JP2008260846A - Photoreactive liquid crystal monomer and production method of main chain type liquid crystal polymer using the same - Google Patents
Photoreactive liquid crystal monomer and production method of main chain type liquid crystal polymer using the same Download PDFInfo
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Abstract
Description
本発明は、エンジニアリングプラスチック、光学フィルター、高強度・高弾性繊維、表示・記録材料などに用いることができる主鎖型液晶ポリマーを製造できる光反応性液晶性モノマー及びそれを用いた主鎖型液晶ポリマーの製造方法に関する。 The present invention relates to a photoreactive liquid crystalline monomer capable of producing a main chain type liquid crystal polymer that can be used for engineering plastics, optical filters, high strength / high elasticity fibers, display / recording materials, and the like, and a main chain type liquid crystal using the same. The present invention relates to a method for producing a polymer.
従来の液晶性ポリマーとくに主鎖型の液晶性ポリマーを合成するためにはしばしば高温(約300℃)や高真空などの厳しい条件が必要であり、また重合触媒をもちいることも多い。しかし、最近このような厳しい条件を必要としない光重合によって主鎖型液晶性ポリマーを合成した例が2件報告されている。
1つはJ. Lubらのエン−チオール反応を利用したもの(非特許文献1参照)であり、
ここには、液晶性モノマー
4-(4-(5-hexenyloxy)benzoyloxy)-1-(4-(5-ercaptopentyloxy)benzoyloxy)-2-methylbenzene の液晶相における光重合および得られたチオエーテル結合を含む主鎖型液晶性ポリマーの性質が開示されている。
もう1つは我々によるケイ皮酸の光二量化反応を利用したものである(特許文献1、非特許文献2参照)。ここには、液晶性モノマー1,4-bis(4-(6-cinnamoyloxyhexyloxy)benzoyloxy)benzeneの液晶相における光重合および得られたシクロブタン環を含む主鎖型液晶性ポリマーの性質が開示されている。
One is based on the ene-thiol reaction of J. Lub et al. (See Non-Patent Document 1),
Here is a liquid crystalline monomer
Photopolymerization of 4- (4- (5-hexenyloxy) benzoyloxy) -1- (4- (5-ercaptopentyloxy) benzoyloxy) -2-methylbenzene in the liquid crystal phase and the main chain type liquid crystalline polymer containing thioether bonds obtained Properties are disclosed.
The other uses our photodimerization reaction of cinnamic acid (see
本発明は、
本発明者によるケイ皮酸の光二量化反応による光重合の例は高温・高真空を必要としないが、J. Lubらの場合は光開始剤を必要とし、また我々が以前報告したものの場合、モノマーからポリマーへの高い転化率を実現させるためには三重項増感剤が必要であった。
しかし、これら重合時に添加する触媒や開始剤、増感剤はほんの少量であっても得られるポリマーにしばしば悪影響を及ぼすことが判明した。
本発明は開始剤や増感剤を用いなくても高い転化率で主鎖型液晶性ポリマーの光重合を実現させる光反応性液晶性モノマー及びそれを用いた液晶性ポリマーの製造方法を提供する。
The present invention
Examples of photopolymerization by the photodimerization reaction of cinnamic acid by the present inventor do not require high temperature and high vacuum, but in the case of J. Lub et al., A photoinitiator is required, and in the case of what we have previously reported, Triplet sensitizers were required to achieve high monomer to polymer conversion.
However, it has been found that even a small amount of the catalyst, initiator and sensitizer added during the polymerization often adversely affects the resulting polymer.
The present invention provides a photoreactive liquid crystalline monomer capable of realizing photopolymerization of a main chain liquid crystalline polymer at a high conversion without using an initiator or a sensitizer, and a method for producing a liquid crystalline polymer using the same. .
光重合の光源には通常水銀ランプを用いるが、水銀ランプの放射する光は254, 365, 405, 436nmなどの輝線スペクトルからなる。我々が以前報告したケイ皮酸の系ではこれらの波長の光を効率よく吸収することができないために三重項増感剤が必要であった。そこで本発明では水銀ランプの輝線の1つである365nmの光を効率よく吸収し、しかもケイ皮酸と同じように二量化反応を起こすアントラセンに着目した。つまり、アントラセンを光反応性部位として分子の両末端に持ち、液晶性に与るメソゲンを分子の中央に持つような化合物を設計・合成し、これに光照射して主鎖型の液晶性ポリマーへ導くことにより、開始剤や増感剤を用いなくても高い転化率で主鎖型液晶性ポリマーが得られることを見出し、本発明を完成させるに至った。
すなわち、本発明は、
一般式
で示される光反応性液晶性モノマーである。
A mercury lamp is usually used as a light source for photopolymerization, but the light emitted from the mercury lamp is composed of emission line spectra such as 254, 365, 405, and 436 nm. Triplet sensitizers were necessary because the cinnamic acid system we reported previously cannot absorb light at these wavelengths efficiently. Therefore, the present invention focuses on anthracene that efficiently absorbs 365 nm light, which is one of the emission lines of a mercury lamp, and causes a dimerization reaction in the same manner as cinnamic acid. In other words, a compound that has anthracene as a photoreactive site at both ends of the molecule and a mesogen that affects liquid crystallinity at the center of the molecule is designed and synthesized, and this is irradiated with light to form a main-chain liquid crystalline polymer. As a result, it was found that a main chain type liquid crystalline polymer can be obtained with a high conversion without using an initiator or a sensitizer, and the present invention has been completed.
