JPH0641263A - Liquid crystal polyurethane - Google Patents
Liquid crystal polyurethaneInfo
- Publication number
- JPH0641263A JPH0641263A JP4195135A JP19513592A JPH0641263A JP H0641263 A JPH0641263 A JP H0641263A JP 4195135 A JP4195135 A JP 4195135A JP 19513592 A JP19513592 A JP 19513592A JP H0641263 A JPH0641263 A JP H0641263A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane
- liquid crystal
- diisocyanate
- formula
- biphenyl
- 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
Landscapes
- Liquid Crystal Substances (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、液晶性ポリウレタン類
に関する。FIELD OF THE INVENTION The present invention relates to liquid crystalline polyurethanes.
【０００２】[0002]
【従来技術とその課題】ポリウレタンは、電気・電子工
業における透明導電フィルム、有機半導体、有機超伝導
体、感光感熱材料として、また塗料、繊維、合成皮革等
の分野で広く使用されている。一般的に、ポリウレタン
には機能性を有するもの、特に液晶性を示すものも見つ
けられているが、液晶転移温度が高温であるため、溶融
加工時に熱分解の虞れのあるものが多かった。BACKGROUND OF THE INVENTION Polyurethane is widely used as a transparent conductive film, an organic semiconductor, an organic superconductor, a light and heat sensitive material in the electric and electronic industries, and in the fields of paints, fibers, synthetic leather and the like. In general, polyurethanes having functionality, especially those exhibiting liquid crystallinity have been found, but due to the high liquid crystal transition temperature, many of them have a risk of thermal decomposition during melt processing.
【０００３】ある有機結晶を融解するとき、結晶から直
ちに液体にならず、一旦濁った液体になり、更に加熱し
て始めて液体になるものを液晶と呼ぶ。電気・電子材料
で使用されている液晶は、光学的性質（散乱、屈折干渉
等）を有しており、その性質には電場や磁場の影響を受
け易く、液晶温度範囲が広く、また化学的な安定性を有
している。When a certain organic crystal is melted, it is called a liquid crystal that does not immediately become a liquid from the crystal but becomes a turbid liquid and then becomes a liquid only when heated. Liquid crystals used in electrical and electronic materials have optical properties (scattering, refraction interference, etc.), which are easily affected by electric and magnetic fields, have a wide liquid crystal temperature range, and have chemical properties. It has excellent stability.
【０００４】ところが、今日まで工業的に使用されてい
る液晶化合物は、単分子化合物が多く、化学的に安定で
剛直な高分子液晶ポリウレタンは未だ知られていない。However, most of the liquid crystal compounds industrially used to date are monomolecular compounds, and a chemically stable and rigid polymer liquid crystal polyurethane has not been known yet.
【０００５】[0005]
【課題を解決するための手段】本発明の目的は、分解温
度以下で液晶を示し、剛直で化学的に安定なビフェニル
骨格を有する新規なポリウレタンを提供することにあ
る。SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel polyurethane having a rigid and chemically stable biphenyl skeleton which exhibits a liquid crystal at a decomposition temperature or lower.
【０００６】本発明のポリウレタン類は、一般式The polyurethanes of the present invention have the general formula
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】で表わされる繰返し単位を有し、分子量が
５０００〜２０００００の範囲にあるポリウレタン類及
び一般式Polyurethanes having a repeating unit represented by the formula and having a molecular weight in the range of 5,000 to 200,000, and general formulas
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】で表わされる繰返し単位を有し、分子量が
５０００〜２０００００の範囲にあるポリウレタン類で
ある。Polyurethanes having a repeating unit represented by and having a molecular weight in the range of 5,000 to 200,000.
