴일-3'-메틸아조벤젠 0.5 g (1.038 mmol), 아조비스아이소부틸로나이트릴 0.0421 g (0.8 wt%), 메틸메타아크릴레이트 2.1 mL (19.722 mmol) 을 N-메틸-2-피롤리돈에 녹인 후 질소 분위기 하에서 80 ℃에서 48 시간 동안 교반하였다. 반응 혼합물을 과량의 메탄올에 침전시켜 반응을 종료하고 필터 후, 소량의 N-메틸-2-피롤리돈에 녹인 후 과량의 메탄올에 재침전 후 필터하였다. 3회 이상 과량의 메탄올을 이용해서 세척하여 주황색의 고체 고분자 (1.9 g, 77%) 를 얻었다.In a reaction vessel, 0.5 g (1.038 mmol) of 4-(6-methacrylooxyhexyloxy)-4'-(2-pyrazinyl)ethynyl-3'-methylazobenzene prepared in Example 7, azobis 0.0421 g (0.8 wt%) of isobutylonitrile and 2.1 mL (19.722 mmol) of methyl methacrylate were dissolved in N-methyl-2-pyrrolidone, followed by stirring at 80° C. under a nitrogen atmosphere for 48 hours. The reaction mixture was precipitated in an excess of methanol to complete the reaction, filtered, dissolved in a small amount of N-methyl-2-pyrrolidone, reprecipitated in an excess of methanol, and then filtered. It was washed three or more times with an excess of methanol to obtain an orange solid polymer (1.9 g, 77%).

GPC Mn 13,848, Mw 21,669, PDI 1.56GPC Mn 13,848, Mw 21,669, PDI 1.56

상기 실시예 8 내지 14에서 제조한 홀로그램 기록용 고분자의 구조를 정리하여 하기 표 2에 나타내었다.The structures of the hologram recording polymers prepared in Examples 8 to 14 are summarized and shown in Table 2 below.

실시예Example 구조structure 실시예Example 구조structure 88

Figure 112019120568208-pat00042
Figure 112019120568208-pat00042
1212
Figure 112019120568208-pat00043
Figure 112019120568208-pat00043
 99
Figure 112019120568208-pat00044
Figure 112019120568208-pat00044
 1313
Figure 112019120568208-pat00045
Figure 112019120568208-pat00045
 1010
Figure 112019120568208-pat00046
Figure 112019120568208-pat00046
 1414
Figure 112019120568208-pat00047
Figure 112019120568208-pat00047
 1111
Figure 112019120568208-pat00048
Figure 112019120568208-pat00048

<실험예 1> 본 발명에 따른 고분자 화합물의 흡광도 측정 실험<Experimental Example 1> Absorbance measurement experiment of the polymer compound according to the present invention

본 발명에 따른 고분자 화합물의 흡광도를 알아보기 위하여, 클로로포름, 디클로로메탄, 아세토니트릴, THF 등의 용매에 고분자 화합물을 녹이고 UV-Vis. 흡수스펙트럼 측정용 셀에 넣고 300 nm에서 800 nm까지의 파장별 흡수도를 측정하여, 그 결과를 도 1에 나타내었다.In order to check the absorbance of the polymer compound according to the present invention, the polymer compound is dissolved in a solvent such as chloroform, dichloromethane, acetonitrile, or THF, followed by UV-Vis. The absorbance was measured for each wavelength from 300 nm to 800 nm in a cell for measuring an absorption spectrum, and the results are shown in FIG. 1 .

도 1은 고분자 화합물의 파장에 따른 흡광도를 나타낸 그래프이다.1 is a graph showing the absorbance according to the wavelength of the polymer compound.

도 1에서 알 수 있는 바와 같이, 본 발명에 따른 고분자 화합물인 실시예 8 내지 12의 경우, 380 내지 390 nm의 파장에서 흡광도가 높게 나타나는 것을 확인할 수 있다.As can be seen from FIG. 1 , in the case of Examples 8 to 12, which is a polymer compound according to the present invention, it can be confirmed that the absorbance is high at a wavelength of 380 to 390 nm.

