JPS63273648A - Production of side-chain-type polymer liquid crystal - Google Patents
Production of side-chain-type polymer liquid crystalInfo
- Publication number
- JPS63273648A JPS63273648A JP10824787A JP10824787A JPS63273648A JP S63273648 A JPS63273648 A JP S63273648A JP 10824787 A JP10824787 A JP 10824787A JP 10824787 A JP10824787 A JP 10824787A JP S63273648 A JPS63273648 A JP S63273648A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- chain
- polymer liquid
- compound
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005264 High molar mass liquid crystal Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 51
- 150000007824 aliphatic compounds Chemical class 0.000 claims abstract description 23
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000011541 reaction mixture Substances 0.000 claims abstract description 15
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 6
- 239000004711 α-olefin Substances 0.000 claims abstract 2
- 239000005266 side chain polymer Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 22
- -1 siloxane skeleton Chemical group 0.000 claims description 19
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 150000003058 platinum compounds Chemical class 0.000 abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000005684 electric field Effects 0.000 description 25
- 125000006850 spacer group Chemical group 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000007704 transition Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000005267 main chain polymer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- ZRMIETZFPZGBEB-UHFFFAOYSA-N 4-(4-hydroxyphenyl)benzonitrile Chemical group C1=CC(O)=CC=C1C1=CC=C(C#N)C=C1 ZRMIETZFPZGBEB-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- BPMBNLJJRKCCRT-UHFFFAOYSA-N 4-phenylbenzonitrile Chemical group C1=CC(C#N)=CC=C1C1=CC=CC=C1 BPMBNLJJRKCCRT-UHFFFAOYSA-N 0.000 description 1
- OZYYQTRHHXLTKX-UHFFFAOYSA-N 7-octenoic acid Chemical compound OC(=O)CCCCCC=C OZYYQTRHHXLTKX-UHFFFAOYSA-N 0.000 description 1
- 101000914484 Homo sapiens T-lymphocyte activation antigen CD80 Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 102100027222 T-lymphocyte activation antigen CD80 Human genes 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical group C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol group Chemical group [C@@H]1(CC[C@H]2[C@@H]3CC=C4C[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)[C@H](C)CCCC(C)C HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は記録材料、表示材料、各種光学素子などに利用
可能なシロキサン骨格を有する側鎖型高分子液晶の新規
な製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a side-chain polymer liquid crystal having a siloxane skeleton, which can be used for recording materials, display materials, various optical elements, etc.
近年高性能高機能性材料として高分子液晶、中でもある
一定温度以上で液晶状態を形成する謂ゆるサーモトロピ
ック液晶高分子が学界および産業界の注目を集めている
。高分子液晶としては主鎖型高分子液晶と側鎖型高分子
液晶に大別されることは周知の通りである。ベンゼン環
、ナフタレン環、ビフェニル環などの剛直な骨格を主鎖
に含んだ主鎖型高分子液晶は高強力、高弾性率素材とし
て産業界より多（の関心を集めており、一部既に工業的
に製造されている。一方、メソーゲンと呼ばれる剛直な
骨格構造を有する化合物をスペーサーと呼ばれる可撓性
を有する柔軟な脂肪族鎖等を介してポリマー主鎖に結合
させた謂ゆる側鎖型高分子液晶に関しても多くの構造の
化合物が提案されており、多くの報告がある。例えば、
Ａｄｖａｎｃｅｓｉｎ Ｐｏｌｙｍｅｒ ８ ｃｉｅｎ
ｃｅ ６０ ／ ６１巻、９９〜１７２頁、および同１
７５〜２５２頁（８ｐｒｉｎｇｅｒ−Ｖｅｒｌａｒｇ
、 Ｂｅｒｌｉｎ 。In recent years, liquid crystal polymers have been attracting attention in academia and industry as high-performance and highly functional materials, and in particular, so-called thermotropic liquid crystal polymers that form a liquid crystal state above a certain temperature. It is well known that polymer liquid crystals are broadly classified into main chain type polymer liquid crystals and side chain type polymer liquid crystals. Main chain polymer liquid crystals containing rigid skeletons such as benzene rings, naphthalene rings, and biphenyl rings in their main chains are attracting a lot of interest from industry as materials with high strength and high elastic modulus, and some of them have already been used in industrial applications. On the other hand, so-called side-chain polymers are produced in which a compound with a rigid skeleton called a mesogen is bonded to the polymer main chain via a flexible aliphatic chain called a spacer. Compounds with many structures have been proposed for molecular liquid crystals, and there are many reports.For example,
Advancesin Polymer 8 cien
ce volume 60/61, pages 99-172, and same 1
pp. 75-252 (8pringer-Verlarg
, Berlin.
Ｈｅｉｄｅｌｂｅｒｇ 、 １９８４ ）を参考文献と
して挙げることかできる。Heidelberg, 1984) may be cited as a reference.
この側鎖型高分子液晶は、低分子液晶の液晶性、機能性
に高分子性を付与したものと見なすことができ、低分子
液晶にはないい（つかの特徴を有している。すなわち、
高分子液晶は低分子液晶に比較してその粘度が高いため
、低分子液晶を用いる場合に比較して高分子液晶では液
晶を含有する装置（デバイス）の加工が著しく容易とな
るため、装置のシールが容易となり、また封入技術も容
易となる。また、装置内における表面処理等の配向方法
も容易となり、更に、装置の大型化、大面積化が可能と
なる。更に高分子液晶では、液晶状態における分子の配
向状態を凍結保持させることが可能となる。すなわち、
側鎖型高分子液晶の薄膜に液晶状態において電場あるい
は磁場等の外部場を＃／ｌｌｌ０すると、分子が該外部
場の影響を受け、一定方向に配向し、次いで温度を下げ
ることによって、該外部場を除去してもその配向状態を
保持することが可能となる。このようなことから、側鎖
型高分子液晶は、記録材料、表示材料、非線形光学材料
、各種光学素子など多くの用途への展開が期待されてい
る。例えば特開昭６０−１１４８２３号公報には側鎖型
高分子液晶を消去可能な情報記録装置として用いること
が提案されている。This side-chain polymer liquid crystal can be considered to have added polymer properties to the liquid crystallinity and functionality of low-molecular liquid crystals, and has certain characteristics that low-molecular liquid crystals do not have. ,
Since polymer liquid crystals have a higher viscosity than low-molecular liquid crystals, it is much easier to process devices containing liquid crystals with polymer liquid crystals than when using low-molecular liquid crystals. It is easier to seal and the encapsulation technique is also easier. In addition, orientation methods such as surface treatment within the device become easier, and furthermore, it becomes possible to increase the size and area of the device. Furthermore, in polymer liquid crystals, it is possible to freeze and maintain the orientation state of molecules in the liquid crystal state. That is,
When an external field such as an electric field or a magnetic field is applied to a thin film of side-chain polymer liquid crystal in the liquid crystal state, the molecules are influenced by the external field and are oriented in a certain direction.Then, by lowering the temperature, the external field Even if the field is removed, the orientation state can be maintained. For these reasons, side-chain polymer liquid crystals are expected to be used in many applications such as recording materials, display materials, nonlinear optical materials, and various optical elements. For example, Japanese Unexamined Patent Publication No. 114823/1983 proposes the use of a side-chain polymer liquid crystal as an erasable information recording device.