That is, the present invention
General formula
Is a photoreactive liquid crystalline monomer represented by
また、本発明は、
一般式
で示される光反応性液晶性モノマーを、開始剤や増感剤を用いることなく、波長365nmの光のみで重合させることを特徴とする主鎖型液晶ポリマーの製造方法である。
The present invention also provides:
General formula
A photoreactive liquid crystalline monomer represented by the formula (1) is polymerized only with light having a wavelength of 365 nm without using an initiator or a sensitizer.
本発明の光反応性液晶性モノマーでは高温・高真空などの厳しい条件を必要としないで、簡便な重合装置で光重合によって液晶性ポリマーが得られ、本発明の光反応性液晶性モノマーを用いた主鎖型液晶ポリマーの製造方法で得られた主鎖型液晶ポリマーは、開始剤や増感剤を用いなくても高い転化率であり、重合後のポリマーの精製というプロセスを省けると言う有利がある。 With the photoreactive liquid crystalline monomer of the present invention, a liquid crystalline polymer can be obtained by photopolymerization with a simple polymerization apparatus without requiring severe conditions such as high temperature and high vacuum, and the photoreactive liquid crystalline monomer of the present invention is used. The main chain type liquid crystal polymer obtained by the production method of the main chain type liquid crystal polymer has a high conversion rate without using an initiator or a sensitizer, and is advantageous in that the process of purification of the polymer after polymerization can be omitted. There is.
本発明で用いる光重合装置の一例を図2に示す。水銀ランプを用いて、光学フィルターなどを用いて紫外光365nmを取り出し、反応物に照射することにより光重合が行える。
本発明において、中央にメソゲンを有する液晶性モノマーは、中央にメソゲン基を有し、スペーサ分子を介して、アントラセンを有する分子である。
本発明では、周知のメソゲンを用いることができる。代表的には前記のMesogenicUnitで示したものを用いる。また、スペーサは、周知のスペーサを用いることができる。
An example of the photopolymerization apparatus used in the present invention is shown in FIG. Photopolymerization can be performed by taking out 365 nm of ultraviolet light using an optical filter or the like using a mercury lamp and irradiating the reaction product.
In the present invention, the liquid crystalline monomer having a mesogen in the center is a molecule having a mesogenic group in the center and anthracene via a spacer molecule.
In the present invention, known mesogens can be used. Typically, those shown in the above Mesogenic Unit are used. As the spacer, a known spacer can be used.
本発明について実施例を用いてさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
(中央にメソゲンを有する液晶性モノマーの合成)
分子の両末端にアントラセン部位を有し、かつ中央にメソゲンを有する液晶性モノマーとし1,4-Bis(4-(anthracene-2-carbonyloxyhexyloxy)benzoyloxy)benzene(A)を図1に示した合成スキームにより合成した。
Aは降温時196℃からネマチック液晶相を示し、186℃で結晶化した。
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(Synthesis of liquid crystalline monomer with mesogen in the center)
1,4-Bis (4- (anthracene-2-carbonyloxyhexyloxy) benzoyloxy) benzene (A) as a liquid crystalline monomer with an anthracene moiety at both ends of the molecule and a mesogen in the center Was synthesized.
A exhibited a nematic liquid crystal phase from 196 ° C. when the temperature was lowered, and crystallized at 186 ° C.