<실험예 2> 본 발명에 따른 고분자 화합물의 등흡수점 측정 실험<Experimental Example 2> Experiment for measuring the isobaric point of the polymer compound according to the present invention

본 발명에 따른 고분자 화합물(실시예 8)의 등흡수점을 알아보기 위하여, 클로로포름, 디클로로메탄, 아세토니트릴, THF 등의 용매에 고분자 화합물을 녹이고 UV-Vis. 흡수스펙트럼 측정용 셀에 넣고 자외선을 조사하여 trans 이정질체를 cis 이성질체로 전환된 후 300 nm에서 800 nm까지의 파장별 흡수도를 측정하여, 그 결과를 도 2에 나타내었다.In order to find out the absorption point of the polymer compound according to the present invention (Example 8), the polymer compound was dissolved in a solvent such as chloroform, dichloromethane, acetonitrile, and THF, followed by UV-Vis. After the trans isomer was converted into the cis isomer by putting it in a cell for measuring an absorption spectrum and irradiating with ultraviolet rays, the absorbance for each wavelength from 300 nm to 800 nm was measured, and the results are shown in FIG. 2 .

도 2는 고분자 화합물의 자외선 조사 후 파장에 따른 흡광도를 나타낸 그래프이다.2 is a graph showing absorbance according to wavelength after UV irradiation of a polymer compound.

도 2에서 알 수 있는 바와 같이, 본 발명에 따른 고분자 화합물인 실시예 8의 경우, 450 내지 470 nm의 파장에서 등흡수점 파장이 나타나는 것을 확인할 수 있다.As can be seen from FIG. 2 , in the case of Example 8, which is a polymer compound according to the present invention, it can be confirmed that the iso-absorption point wavelength appears at a wavelength of 450 to 470 nm.

따라서, 본 발명에 따른 고분자 화합물은 종래 홀로그램 기록 고분자가 낼 수 없었던 청색 파장 영역에서의 등흡수점 파장을 보이므로, 청색 색상을 포함하는 홀로그램의 제조용 조성물로써 유용하게 사용될 수 있다.Therefore, since the polymer compound according to the present invention exhibits an isobaric wavelength in the blue wavelength region that cannot be produced by conventional hologram recording polymers, it can be usefully used as a composition for producing a hologram including a blue color.

<실험예 3> 본 발명에 따른 고분자 화합물의 회절효율 측정 실험<Experimental Example 3> Diffraction efficiency measurement experiment of the polymer compound according to the present invention

본 발명에 따른 고분자의 회절효율 특성분석을 위하여 Four wave mixing(FWM) 측정법을 이용하였다. FWM 측정 셋업은 크게 기록빔을 이용하여 필름에 홀로그램을 기록하는 부분과, 이와 동기화하여 실시간으로 아조벤젠 고분자 필름의 회절 효율 값을 측정하기 위한 부분으로 구성된다. 460 nm 레이저를 이용하여 회절무늬를 기록하였으며, 기록된 홀로그램의 회절효율 측정을 위하여 필름의 normal direction으로 입사되는 레이저 빔과 반대편에서 동일한 각도를 가지고 입사하도록 재생 빔을 설계하였다. 샘플에 입사된 재생빔은 기록된 홀로그램에 의해 회절되고 포토 다이오드를 통해 회절된 빔의 세기를 실시간으로 측정할 수 있다. 입사한 빔의 세기와 회절되어 나온 빔의 세기의 비로부터 회절 효율을 구할 수 있다. FWM의 개념도는 도 4와 같다.Four wave mixing (FWM) measurement method was used to characterize the diffraction efficiency of the polymer according to the present invention. The FWM measurement setup is largely composed of a part for recording a hologram on a film using a recording beam, and a part for measuring the diffraction efficiency value of the azobenzene polymer film in real time in synchronization with this. A diffraction pattern was recorded using a 460 nm laser, and a reproducing beam was designed to have the same angle as the laser beam incident in the normal direction of the film to measure the diffraction efficiency of the recorded hologram. The reproduction beam incident on the sample is diffracted by the recorded hologram, and the intensity of the diffracted beam can be measured in real time through the photodiode. The diffraction efficiency can be obtained from the ratio of the intensity of the incident beam to the intensity of the diffracted beam. A conceptual diagram of the FWM is shown in FIG. 4 .