側鎖型高分子液晶の主鎖として用いられるポリマー骨格
としてはアクリル酸ポリマー、メタクリル酸ポリマー、
シロキサンポリマー、ビニルエーテルポリマーなどが提
案されている。メソーゲンとしては、シアノ基、ハロゲ
ン、アルキル基、シクロアルキル基、アルコキシル基な
どで置換されたフェニル基、ビフェニル基あるいはシッ
フ塩基、コレステリル基などが知られている。側鎖型高
分子液晶においては、上記の主鎖ポリマーおよびメソー
ゲンだけでなく、主鎖ポリマーおよびメソーゲンをつな
ぐスペーサ一部分も液晶の機能発現に対して重要な役割
を演じていることも知られている。すなわち、スペーサ
一部分は主鎖ポリマーとメソーゲン基の運動性を切り離
す作用を有しており、液晶への転移温度ならびに液晶か
ら等吉相への転移温度は、このスペーサーの種類に著し
く影響される。更に、前述したように、側鎖型高分子液
晶を電場あるいは磁場等の外部場によりその配向状態を
変化させようとした場合には、スペーサーの種類によっ
ては配向状態が変化しなかったり、変化する場合でも変
化に要する時間に差があることが知られている。Polymer skeletons used as the main chain of side-chain polymer liquid crystals include acrylic acid polymers, methacrylic acid polymers,
Siloxane polymers, vinyl ether polymers, etc. have been proposed. As mesogens, phenyl groups, biphenyl groups, Schiff bases, cholesteryl groups, etc. substituted with cyano groups, halogens, alkyl groups, cycloalkyl groups, alkoxyl groups, etc. are known. In side-chain polymer liquid crystals, it is known that not only the main chain polymer and mesogen mentioned above, but also a part of the spacer that connects the main chain polymer and mesogen play an important role in the function expression of the liquid crystal. . That is, a portion of the spacer has the effect of separating the mobility of the main chain polymer and the mesogen group, and the transition temperature to liquid crystal and the transition temperature from liquid crystal to the isotonic phase are significantly influenced by the type of spacer. Furthermore, as mentioned above, when trying to change the orientation of side-chain polymer liquid crystals using an external field such as an electric or magnetic field, the orientation may not change or may change depending on the type of spacer. It is known that there are differences in the time required for change even in different cases.
側鎖型高分子液晶の内でもシロキサンを主鎖骨格ポリマ
ーとするものは、骨格ポリマーの柔軟性が高いこと、ま
た末端二重結合を有するスペーサーとヒドロシリル化反
応により骨格ポリマーにメソーゲンを結合させることが
可能であることなどから最近注目を集めており、該側鎖
型高分子液晶の電気熱光学特性について詳細に研究され
ている。Among side-chain polymer liquid crystals, those with siloxane as the main chain skeleton polymer have high flexibility of the skeleton polymer, and mesogens can be bonded to the skeleton polymer through a hydrosilylation reaction with a spacer having a terminal double bond. Recently, it has been attracting attention due to its ability to perform the following steps, and the electrothermo-optical properties of the side-chain polymer liquid crystal have been studied in detail.
例えばＨ，Ｊ、 Ｃｏ１ｅｓらによる以下の報告Ｐｏｌ
ｙｍａｒ。For example, the following report by H. J. Coles et al.
ymar.
１９８５年、２０巻、１８０１〜１８０６頁、Ｍｏｌｅ
ｍｌａｒＣｒｙｓｔａｌｓ ａｎｄ Ｌｉｑｕｉｄ Ｃ
ｒｙｓｔａｌｓ Ｌｅｔｔｅｒ 、 １９８５年、１巻
７５〜８１頁およびＭｏ１ｅ＊ｌａｒ Ｃｒｙｓｔａｌ
ｓ ａｎｄＬｉｑｕｉｄ Ｃｒｙｓｔａｌｓ 、 １９
８４年、１０２巻、４３〜４８頁などを参考文献として
挙げることができる。1985, Vol. 20, pp. 1801-1806, Mole
mlarCrystals and Liquid C
crystals Letter, 1985, Vol. 1, pp. 75-81 and Mole*lar Crystal
s and Liquid Crystals, 19
References include 1984, volume 102, pages 43-48.
シロキサンポリマーを主鎖骨格とする側鎖型高分子液晶
は有機溶媒中、ケイ素原子に結合した水素原子を有する
シロキサンポリマー、例えばポリメチルヒドロシロキサ
ンとメソーゲンに結合した末端二重結合を有するスペー
サー成分とを、白金化合物触媒、例えば塩化白金酸を用
いて製造されることが知られている。A side-chain polymer liquid crystal having a siloxane polymer main chain skeleton is prepared by combining a siloxane polymer having a hydrogen atom bonded to a silicon atom, such as polymethylhydrosiloxane, and a spacer component having a terminal double bond bonded to a mesogen in an organic solvent. are known to be produced using platinum compound catalysts, such as chloroplatinic acid.
ここでＡはメソーゲンおよびスペーサーの一部を表わす
。Here, A represents a mesogen and a part of a spacer.
該反応はトルエンあるいはテトラハイドロフランのよう
な各原料化合物を溶解する有機溶媒中で行なわれる。反
応終了後生成したポリマーを溶解しない溶液、例えばメ
タノール中に反応混合液を注ぎ込むことにより生成した
ポリマーは単離される。その後クロロホルム等に溶解し
、再び再沈殿を繰り返すことによって精製される。上記
のシロキサンポリマーを主骨格とする側鎖型高分子液晶
の合成、単離精製法に関してはＭｏ１ｅｃｕ１．ａｒ
Ｃｒｙｓｔａｌｓａｎｄ Ｌｉｑｕｉｄ Ｃｒｙｓｔａ
ｌｓ 、 １９８５年、１２２巻、２０５〜２０８頁を
参考文献として挙げることができる。The reaction is carried out in an organic solvent such as toluene or tetrahydrofuran that dissolves each starting material compound. After the reaction is complete, the produced polymer is isolated by pouring the reaction mixture into a solution that does not dissolve the produced polymer, such as methanol. Thereafter, it is purified by dissolving it in chloroform or the like and repeating reprecipitation again. Regarding the synthesis, isolation and purification method of the side-chain polymer liquid crystal having the above-mentioned siloxane polymer as the main skeleton, see Molecu1. ar
Crystalsand Liquid Crystal
ls, 1985, volume 122, pages 205-208.
本発明者らの詳細なる検討によると、従来提案されてい
る方法に従い合成、単離、精製したシロキサン骨格の側
鎖型高分子液晶にはいくつかの改良すべき問題点が残さ
れていることが明らかとなつた。According to detailed studies by the present inventors, there remain some problems that need to be improved in side-chain polymer liquid crystals with siloxane skeletons synthesized, isolated, and purified according to conventionally proposed methods. It became clear.
まず、従来提案されている方法に従って合成、単離、精
製したシロキサン骨格側鎖型高分子液晶は熱安定性が必
ずしも充分ではないことが明らかとなった。First, it has become clear that the siloxane skeleton side chain polymer liquid crystals synthesized, isolated, and purified according to conventionally proposed methods do not necessarily have sufficient thermal stability.