(主鎖型液晶ポリマーの製造)
ポリマーの合成には溶媒を使わないバルク状態での光重合および溶液での光重合を用いることができる。
1.バルクでの光重合
2 mgのAをカバーガラスに挟み、ホットステージ上で190 ℃に加熱してネマチック液晶状態とした。190 ℃に保ったまま、水銀ランプを用いて紫外光(365 nm, 5 mW/cm2)を30分間照射した。重合装置の模式図を図2に示す。照射したサンプルは190℃では等方性の液体となったが、温度を下げていくと175 ℃付近からネマチック液晶相を示しはじめ、約150 ℃で完全に液晶相となった。光照射後150 ℃での偏光顕微鏡写真を図3に示す。ネマチック相に特有のシュリーレンテクスチャーであることがわかる。この光照射後のサンプルと照射前のAの1H-NMRスペクトルとGPCクロマトグラムを比較した。図4の1H-NMRスペクトルでは光照射前には見られなかったアントラセンの二量体に由来する4.63, 6.83, 7.62 ppmのピークが光照射後では見られ、光二量化反応が進行していたことが確認できた。また図5のGPCクロマトグラムでは光照射前はモノマーAに基づく鋭い1本のピークが見られたが、光照射後は短時間側にもピークが現れかつブロードになっていたことから高分子量の成分が生成していたことがわかった。以上の結果からモノマーAのバルクの状態に光照射することにより主鎖型液晶性ポリマーが得られることが確かめられた。このポリマーの構造式を図6に示した。
2.溶液での光重合
磁気攪拌子の入ったサンプル管にAの10 wt%−1,1,2,2-テトラクロロエタン溶液を100℃のシリコンオイルバス中で調整した。セプタムキャップでサンプル管を密栓し、アルゴンガスで10分間バブリングを行った。その後シリコンオイルバスの温度を100℃に保ち、マグネチックスターラーで溶液を攪拌しながら紫外光(365 nm, 8 mW/cm2)を24時間照射した。この重合装置の模式図を図7に示す。光照射後のサンプルと照射前のAのGPCクロマトグラムを比較した(図8)。バルクでの光重合と比べても今回はさらに短時間側にピークがシフトしている、つまりより高分子量体が生成していることがわかった。またモノマーもほとんど残っていないことが確認できた。このGPCクロマトグラムからここで得られたポリマーの分子量はポリスチレン換算で重量平均分子量:88000(重合度91)、数平均分子量:36000(重合度38)と見積もられた。光照射後のポリマーの偏光顕微鏡観察を行ったところ150℃以下でネマチック液晶相を発現することがわかった。図9に140℃でのシュリーレンテクスチャーの偏光顕微鏡写真を示す。
以上から今回合成した液晶性モノマーを用いれば増感剤なしでも効率よく光重合が進行し、主鎖型液晶性ポリマーが得られることがわかった。
(Manufacture of main chain type liquid crystal polymer)
For polymer synthesis, photopolymerization in a bulk state without using a solvent and photopolymerization in a solution can be used.
1. Photopolymerization in bulk
2 mg of A was sandwiched between cover glasses and heated to 190 ° C. on a hot stage to obtain a nematic liquid crystal state. While maintaining at 190 ° C., ultraviolet light (365 nm, 5 mW / cm 2 ) was irradiated for 30 minutes using a mercury lamp. A schematic diagram of the polymerization apparatus is shown in FIG. The irradiated sample became an isotropic liquid at 190 ° C, but began to show a nematic liquid crystal phase from around 175 ° C as the temperature was lowered, and became a completely liquid crystal phase at about 150 ° C. FIG. 3 shows a polarizing microscope photograph at 150 ° C. after the light irradiation. It can be seen that this is a schlieren texture unique to the nematic phase. The 1 H-NMR spectrum and GPC chromatogram of A after irradiation and A before irradiation were compared. In the 1 H-NMR spectrum of FIG. 4, peaks at 4.63, 6.83, and 7.62 ppm derived from the anthracene dimer that were not observed before light irradiation were observed after light irradiation, and the photodimerization reaction was in progress. I was able to confirm. In the GPC chromatogram in Fig. 5, a sharp single peak based on monomer A was observed before light irradiation. However, after light irradiation, a peak appeared on the short time side and was broad. It turned out that the component was producing | generating. From the above results, it was confirmed that a main-chain liquid crystalline polymer can be obtained by irradiating the monomer A in the bulk state. The structural formula of this polymer is shown in FIG.
2. A 10 wt% -1,1,2,2-tetrachloroethane solution of A was prepared in a 100 ° C silicon oil bath in a sample tube containing a photopolymerization magnetic stirrer in solution. The sample tube was sealed with a septum cap and bubbled with argon gas for 10 minutes. Thereafter, the temperature of the silicon oil bath was kept at 100 ° C., and the solution was irradiated with ultraviolet light (365 nm, 8 mW / cm 2 ) for 24 hours while stirring the solution with a magnetic stirrer. A schematic diagram of this polymerization apparatus is shown in FIG. The GPC chromatogram of the sample after light irradiation and A before irradiation was compared (FIG. 8). Compared with bulk photopolymerization, it was found that the peak shifted to a shorter time this time, that is, a higher molecular weight was formed. It was also confirmed that almost no monomer remained. From this GPC chromatogram, the molecular weight of the polymer obtained here was estimated in terms of polystyrene as weight average molecular weight: 88000 (polymerization degree 91) and number average molecular weight: 36000 (polymerization degree 38). When the polymer after light irradiation was observed with a polarizing microscope, it was found that a nematic liquid crystal phase was developed at 150 ° C. or lower. FIG. 9 shows a polarizing microscope photograph of the schlieren texture at 140 ° C.