도 3은 본 발명에 따른 아조벤젠 고분자 필름의 청색 레이저로 기록한 홀로그램의 회절효율을 나타낸 그래프이다.3 is a graph showing the diffraction efficiency of a hologram recorded with a blue laser of an azobenzene polymer film according to the present invention.

도 3에서 알 수 있는 바와 같이, 본 발명에 따른 아조벤젠 고분자 필름의 청색 레이저로 기록한 홀로그램의 회절 효율은 우수함을 알 수 있다.As can be seen from FIG. 3 , it can be seen that the diffraction efficiency of the hologram recorded with the blue laser of the azobenzene polymer film according to the present invention is excellent.

따라서, 본 발명에 따른 아조벤젠 단량체 화합물을 포함하는 고분자는 청색 레이저 조사에 의한 홀로그램 기록/재기록 소재로 유용하게 사용될 수 있다.Therefore, the polymer containing the azobenzene monomer compound according to the present invention can be usefully used as a hologram recording/rewriting material by blue laser irradiation.

Claims (12)

하기 화학식 1로 표시되는 아조벤젠 단량체:
[화학식 1]
Figure 112019120568208-pat00049

상기 화학식 1에서,
R1은 수소, 또는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬이고, 상기 n은 1 내지 4의 정수이고;
R2는 질소를 하나 이상 포함하는 5 내지 10 원자의 헤테로아릴이고;
L은 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-20알킬렌이고; 및
Q는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기이다.
Azobenzene monomer represented by the following formula (1):
[Formula 1]
Figure 112019120568208-pat00049