たとえば、後の比較例で示されるように、従来提案され
ている方法に従って合成、単離、精製されたシーキサン
骨格側鎖型高分子液晶を、液晶から等吉相への転移温度
近辺で一定時間電場を印加したのち冷却し、再び該温度
で電場を印加した場合には、電場に対する配向状態の変
化の応答性が著しく低下する。このことは、該側鎖型高
分子液晶の電場による配向状態の変化をくり返した場合
には応答性が次第に低下することを意味しており該側鎖
型高分子液晶を実用に供す場合には耐久性の面で好まし
くない。この一つの原因は、本発明者らの検討によると
出発原料として用いたシロキサンポリマー中の８ｉ−Ｈ
結合の水素原子が側鎖成分で完全に置換されず一部８ｉ
−Ｈ結合が生成した側鎖型高分子液晶中に残存し、この
ことが該高分子液晶の熱安定性の低下の一因となってい
ると推定される。また、たとえ側鎖成分の原料化合物で
ある芳香族化合物誘導体を出発原料シロキサンポリマー
中の８ｉ−Ｈ結合の量に対して、大過剰用いてヒドロシ
リル化反応を実施しても、生成した側鎖型高分子液晶中
には、かなりの量の８ｉ−Ｈ結合が残存することが明ら
かとなった。For example, as shown in the comparative example below, a hexane skeleton side-chain polymer liquid crystal synthesized, isolated, and purified according to a conventionally proposed method is subjected to an electric field for a certain period of time near the transition temperature from liquid crystal to isotokic phase. If a temperature is applied, the temperature is cooled, and an electric field is applied again at that temperature, the responsiveness of the change in orientation state to the electric field is significantly reduced. This means that if the alignment state of the side-chain polymer liquid crystal is repeatedly changed by an electric field, the response will gradually decrease, and when the side-chain polymer liquid crystal is put into practical use, Unfavorable in terms of durability. One of the reasons for this is that 8i-H in the siloxane polymer used as a starting material, according to the inventors' study
The hydrogen atom of the bond is not completely replaced by the side chain component and some 8i
-H bonds remain in the generated side-chain polymer liquid crystal, and this is presumed to be one of the causes of the decrease in thermal stability of the polymer liquid crystal. In addition, even if the hydrosilylation reaction is carried out by using the aromatic compound derivative, which is the raw material compound for the side chain component, in large excess with respect to the amount of 8i-H bonds in the starting material siloxane polymer, the side chain type formed It has become clear that a considerable amount of 8i-H bonds remain in the polymer liquid crystal.
更に、従来提案されている方法に従い合成、単離、精製
したシロキサン骨格の側鎖型高分子液晶中には、触媒と
して用いた白金化合物の大半がそのまま残存し、従来提
案されている再沈殿による精製方法を何回くり返しても
、この残存する白金化合物の量は、大きくは減少しない
ことが明らかとなった。この高分子液晶中に残存する白
金化合物は、該高分子液晶の物性に悪影響を及ぼすこと
が確かめられた。特に白金のような金属成分か含まｎる
と、この高分子液晶を電気用途に用いた場合には種々の
悪影響を及ぼす。更に、触媒成分を含んだ高分子液晶は
長期にわたる使用あるいは高温度下での使用において望
ましからざる副反応を誘発し、該高分子液晶の物性変化
が生じることが碕かめられた。Furthermore, most of the platinum compound used as a catalyst remains in the side-chain polymer liquid crystal with a siloxane skeleton synthesized, isolated, and purified according to the conventionally proposed method, and the platinum compound used as a catalyst remains as it is. It has become clear that no matter how many times the purification process is repeated, the amount of the remaining platinum compound does not decrease significantly. It was confirmed that the platinum compound remaining in this polymeric liquid crystal has an adverse effect on the physical properties of the polymeric liquid crystal. In particular, if metal components such as platinum are included, various adverse effects will occur when this polymeric liquid crystal is used for electrical purposes. Furthermore, it has been confirmed that polymer liquid crystals containing catalyst components induce undesirable side reactions when used for long periods of time or at high temperatures, resulting in changes in the physical properties of the polymer liquid crystals.
このように、従来提案されているシロキサン骨格側儲型
高分子液晶の製造方法には、いくつかの解決すべき問題
点が残されている。As described above, there are still some problems that need to be solved in the conventionally proposed methods for producing siloxane skeleton-side polymer liquid crystals.
本発明者らは、前記のような問題点−のないシロキサン
骨格側鎖型高分子液晶の製造方法について鋭属検肘を重
ねた結果、本発明を完成するに至った。本発明に従えば
、有機溶媒中、第■族遷移金属化合物触媒の存在下、主
鎖骨格を形成するケイ累原子に結合した水素原子を有す
るシロキサンポリマーと、側鎖成分を与える原料化合物
である芳香族化合物誘導体とより、ヒドロシリル化反応
によりシロキサン骨格を有する側鎖型高分子液晶を製造
する方法において、一定時間ヒドロシリル化反応を行な
った後の反応混合液に、または、ヒドロシリル化反応後
生成した側鎖型高分子液晶を単離し、再び適当な有機溶
媒に溶解させた溶液に末端炭素−炭素二重結合を有する
脂肪族化合物を添加し、一定時間処理を行なうことを特
徴とする側鎖型高分子液晶°の製造方法が提供される。The present inventors have completed the present invention as a result of extensive research into a method for producing a siloxane skeleton side chain type polymer liquid crystal free from the above-mentioned problems. According to the present invention, in an organic solvent, in the presence of a Group Ⅰ transition metal compound catalyst, a siloxane polymer having a hydrogen atom bonded to a silicon atom forming a main chain skeleton and a raw material compound providing a side chain component. In a method for producing a side-chain polymer liquid crystal having a siloxane skeleton by a hydrosilylation reaction using an aromatic compound derivative, the reaction mixture after the hydrosilylation reaction has been carried out for a certain period of time, or the product formed after the hydrosilylation reaction A side chain type polymer liquid crystal is isolated and redissolved in an appropriate organic solvent, an aliphatic compound having a terminal carbon-carbon double bond is added to the solution, and the treatment is carried out for a certain period of time. A method of manufacturing a polymeric liquid crystal is provided.
本発明においては、メソーゲンを含む側鎖成分をシロキ
サン骨格ポリマーに付加させ側鎖型高分子液晶を合成し
たのち、該側鎖型高分子液晶に末を
端炭素−炭素二重結８省する脂肪族化合物を反応させる
ことが特徴であり、本方法により従来提案されている方
法により得られるシロキサン骨格側鎖型高分子液晶中に
残存する触媒の量を著しく低減化させることが可能とな
り、かつ本発明の方法により得られたシロキサン骨格側
鎧型高分子液晶は良好な熱安定性を有する。In the present invention, a side chain component containing a mesogen is added to a siloxane skeleton polymer to synthesize a side chain polymer liquid crystal, and then a terminal carbon-carbon double bond is added to the side chain polymer liquid crystal. This method makes it possible to significantly reduce the amount of catalyst remaining in the siloxane skeleton side-chain type polymer liquid crystal obtained by the conventionally proposed method. The siloxane skeleton side armor polymer liquid crystal obtained by the method of the invention has good thermal stability.