From the above, it was found that when the liquid crystalline monomer synthesized this time was used, photopolymerization proceeded efficiently without a sensitizer, and a main chain liquid crystalline polymer was obtained.
本発明の光反応性液晶性モノマー及び光反応性液晶性モノマーを用いた主鎖型液晶ポリマーは、高純度で製造できるため、性能が良く、種種の表示装置に用いることができ、産業上の利用可能性は高い。 Since the main chain type liquid crystal polymer using the photoreactive liquid crystalline monomer and the photoreactive liquid crystalline monomer of the present invention can be produced with high purity, it has good performance and can be used for various display devices. The availability is high.
Claims (2)
で示される光反応性液晶性モノマー。 General formula
A photoreactive liquid crystalline monomer represented by
で示される光反応性液晶性モノマーを、開始剤や増感剤を用いることなく、波長365nmの光のみで重合させることを特徴とする主鎖型液晶ポリマーの製造方法。 General formula
A method for producing a main-chain liquid crystal polymer, wherein the photoreactive liquid crystalline monomer represented by the formula (1) is polymerized only with light having a wavelength of 365 nm without using an initiator or a sensitizer.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009256485A (en) * | 2008-04-17 | 2009-11-05 | National Institute Of Advanced Industrial & Technology | Amorphous polymer of dianthracene and optical information recording thin film material using it |
JP2010006712A (en) * | 2008-06-24 | 2010-01-14 | National Institute Of Advanced Industrial & Technology | Anthracene derivative, its dimer, optical information-recording material using them, and method for recording optical information |
JP2012045864A (en) * | 2010-08-27 | 2012-03-08 | National Institute Of Advanced Industrial Science & Technology | Optical information recording medium using liquid crystal polymer, optical information recording method, and method for manufacturing optical information recording medium |
JP2014037496A (en) * | 2012-08-17 | 2014-02-27 | National Institute Of Advanced Industrial & Technology | Resin composition capable of phase separation, writable resin composition for optical recording and optical recording medium using the same, method of recording information using the optical recording medium |
JP2017528429A (en) * | 2014-07-17 | 2017-09-28 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | Bimesogenic compounds and mesogenic media |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005005572A1 (en) * | 2003-07-10 | 2005-01-20 | Merck Patent Gmbh | Substituted anthracenes |
JP2006299100A (en) * | 2005-04-21 | 2006-11-02 | National Institute Of Advanced Industrial & Technology | Liquid crystal monomer, liquid crystal oligomer, liquid crystal polymer, and method for producing the same |
JP2008083394A (en) * | 2006-09-27 | 2008-04-10 | Fujifilm Corp | Optical anisotropic film and method of manufacturing the same |
-
2007
- 2007-04-12 JP JP2007104629A patent/JP5051520B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005005572A1 (en) * | 2003-07-10 | 2005-01-20 | Merck Patent Gmbh | Substituted anthracenes |
JP2006299100A (en) * | 2005-04-21 | 2006-11-02 | National Institute Of Advanced Industrial & Technology | Liquid crystal monomer, liquid crystal oligomer, liquid crystal polymer, and method for producing the same |
JP2008083394A (en) * | 2006-09-27 | 2008-04-10 | Fujifilm Corp | Optical anisotropic film and method of manufacturing the same |
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JP2009256485A (en) * | 2008-04-17 | 2009-11-05 | National Institute Of Advanced Industrial & Technology | Amorphous polymer of dianthracene and optical information recording thin film material using it |
JP2010006712A (en) * | 2008-06-24 | 2010-01-14 | National Institute Of Advanced Industrial & Technology | Anthracene derivative, its dimer, optical information-recording material using them, and method for recording optical information |
JP2012045864A (en) * | 2010-08-27 | 2012-03-08 | National Institute Of Advanced Industrial Science & Technology | Optical information recording medium using liquid crystal polymer, optical information recording method, and method for manufacturing optical information recording medium |
JP2014037496A (en) * | 2012-08-17 | 2014-02-27 | National Institute Of Advanced Industrial & Technology | Resin composition capable of phase separation, writable resin composition for optical recording and optical recording medium using the same, method of recording information using the optical recording medium |
JP2017528429A (en) * | 2014-07-17 | 2017-09-28 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | Bimesogenic compounds and mesogenic media |
US10450508B2 (en) | 2014-07-17 | 2019-10-22 | Merck Patent Gmbh | Bimesogenic compounds and mesogenic media |
US10465040B2 (en) | 2014-10-31 | 2019-11-05 | National Institute Of Advanced Industrial Science And Technology | Photocurable composition and anthracene derivative used with the same |
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