In Formula 1,
R 1 is hydrogen or straight-chain or branched C 1-20 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer from 1 to 4;
R 2 is 5 to 10 membered heteroaryl containing at least one nitrogen;
L is straight or branched C 1-20 alkylene unsubstituted or substituted with one or more fluoro; and
Q is a photocrosslinkable functional group including at least one radically polymerizable double bond in the molecule.
 제1항에 있어서,
R1은 수소, 또는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-10알킬이고, 상기 n은 1 내지 3의 정수이고;
R2는 질소를 하나 이상 포함하는 6 원자의 헤테로아릴이고;
L은 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-10알킬렌이고; 및
Q는 분자 내에 라디칼 중합성의 이중결합을 하나 이상 포함하는 광가교성 관능기인 것을 특징으로 하는 아조벤젠 단량체.
According to claim 1,
R 1 is hydrogen or straight or branched C 1-10 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer from 1 to 3;
R 2 is 6 membered heteroaryl containing at least one nitrogen;
L is straight or branched C 1-10 alkylene unsubstituted or substituted with one or more fluoro; and
Q is an azobenzene monomer, characterized in that it is a photocrosslinkable functional group containing at least one radical polymerizable double bond in the molecule.
 제1항에 있어서,
R1은 수소, 또는 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-5알킬이고, 상기 n은 1 내지 2의 정수이고;
R2는 피리딘, 또는 피리미딘이고;
L은 비치환 또는 하나 이상의 플루오로로 치환된 직쇄 또는 분지쇄의 C1-6알킬렌이고; 및
Q는
Figure 112019120568208-pat00050
,
Figure 112019120568208-pat00051
,
Figure 112019120568208-pat00052
,
Figure 112019120568208-pat00053
,
Figure 112019120568208-pat00054
,
Figure 112019120568208-pat00055
,
Figure 112019120568208-pat00056
,
Figure 112019120568208-pat00057
,
Figure 112019120568208-pat00058
,
Figure 112019120568208-pat00059
또는
Figure 112019120568208-pat00060
인 것을 특징으로 하는 아조벤젠 단량체.
According to claim 1,
R 1 is hydrogen or straight-chain or branched C 1-5 alkyl unsubstituted or substituted with one or more fluoro, wherein n is an integer from 1 to 2;
R 2 is pyridine or pyrimidine;
L is straight or branched C 1-6 alkylene unsubstituted or substituted with one or more fluoro; and
Q is
Figure 112019120568208-pat00050
,
Figure 112019120568208-pat00051
,
Figure 112019120568208-pat00052
,
Figure 112019120568208-pat00053
,
Figure 112019120568208-pat00054
,
Figure 112019120568208-pat00055
,
Figure 112019120568208-pat00056
,
Figure 112019120568208-pat00057
,
Figure 112019120568208-pat00058
,
Figure 112019120568208-pat00059
or
Figure 112019120568208-pat00060
Azobenzene monomer, characterized in that.
 제1항에 있어서,
상기 화학식 1로 표시되는 아조벤젠 단량체는, 하기 화합물 군으로부터 선택되는 어느 하나의 화합물인 것을 특징으로 하는 아조벤젠 단량체:
Figure 112021057153750-pat00061
,
Figure 112021057153750-pat00062
,
Figure 112021057153750-pat00063
,
Figure 112021057153750-pat00064
,
Figure 112021057153750-pat00065
,
Figure 112021057153750-pat00066
,
Figure 112021057153750-pat00067
.
According to claim 1,
The azobenzene monomer represented by Formula 1 is an azobenzene monomer, characterized in that it is any one compound selected from the following compound group:
Figure 112021057153750-pat00061
,
Figure 112021057153750-pat00062
,
Figure 112021057153750-pat00063
,
Figure 112021057153750-pat00064
,
Figure 112021057153750-pat00065
,
Figure 112021057153750-pat00066
,
Figure 112021057153750-pat00067
.
 제1항의 화학식 1로 표시되는 아조벤젠 단량체; 및
바이닐 아크릴기를 가지는 단량체;의 중합에 의해 형성되는 고분자.
An azobenzene monomer represented by Formula 1 of claim 1; and
A polymer formed by polymerization of a monomer having a vinyl acryl group.
 제5항에 있어서,
상기 고분자는 상기 화학식 1로 표시되는 아조벤젠 단량체 내 Q의 이중결합과, 상기 바이닐 아크릴기를 가지는 단량체 내 바이닐기가 중합 반응되어 형성되는 것을 특징으로 하는 고분자.
6. The method of claim 5,
The polymer is a polymer, characterized in that it is formed by a polymerization reaction of the double bond of Q in the azobenzene monomer represented by Formula 1 and the vinyl group in the monomer having the vinyl acryl group.
 제5항의 고분자를 포함하는 광 굴절율 변조 중합체 조성물.
A light refractive index modulating polymer composition comprising the polymer of claim 5 .
 제5항의 고분자를 포함하는 홀로그램 기록용 조성물.
A hologram recording composition comprising the polymer of claim 5 .
 제8항에 있어서,
상기 홀로그램 기록용 조성물은 400 내지 600 nm의 파장을 흡수하는 것을 특징으로 하는 홀로그램 기록용 조성물.
9. The method of claim 8,
The composition for recording a hologram, characterized in that it absorbs a wavelength of 400 to 600 nm.
 제8항의 홀로그램 기록용 조성물로 이루어진 기록층이 기판 위에 형성된 홀로그램 기록 매체.
A hologram recording medium in which a recording layer made of the hologram recording composition of claim 8 is formed on a substrate.
 제5항의 고분자로 박막을 제조하는 단계(단계 1); 및
상기 단계 1에서 제조한 박막에 레이저 회절무늬를 조사하는 단계(단계 2);를 포함하는 홀로그램 기록 방법.
Preparing a thin film with the polymer of claim 5 (step 1); and
and irradiating a laser diffraction pattern on the thin film prepared in step 1 (step 2).
 제10항의 홀로그램 기록 매체에 홀로그램을 기록할 때 사용된 기준광만을, 상기 홀로그램 기록 매체에 조사하는 단계를 포함하는 홀로그램 재기록 방법.A hologram re-recording method comprising the step of irradiating only the reference light used when recording the hologram on the hologram recording medium of claim 10 to the hologram recording medium.
KR1020190151521A 2019-11-22 2019-11-22 Nitrogen heteroaromatic containing azobenzene compound and composition for blue hologram recording comprising thereof KR102311861B1 (en)

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