本発明において主鎖骨格の原料ポリマーとして用いられ
るシロキサンポリマーは、ケイ素原子に結合した水素原
子を有する任意のシロキサンポリマーであり、好ましく
は平均くり返し単位数が１０〜２００であり、分子内に
１０〜１５０個の８ｉ−Ｈ結合を有するシロキサンポリ
マーである。The siloxane polymer used as a raw material polymer for the main chain skeleton in the present invention is any siloxane polymer having a hydrogen atom bonded to a silicon atom, and preferably has an average repeating unit number of 10 to 200, with 10 to 200 repeating units in the molecule. It is a siloxane polymer with 150 8i-H bonds.
側鎖成分を与える芳香族化合物誘導体とは、従来公知の
側鎖型高分子液晶のスペーサーおよびメソーゲン部分を
与える原料化合物であり、末端に二重結合を有する脂肪
族化合物と液晶を形成する芳香族化合物である。好まし
くは該化合物は以下の一般式（Ｉ）で表わすことができ
る。The aromatic compound derivative that provides the side chain component is a raw material compound that provides the spacer and mesogen portion of the conventionally known side chain type polymer liquid crystal, and is an aromatic compound that forms the liquid crystal with an aliphatic compound having a double bond at the terminal. It is a compound. Preferably, the compound can be represented by the following general formula (I).
Ｃ１１ｚ −（Ｊｌ （ＣＨｚ ）ｎ＋１−＋ｎＡ
（Ｉ）式中ｎは０から２０であり、Ｘは０、（Ｘ）
２ 、ＮＨＣＯであり、ｍはＯまたはｌであり、Ａは置
換基を有していてもよい少なくとも一個以上の芳香域を
含む一種もしくは二種以上の芳香族残基である。式（Ｉ
）で表わされる化合物はｎ、ｍおよびΔが異なる二種以
上の化合物を同時に用いることができることは言うまで
もない。Ａの具体例としては、以下の基を挙げることが
できる。C11z −(Jl (CHz)n+1−+nA
(I) In the formula, n is 0 to 20, X is 0, (X)
2, NHCO, m is O or l, and A is one or more aromatic residues containing at least one aromatic region which may have a substituent. Formula (I
It goes without saying that two or more kinds of compounds represented by () having different n, m and Δ can be used at the same time. Specific examples of A include the following groups.
側鎖型高分子液晶は公知のようにベンゼン、トルエン、
テトラヒドロフラン等の適当な溶媒中、シーキサンポリ
マーと側鎖成分を与える芳香族化合物誘導体とを第■族
遷移金属化合物触媒、好ましくは白金化合物触媒、例え
ば塩化白金酸あるいはジシクーペンタジエニル白金クロ
ライド触媒の存在下、ヒドロシリル化反応を行なうこと
により製造できる。その触媒濃度としては、一般にはシ
ロキサンポリマーに対して通常ｏ、ｏ ｏ ｉ〜５重量
％、好ましくはｏ、ｏｏｓ〜３重ｆｊｋｇ６の範囲内の
量で用いられる。反応温度としては、室温から２００℃
、好ましくは４０〜１２０℃の範囲内である。反応時間
としては、１０分から１００時間、好ましくは３０分か
ら５０時間の範囲内である。側鎖成分を与える原料化合
物である芳香族化合物誘導体とシロキサンポリマーの量
比は任意の割合とすることができるが、通常該芳香族化
合物誘導体とシロキサンポリマー中の水素原子のそル比
が０．２〜５．０好ましくは０，３〜２．０の範囲内で
ある。該当量比か０．２よりも小ざな場合には側鎖成分
の割合が少なすぎて高分子液晶を形成しない場合がある
。上記の当量比が５を越える場合には生成した側鎖型高
分子液晶の物性には全く問題はないか、未反応の側鎖成
分原料化合物が多量残存するため、経済的に不利である
。Side-chain polymer liquid crystals are known to contain benzene, toluene,
In a suitable solvent such as tetrahydrofuran, the shexane polymer and the aromatic compound derivative providing the side chain component are combined with a Group I transition metal compound catalyst, preferably a platinum compound catalyst, such as chloroplatinic acid or dicyclopentadienyl platinum chloride catalyst. It can be produced by carrying out a hydrosilylation reaction in the presence of. The catalyst concentration is generally in the range of o, o o i to 5% by weight, preferably o, oos to 3 fjkg6, based on the siloxane polymer. The reaction temperature is from room temperature to 200℃
, preferably within the range of 40 to 120°C. The reaction time is within the range of 10 minutes to 100 hours, preferably 30 minutes to 50 hours. The ratio of the aromatic compound derivative, which is the raw material compound providing the side chain component, to the siloxane polymer can be set to any desired ratio, but usually the solubility ratio of the hydrogen atoms in the aromatic compound derivative and the siloxane polymer is 0. It is within the range of 2 to 5.0, preferably 0.3 to 2.0. If the ratio is less than 0.2, the proportion of side chain components may be too small to form a polymeric liquid crystal. If the above equivalent ratio exceeds 5, there may be no problem at all with the physical properties of the side chain type polymer liquid crystal produced, or there will be a large amount of unreacted side chain component raw material remaining, which is economically disadvantageous.
ヒドロシリル化反応の追跡は、系中に残存する未反応の
側鎖成分の原料である芳香族化合物誘導体を液体クロマ
トグラフィー等で定量する方法、赤外吸収スペクトルで
、８１−Ｍ結合を定量する方法あるいは核磁気共鳴スペ
クトルで８ｉ−Ｒ結合あるいは側鎖成分を定量する方法
などにより行ない得る。所望量の側鎖成分がシロキサン
ポリマーに付加したのち、１）ヒドロシリル化反応混合
液中に、もしくは２）生成した側鎖型高分子液晶を公知
の方法により単離した後、再び適当な有機溶媒に溶解さ
せた溶液中に末端炭素−炭素二重結合を有する脂肪族化
合物を添加し、一定時間反応を行なった後、側鎖型高分
子液晶を単離することによって、従来提案されている方
法に比べて残存する触媒化合物の量が著しく少なく、か
つ、熱安定性のすぐれた側鎖型高分子液晶が得られる。The hydrosilylation reaction can be tracked by quantifying the aromatic compound derivative, which is the raw material for the unreacted side chain components remaining in the system, using liquid chromatography, etc., or by quantifying the 81-M bond using infrared absorption spectroscopy. Alternatively, it can be carried out by a method of quantifying 8i-R bonds or side chain components using nuclear magnetic resonance spectroscopy. After the desired amount of the side chain component has been added to the siloxane polymer, it is added to the siloxane polymer either 1) in the hydrosilylation reaction mixture, or 2) after isolating the formed side chain polymer liquid crystal by a known method, it is added again to a suitable organic solvent. A conventional method proposed by adding an aliphatic compound having a terminal carbon-carbon double bond to a solution dissolved in A side-chain polymer liquid crystal with significantly less residual catalyst compound and excellent thermal stability can be obtained.
末端炭素−炭素二重結合を有する脂肪族化合物との反応
は、０〜２００℃好ましくは２０〜１５０℃の温度範囲
内で一定時間、例えば１分から１００時間、通常は１０
分から５０時間行なわれる。該反応は、通常は大気圧下
で行なわれるが、用いる末端炭素−炭素二’Ｍｉｓ ｆ
’ｏ鷺ａ ｂｓ低い場合、例え４ばエチレンを用いる場
合には加圧下で行なった方が好ましい場合もある。該反
応は通常は機械的撹拌を行なうことにより実施されるが
、窒素等の不活性ガスあるいは用いる末端炭素−炭素二
重結合を有する脂肪族化合物の沸点が低い場合には該化
合物を反応混合液中に流通させることによって撹拌を行
なうこともできる。The reaction with an aliphatic compound having a terminal carbon-carbon double bond is carried out at a temperature range of 0 to 200°C, preferably 20 to 150°C, for a certain period of time, for example 1 minute to 100 hours, usually 10
It is held for 50 hours. The reaction is usually carried out under atmospheric pressure, but depending on the terminal carbon-carbon di'Mis f
In cases where ethylene is low, for example, when ethylene is used, it may be preferable to carry out the reaction under pressure. The reaction is usually carried out by mechanical stirring, but if the boiling point of the aliphatic compound having a terminal carbon-carbon double bond is low, the reaction mixture may be stirred with an inert gas such as nitrogen or the like. Stirring can also be effected by flowing the mixture through the medium.
用いる末端炭素−炭素二重結合を有する脂肪族化合物と
しては、末端に炭素−炭素二重結合を有する脂肪族化合
物であれば任意の化合物を用いることができるか、中で
も末端がＣＨ４＝Ｏｎ−で辰わされるビニル基を有する
炭素数２〜２２の脂肪族化合物が好ましい。好ましい具
体例としては、例えばエチレン、フロペン、１−ブテン
、１−ヘキセン、１−ヘプテン、１−オクテン、３−メ
チル−１−ブテン等の分岐を有していてもよいａ−オレ
フィン；２−プロペン−１−オール、３−フｆンー１−
オール、４−ペンテン−１−オール等の不飽和アルコー
ル；アクリル酸、３−ブテン酸等の不飽和カルボン酸；
アクリル酸メチルエステル等の不飽和カルボン酸アルキ
ルエステル；アクロレイン、２−プロペナール、３−−
ｊテナール等ノ不飽和アルデヒドなどを挙げることがで
きる。As the aliphatic compound having a terminal carbon-carbon double bond to be used, any aliphatic compound having a carbon-carbon double bond at the terminal can be used. An aliphatic compound having 2 to 22 carbon atoms and having a vinyl group is preferred. Preferred specific examples include optionally branched a-olefins such as ethylene, flopene, 1-butene, 1-hexene, 1-heptene, 1-octene, and 3-methyl-1-butene; Propen-1-ol, 3-fhun-1-
unsaturated alcohols such as ol, 4-penten-1-ol; unsaturated carboxylic acids such as acrylic acid and 3-butenoic acid;
Unsaturated carboxylic acid alkyl esters such as acrylic acid methyl ester; acrolein, 2-propenal, 3--
Examples include unsaturated aldehydes such as j-tenal and the like.
これらの中でもエチレンおよび（ｊＨ２＝ ＯＨ（Ｃ１
１ｉｚ ）ｎＣＨｓ（ｎ＝０〜１９）で表わざ几る末端
ビニル基を有する直釦脂肪族炭化水素か得られた側鎖型
高分子液晶の安定性、操作性等の面で最も好ましい。Among these, ethylene and (jH2=OH(C1
A straight button aliphatic hydrocarbon having a terminal vinyl group represented by nCHs (n=0 to 19) is most preferred in terms of stability, operability, etc. of the obtained side chain type polymer liquid crystal.
用いる末端炭素−炭素二重結合を有する脂肪族化合物の
量としては任意の量を用いることができる。触媒として
用いた第■族遷移金属化合物に対して１０当量以上用い
た場合に顕著な効果が得られるので好ましい。用いる末
端炭素−炭素二重結合を有する脂肪族化合物の量の臨界
的な上限値はないが、本発明により得られる側鎖型高分
子液晶化合物は、該脂肪族化合物に通常の場合には溶解
しないので、多量に用いた場合には反応混合液が二相に
分離し、側鎖型高分子液晶を溶解する相での該脂肪族化
合物の濃度は上昇しないので系が二相に分離する量を越
えて該脂肪族化合物を用いても本発明の効果は顕著には
上昇しない。Any amount of aliphatic compound having a terminal carbon-carbon double bond can be used. It is preferable to use the compound in an amount of 10 equivalents or more based on the Group I transition metal compound used as a catalyst because a remarkable effect can be obtained. Although there is no critical upper limit for the amount of the aliphatic compound having a terminal carbon-carbon double bond to be used, the side-chain polymeric liquid crystal compound obtained by the present invention is normally soluble in the aliphatic compound. Therefore, if a large amount is used, the reaction mixture will separate into two phases, and the concentration of the aliphatic compound in the phase in which the side-chain polymer liquid crystal is dissolved will not increase, so the amount at which the system will separate into two phases will increase. Even if the aliphatic compound is used in an amount exceeding 100%, the effects of the present invention will not increase significantly.
本発明の脂肪族化合物による処理は前述したように、シ
ロキサンポリマーと側鎖成分を与える原料化合物とのヒ
ドロシリル化反応の反応混合液中に末端炭素−炭素二重
結合を有する脂肪族化合物を添加する方法およびヒドロ
シリル化反応の終了後、生成した側鎖型高分子液晶を−
たん単離したのら、再び適当な有機溶媒に溶解させ、該
溶液中に該脂肪族化合物を添加して行なうこともできる
が、通常は側鎖型高分子液晶を単離することな（、ヒド
ロシリル化反応混合液中に直接、末端炭素−炭素二重結
合を有する脂肪族化合物を添加する方が操作が容易であ
り、工業的に有利である。As described above, the treatment with an aliphatic compound of the present invention involves adding an aliphatic compound having a terminal carbon-carbon double bond to the reaction mixture of the hydrosilylation reaction between the siloxane polymer and the raw material compound providing the side chain component. After the completion of the method and hydrosilylation reaction, the side-chain polymer liquid crystals produced are
After isolation, the aliphatic compound can be redissolved in a suitable organic solvent and the aliphatic compound added to the solution, but usually the side chain type polymer liquid crystal is not isolated ( Directly adding an aliphatic compound having a terminal carbon-carbon double bond to the hydrosilylation reaction mixture is easier to operate and is industrially advantageous.
該処理の終了後、公知の方法により側釦型高分子液晶が
単離される。After completion of this treatment, the side button type polymer liquid crystal is isolated by a known method.
本発明の方法により得られた側鎖型高分子液晶は、従来
提案されている方法によるものに比べて含有される金属
触媒化合物の量が著しく低減化されているため、各種機
能材料として用いる場合に極めて有利である。また、高
温での長時間の使用における安定性が著しくすぐれてい
る。本発明により得られる側鎖型高分子液晶は、消去書
き変え可能な各種記録媒体、各種光学素子等の用途に適
している。The side-chain type polymer liquid crystal obtained by the method of the present invention contains a significantly reduced amount of metal catalyst compound compared to those obtained by conventionally proposed methods, so it can be used as various functional materials. This is extremely advantageous. Furthermore, it has excellent stability during long-term use at high temperatures. The side-chain polymer liquid crystal obtained by the present invention is suitable for use in various erasable and rewritable recording media, various optical elements, and the like.
゛〔実 施 例〕 以下実施例により本発明を具体的に説明する。[Example of implementation] The present invention will be specifically explained below using Examples.
実施例１
特開昭５６−１３８１２９号公報および特開昭５８−８
０３３号公報記載の方法に従って、ブタジェンよりツー
オクテン酸を合成し７−オクチン酸り一ロライドに変換
したのち、４−ヒドロキシ−４′−シアノビフェニルと
エステル化反応を行なうことによって、４−シアノビフ
ェニル−４−イル、７−オクテノエートを合成した。Example 1 JP-A-56-138129 and JP-A-58-8
According to the method described in Publication No. 033, two-octenoic acid is synthesized from butadiene, converted to 7-octinoic acid monoloride, and then subjected to an esterification reaction with 4-hydroxy-4'-cyanobiphenyl to form 4-cyanobiphenyl- 4-yl, 7-octenoate was synthesized.
撹拌装置、ガス吹込み口および還流装置を備えた５００
ｍ１の三つロフラスコに、上記の４′−シアノビフェニ
ル−４−イル ７−オクテノエート１０．０ｇ、ポリメ
チルハイドロシロキサン（平均くり返し単位数および一
分子内の平均８ｉ−ｆｉ結合数共に４０）１．８１ｇ、
触媒として塩化白金酸６水和物０．００５９およびトル
エン２５０ｙｎＪＩを仕込み窒素ガス流通下６０℃で４
時間撹拌した。４時間後、反応混合液の微量を液体クロ
マトグラフィーで分析することによって仕込んだ４′−
シアノビフェニル−４−イル ７−オクテノエートの約
８０％が反応し、消失していることがわかった。次いで
反応混合液にプロペンを１０１／時の速度でバブリング
させながら、更に２時間激しく撹拌を続けた後、撹拌を
停止した。反応混合液を多量のメタノール中に注ぎ込み
、生成したポリマーを単離したのち、クロロホルムに溶
解し、メタノール中に再沈殿させる方法を合計３回くり
返して精製したのち６０℃で真空乾燥した。得られたポ
リマーは７．５ｇであった。本ポリマー中に含まれる白
金化合物の量を原子吸光スペクトルにより定量したとこ
ろ１．４ｐｐ（白金として）であることがわかった。本
ポリマーの薄片を加熱値＠（Ｌｉｎｋａｍ ＴＨ−６０
０）を備えた偏光顕微鏡直交二フル下で観察したところ
１６３℃から光の透過量は増大しはじめ１７５℃で最大
となったのち、急激に透過光量は減少し視野は暗黒にな
り、本ポリマーはサーモトロピック液晶を示すことが確
認された。また、本ポリマーを水差走査熱量計ＣＤ８０
月ζてｌＯｃ麿の昇温速度で測定したところ、６℃にガ
ラス転移亭
点が１７５℃に液晶から等吉相流体の転移に基づ（吸熱
ピークが観測された。本ポリマーをＣＤ（Ｊ３溶液中、
”Ｈ−ＮＭＢにて分析したところ、未反応の８ｉ−Ｈ結
合はほとんど残存していないことがわかった。500 with stirring device, gas inlet and reflux device
10.0 g of the above 4'-cyanobiphenyl-4-yl 7-octenoate, polymethylhydrosiloxane (both the average number of repeating units and the average number of 8i-fi bonds in one molecule are 40). 81g,
As a catalyst, 0.0059 chloroplatinic acid hexahydrate and 250 ynJI toluene were charged, and the mixture was heated at 60°C under nitrogen gas flow.
Stir for hours. After 4 hours, a trace amount of the reaction mixture was analyzed by liquid chromatography to determine the amount of 4'-
It was found that about 80% of cyanobiphenyl-4-yl 7-octenoate had reacted and disappeared. Then, vigorous stirring was continued for another 2 hours while propene was bubbled into the reaction mixture at a rate of 10 1/hour, and then stirring was stopped. The reaction mixture was poured into a large amount of methanol, the resulting polymer was isolated, dissolved in chloroform, reprecipitated in methanol, and purified three times in total, followed by vacuum drying at 60°C. The amount of polymer obtained was 7.5 g. The amount of platinum compound contained in this polymer was determined by atomic absorption spectroscopy and was found to be 1.4 pp (in terms of platinum). Heating a thin piece of this polymer @ (Linkam TH-60
When observed under an orthogonal polarizing microscope equipped with was confirmed to exhibit thermotropic liquid crystal. In addition, this polymer was measured using a water difference scanning calorimeter CD80.
When measured at a heating rate of 1Oc over the course of a month, the glass transition point was observed at 6℃, and an endothermic peak was observed at 175℃ due to the transition from liquid crystal to 175℃. During,
``Analysis by H-NMB revealed that almost no unreacted 8i-H bonds remained.
本ポリマーを第１図に示す透明電極を有するネサガラス
中に２０μｍのスペーサーを介して封入し、周波数３
ＫＨ２の交流電場を印加したところ、本ポリマーの絶縁
破壊電圧は５００Ｖ（実効値）であった。This polymer was encapsulated in Nesa glass having a transparent electrode as shown in Fig. 1 via a 20 μm spacer, and
When an alternating current electric field of KH2 was applied, the dielectric breakdown voltage of this polymer was 500 V (effective value).
本ポリマーを第２図に示すセル中に封入し、該セルを前
出の加熱装置内で加熱し、１７５℃において３．５皿、
５７０Ｖの交流電場を印加したところ、直ちに視野は暗
黒に変化し、配向状態が変化することが確認された。な
お、第２図に示したセルにおいて、スペーサーとして厚
さ２０μｍのポリイミドフィルムを、また、絶縁膜とし
て厚さ７．５μｍのポリイミドフィルムをそれぞれ用い
た。This polymer was encapsulated in the cell shown in FIG. 2, and the cell was heated in the heating device described above to produce 3.5 plates at 175°C.
When an alternating current electric field of 570 V was applied, the visual field immediately changed to darkness, and it was confirmed that the orientation state changed. In the cell shown in FIG. 2, a 20 μm thick polyimide film was used as a spacer, and a 7.5 μm thick polyimide film was used as an insulating film.
電圧印加後の時間と偏光透過量の関係を第３図に示した
。なお、この測定には横向電気製アナライジングレコー
ダー（３６５５型）を用いた。第３図より偏光透過量が
１／２になる時間（応答時間）を求めると、４０ミリ秒
であることがわかった。FIG. 3 shows the relationship between the time after voltage application and the amount of polarized light transmitted. Note that an analyzing recorder (Model 3655) manufactured by Yokogi Denki was used for this measurement. From FIG. 3, the time (response time) for the amount of transmitted polarized light to be halved was found to be 40 milliseconds.
次いで、本側鎖型高分子液晶の電場配向のくり返し安定
性を知るために、以下のような実験を行ない本側鎖型高
分子液晶の熱安定性を調べた。すなわち、第２図に示し
たセル内で１７５℃で、３．５ＫＨ２，５７０Ｖの交流
電場を１時間印加したのち、電場の印加を停止し、−た
ん冷却し、再び１７５℃で３．５ ＫｎＺ、 ５７０
Ｖの交流電場を印加したところ、配向状態の変化に要す
る時間は第１回目とほぼ同一であった。配向の変化に要
する時間は１秒以内なので、本実験より、本側鎗高分子
液晶の電場配向時のくり返し安定性は、極めてすぐれる
ことかわかる。Next, in order to understand the repeated stability of electric field orientation of the present side chain type polymer liquid crystal, the following experiment was conducted to examine the thermal stability of the present side chain type polymer liquid crystal. That is, after applying an alternating current electric field of 3.5KH2,570V for one hour at 175℃ in the cell shown in FIG. , 570
When an alternating current electric field of V was applied, the time required for the orientation state to change was almost the same as the first time. Since the time required for the alignment to change is within 1 second, it can be seen from this experiment that the repeated stability of the main-sided polymer liquid crystal during electric field alignment is extremely excellent.
実施例２
実施例１において４′−シアノビフェニル−４−イル
７−オクテンエートに代えて４−（３−ブテノキシン−
４′−シアノビフェニルｓ、ｓａｇ＋用いたこと以外は
、実施例１と同様にしてヒドロシリル化反応を４時向行
なったのち、実施例１と同様にしてプロピレンを導入し
て更に２時間反応を続けた。単離精製したのち６．４ｇ
のポリマーが得られた。本ポリマー中に含まれる白金の
量は原子吸光スペクトルによる分析の結果、１．Ｉ胛で
あることがわかった。偏光顕微鏡およびＤ８０による分
析の結果、本ポリマーはサーモトロピック液晶を形成し
、ガラス転移温度は２８℃であり液晶から等吉相への転
移温度は１３４℃であることが確かめられた。実施例１
と同様にして本側鎖型高分子液晶の絶縁破壊電圧を測定
したところ５００Ｖであった。Example 2 In Example 1, 4'-cyanobiphenyl-4-yl
4-(3-butenoxin-
The hydrosilylation reaction was carried out for 4 hours in the same manner as in Example 1, except that 4'-cyanobiphenyl s, sag+ was used, and then propylene was introduced in the same manner as in Example 1 and the reaction was continued for an additional 2 hours. Ta. 6.4g after isolation and purification
of polymer was obtained. As a result of analysis using atomic absorption spectroscopy, the amount of platinum contained in this polymer was determined as follows: It turned out to be I. As a result of polarizing microscopy and D80 analysis, it was confirmed that this polymer forms a thermotropic liquid crystal, the glass transition temperature is 28°C, and the transition temperature from liquid crystal to the isotonic phase is 134°C. Example 1
The dielectric breakdown voltage of the present side-chain polymer liquid crystal was measured in the same manner as above and found to be 500V.
実施例１と同様にして本側鎖型高分子液晶を第２図に示
すセル中に封入し、１３４℃において３Ｋｌｌｚ、 ３
００ Ｖの交流電場を印加したところ、応答時間は約１
秒であった。次いで実施例１と同様にして本セル内で１
３５℃に２時間放置したのち、再び電場を印加したとこ
ろ、応答速度は第１回目とほぼ同じであった。このこと
から、本側鎖型高分子液晶の電場配向時の安定性は極め
てすぐれていることがわかる。In the same manner as in Example 1, this side chain type polymer liquid crystal was sealed in the cell shown in FIG. 2, and at 134° C.
When an AC electric field of 00 V was applied, the response time was approximately 1
It was seconds. Next, in the same manner as in Example 1, 1
When the electric field was applied again after being left at 35° C. for 2 hours, the response speed was almost the same as the first time. From this, it can be seen that the stability of the present side chain type polymer liquid crystal during electric field orientation is extremely excellent.
実施例３
実施例１で用いたフラスコに、４′−シアノビフェニル
−４−イル ７−オクテンエート４．６７ Ｑ。Example 3 Into the flask used in Example 1, add 4.67 Q of 4'-cyanobiphenyl-4-yl 7-octenoate.
ｐ−メトキシフェニル Ｐ−（３−フチツキシンベンゾ
エートｓ、ｏ ｏ ｇ 、塩化白金酸０．００５ｇ、実
施例１と同じポリメチルヒト−シロキサン１．８１ｇお
よびトルエン２５０ｒａｌｌを仕込み、窒素ガス流通下
６０℃で２４時間撹拌を行なった。しかるのち、１−オ
クテン５．０ｇを反応混合液に添加し、更に１時間撹拌
を続けたのち実施例１と同様にして、生成したポリマー
を単離精製した。偏光顕微鏡およびＤ８０による測定の
結果、本ポリマーはサーモトロピック液晶を形成し、ガ
ラス転移温度は４℃であり、液晶から等吉相への転移温
度は１６１℃であった。原子吸光スペクトルによる分析
の結果、本ポリマー中の白金残存量は３．５Ｉ？Ｉｍで
あった。実施例１と同様にして測定した本側鎖型高分子
液晶の絶縁破壊電圧は４００ｖであった。p-Methoxyphenyl P-(3-futituxin benzoate s, o g ), 0.005 g of chloroplatinic acid, 1.81 g of the same polymethylhydrosiloxane as in Example 1, and 250 rall of toluene were charged, and the mixture was heated at 60°C under nitrogen gas flow. Stirring was carried out for 24 hours. Then, 5.0 g of 1-octene was added to the reaction mixture, and stirring was continued for an additional 1 hour, and the produced polymer was isolated and purified in the same manner as in Example 1. Polarized light As a result of measurements using a microscope and D80, this polymer formed a thermotropic liquid crystal, with a glass transition temperature of 4°C, and a transition temperature from liquid crystal to an isotonic phase of 161°C.As a result of analysis using atomic absorption spectroscopy, The residual amount of platinum in this polymer was 3.5 I?Im.The dielectric breakdown voltage of this side chain type polymer liquid crystal measured in the same manner as in Example 1 was 400V.
また実施例１と同様にして測定した本側鎖型高分子液晶
の電場配向時の安定性はすぐれていることが確かめらｒ
した。In addition, it was confirmed that the stability of the present side chain type polymer liquid crystal during electric field alignment was measured in the same manner as in Example 1.
did.
比較例１
実施例１において、ヒドロシリル化反応混合液にプロペ
ンを導入しないこと以外は実施例１を（り返した。得ら
れたポリマーのガラス転移温度は６℃であり、液晶から
等吉相への転移温度は１７５℃であった。原子吸光スペ
クトルＣ（よる分析の結果、本ポリマー中には１５４Ｆ
の白金が残存していることがわかった。本ポリマーをＧ
ＩＸ３１３溶液中で’Ｅｌ−ＮＭＲを測定し、５ｉ−Ｈ
結合のプロトン（４，７０ＷＩｉ）と４−シアノビフェ
ニル−４−イル７−オクテンエート側鎖成分との比較よ
り、本ポ比は３６：４であることがわかった。Comparative Example 1 Example 1 was repeated except that propene was not introduced into the hydrosilylation reaction mixture. The glass transition temperature of the obtained polymer was 6°C, and the transition from liquid crystal to isotokic phase was repeated. The transition temperature was 175°C.As a result of atomic absorption spectrum analysis (C), 154F was present in this polymer.
It was found that some platinum remained. This polymer is
'El-NMR was measured in IX313 solution, and 5i-H
A comparison of the proton (4,70WIi) of the bond and the 4-cyanobiphenyl-4-yl 7-octenoate side chain component revealed that the present polyratio was 36:4.
実施例１と同様にして本ポリマーの絶縁破壊電圧を測定
したところ１．わずが５０Ｖであった。When the dielectric breakdown voltage of this polymer was measured in the same manner as in Example 1, 1. It was only 50V.
本側鎖型高分子液晶を実施例１と同様にして、１７５℃
において３．５ ＫＨ２，５７０Ｖの交流電場を印加し
たところ、応答時間は約４０ミリ秒であった。ところが
１７５℃にて３．５ＫＨｚ、 ５７０Ｖの交流電場を１
時間印加した後、冷却し、再び１７５℃で電場を印加し
たところ、偏光透過光は初期値の１／２には減少せず、
また、視野中には、多（の異物が観察された。This side chain type polymer liquid crystal was heated to 175°C in the same manner as in Example 1.
When an alternating current electric field of 3.5 KH2,570V was applied at the time, the response time was about 40 milliseconds. However, when an AC electric field of 3.5 KHz and 570 V at 175°C is
When the electric field was applied again at 175°C after being applied for a period of time, the polarized transmitted light did not decrease to 1/2 of its initial value.
In addition, many foreign objects were observed in the visual field.
このことから、従来提案されている方法に従って製造さ
れた側鎖型高分子液晶中には多くの触媒金属が残存し、
絶縁破壊電圧も低いことがわかる。Therefore, a large amount of catalytic metal remains in the side-chain polymer liquid crystal produced according to the conventionally proposed method.
It can be seen that the dielectric breakdown voltage is also low.
更に、等吉相への転移温度近辺に電場印加して放置した
のちには、電場により配向状態か変化しなくなることか
ら、本側鎮型高分子液晶の電場応答の安定性は充分では
ないことが推定される。Furthermore, after applying an electric field near the transition temperature to the Tokichi phase and leaving it for a while, the orientation state no longer changes due to the electric field, indicating that the stability of the electric field response of the main-quenched polymer liquid crystal is not sufficient. Presumed.
以上、説明したように、本発明の製造法に従って得られ
た側鎖型高分子液晶は、触媒金属の残存量が著しく少な
（、また８ｉ、−Ｈ結合の残存量も著しく少ない。その
ため、従来提案されている方法に従って！ｌｉＩ造され
たシロキサン骨格側鎖型高分子液晶に較べて、絶縁破壊
電圧が高く、また高温での安定性にすぐれており、耐久
性を有する特長がある。As explained above, the side chain type polymer liquid crystal obtained according to the production method of the present invention has a significantly small amount of remaining catalyst metal (and also a very small amount of remaining 8i and -H bonds. Compared to the siloxane skeleton side chain type polymer liquid crystal produced according to the proposed method, it has a higher dielectric breakdown voltage, excellent stability at high temperatures, and has the characteristics of durability.
第１図は液晶の絶縁破壊電圧を測定するための装置を示
す断面図、第２図は液晶に電場を印加するために用いた
セルの断面図、第３図は本発明の液晶の薄膜を液晶から
等方性流体への転移温度近傍において、電場を印加した
ときの、電場印加時からの偏光透過量の変化を示す図で
ある。Figure 1 is a cross-sectional view of a device for measuring the dielectric breakdown voltage of liquid crystal, Figure 2 is a cross-sectional view of a cell used to apply an electric field to liquid crystal, and Figure 3 is a cross-sectional view of a cell used to apply an electric field to liquid crystal. FIG. 6 is a diagram showing a change in the amount of polarized light transmission from when an electric field is applied when an electric field is applied near the transition temperature from liquid crystal to isotropic fluid.
Claims (1)
、主鎖骨格を形成するケイ素原子に結合した水素原子を
有するシロキサンポリマーと、側鎖成分を与える原料化
合物である芳香族化合物誘導体とより、ヒドロシリル化
反応によりシロキサン骨格を有する側鎖型高分子液晶を
製造する方法において、一定時間ヒドロシリル化反応を
行なった後の反応混合液に、または、ヒドロシリル化反
応後生成した側鎖型高分子液晶を単離し、再び適当な有
機溶媒に溶解させた溶液に、末端炭素−炭素二重結合を
有する脂肪族化合物を添加し、一定時間処理を行なうこ
とを特徴とする側鎖型高分子液晶の製造方法。 ２、末端炭素−炭素二重結合を有する脂肪族化合物が炭
素数が２から２２であるα−オレフィンであることを特
徴とする特許請求の範囲第１項記載の側鎖型高分子液晶
の製造方法。 ３、末端炭素−炭素二重結合を有する脂肪族化合物を、
触媒として用いた第VIII族遷移金属化合物に対して１０
当量以上用いることを特徴とする特許請求の範囲第１項
記載の側鎖型高分子液晶の製造方法。[Claims] 1. In an organic solvent, in the presence of a Group VIII transition metal compound catalyst, a siloxane polymer having a hydrogen atom bonded to a silicon atom forming a main chain skeleton, and a raw material compound providing a side chain component. In a method for producing a side-chain polymer liquid crystal having a siloxane skeleton by a hydrosilylation reaction using a certain aromatic compound derivative, the reaction mixture after the hydrosilylation reaction is carried out for a certain period of time, or the product formed after the hydrosilylation reaction. A side-chain polymer liquid crystal is isolated and redissolved in an appropriate organic solvent, an aliphatic compound having a terminal carbon-carbon double bond is added to the solution, and the treatment is carried out for a certain period of time. A method for producing chain-type polymer liquid crystals. 2. Production of a side-chain polymer liquid crystal according to claim 1, wherein the aliphatic compound having a terminal carbon-carbon double bond is an α-olefin having 2 to 22 carbon atoms. Method. 3. An aliphatic compound having a terminal carbon-carbon double bond,
10 for the Group VIII transition metal compound used as a catalyst.
2. A method for producing a side-chain polymer liquid crystal according to claim 1, characterized in that an equivalent amount or more is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10824787A JPS63273648A (en) | 1987-04-30 | 1987-04-30 | Production of side-chain-type polymer liquid crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10824787A JPS63273648A (en) | 1987-04-30 | 1987-04-30 | Production of side-chain-type polymer liquid crystal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63273648A true JPS63273648A (en) | 1988-11-10 |
Family
ID=14479815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10824787A Pending JPS63273648A (en) | 1987-04-30 | 1987-04-30 | Production of side-chain-type polymer liquid crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63273648A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0267393A (en) * | 1988-08-31 | 1990-03-07 | Ricoh Co Ltd | Liquid crystal element |
| JPH02231460A (en) * | 1989-03-03 | 1990-09-13 | Adeka Argus Chem Co Ltd | Alkenoxycyanobiphenyl compound |
| JPH07316257A (en) * | 1994-05-20 | 1995-12-05 | Fuji Photo Film Co Ltd | Polymer composition, optically anisotropic sheet, production thereof, and liquid display made by using the same |
| JP2006282820A (en) * | 2005-03-31 | 2006-10-19 | Dow Corning Toray Co Ltd | Method for producing organic-modified silicone |
-
1987
- 1987-04-30 JP JP10824787A patent/JPS63273648A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0267393A (en) * | 1988-08-31 | 1990-03-07 | Ricoh Co Ltd | Liquid crystal element |
| JPH02231460A (en) * | 1989-03-03 | 1990-09-13 | Adeka Argus Chem Co Ltd | Alkenoxycyanobiphenyl compound |
| JPH07316257A (en) * | 1994-05-20 | 1995-12-05 | Fuji Photo Film Co Ltd | Polymer composition, optically anisotropic sheet, production thereof, and liquid display made by using the same |
| JP2006282820A (en) * | 2005-03-31 | 2006-10-19 | Dow Corning Toray Co Ltd | Method for producing organic-modified silicone |
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