【００１１】上記一般式（１）で表わされるポリウレタ
ン類は、例えば式Polyurethanes represented by the above general formula (1) are represented by the formula
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】で表わされる４，４´−ビス（ヒドロキシ
メチル）ビフェニル（以下「ＢＨＢ」という）と一般式 ＯＣＮ−Ｒ1 −ＮＣＯ （４） （式中Ｒ1 は前記に同じ。）で表わされるジイソシアナ
ート類とを反応させることにより製造される。一般式
（４）のジイソシアナート類としては、例えばメチレン
ジイソシアナート、エチレンジイソシアナート、トリメ
チレンジイソシアナート、テトラメチレンジイソシアナ
ート、ペンタメチレンジイソシアナート、ヘキサメチレ
ンジイソシアナート（以下「ＨＤＩ」という）、２，４
−トルイレンジイソシアナート（以下「ＴＤＩ」とい
う）等を挙げることができる。ＢＨＢとジイソシアナー
ト類との使用割合としては、特に限定されるものではな
いが、通常両者を等モルずつ用いるのがよい。該反応
は、無溶媒下又は溶媒中で行なわれる。ここで溶媒とし
ては、例えばジメチルホルムアミド、ジメチルスルホキ
シド、トルエン、ベンゼン、クロロベンゼン、ジクロロ
ベンゼン、キシレン等を例示できる。該反応は、通常８
０〜２００℃程度、好ましくは１００〜１３０℃の温度
条件下、３〜４時間程度で完結する。4,4'-bis (hydroxymethyl) biphenyl (hereinafter referred to as "BHB") and the general formula OCN-R 1 -NCO (4) (wherein R 1 is the same as above). It is produced by reacting with diisocyanates. Examples of the diisocyanates of the general formula (4) include methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (hereinafter referred to as “ HDI "), 2, 4
-Toluylene diisocyanate (hereinafter referred to as "TDI") and the like can be mentioned. The ratio of BHB and diisocyanates used is not particularly limited, but it is usually preferable to use both of them in equimolar amounts. The reaction is carried out without solvent or in a solvent. Examples of the solvent here include dimethylformamide, dimethylsulfoxide, toluene, benzene, chlorobenzene, dichlorobenzene, and xylene. The reaction is usually 8
It is completed in about 3 to 4 hours under the temperature condition of about 0 to 200 ° C, preferably 100 to 130 ° C.
【００１４】上記一般式（１）で表わされるポリウレタ
ン類は、例えば式（３）で表わされるＢＨＢ、一般式
（４）で表わされるジイソシアナート類及び一般式 ＨＯ−Ｒ2 −ＯＨ （５） （式中Ｒ2 は前記に同じ。）で表わされるα，ω−ジヒ
ドロキシ化合物を反応させることにより製造される。一
般式（５）で表わされるα，ω−ジヒドロキシ化合物と
しては、従来公知のものを広く使用でき、例えばポリエ
チレングリコール、ポリプロピレングリコール、ポリテ
トラメチレングリコール等の重合体等の両末端が水酸基
である化合物を挙げることができる。ＢＨＢ、ジイソシ
アナート類及びα，ω−ジヒドロキシ化合物の使用割合
としては、特に限定されるものではないが、通常ＢＨＢ
１モルに対して、ジイソシアナート類を２モル程度、
α，ω−ジヒドロキシ化合物を１モル程度用いるのがよ
い。該反応も、無溶媒下又は溶媒中で行なわれる。溶媒
としては、上記の溶媒をいずれも使用することができ
る。該反応は、通常８０〜２００℃程度、好ましくは１
００〜１３０℃の温度条件下、３〜４時間程度で完結す
る。The polyurethanes represented by the general formula (1) include, for example, BHB represented by the formula (3), diisocyanates represented by the general formula (4) and general formula HO-R 2 —OH (5). It is produced by reacting an α, ω-dihydroxy compound represented by the formula (R 2 is the same as above). As the α, ω-dihydroxy compound represented by the general formula (5), conventionally known compounds can be widely used. For example, a polymer such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like compound having hydroxyl groups at both ends. Can be mentioned. The ratio of BHB, diisocyanates and α, ω-dihydroxy compound used is not particularly limited, but is usually BHB.
About 2 moles of diisocyanates to 1 mole,
It is preferable to use about 1 mol of the α, ω-dihydroxy compound. The reaction is also performed without a solvent or in a solvent. As the solvent, any of the above solvents can be used. The reaction is usually about 80 to 200 ° C., preferably 1
It is completed in about 3 to 4 hours under the temperature condition of 00 to 130 ° C.
【００１５】斯くして生成する本発明の一般式（１）及
び（２）で表わされるポリウレタン類は、反応終了後、
再沈殿法等の慣用の手段により単離、精製される。The polyurethanes represented by the general formulas (1) and (2) of the present invention thus produced are
It is isolated and purified by a conventional means such as a reprecipitation method.
【００１６】[0016]
【発明の効果】本発明によれば、液晶を示す、剛直で化
学的に安定なビフェニル骨格を有するポリウレタンが提
供される。According to the present invention, there is provided a polyurethane having a rigid and chemically stable biphenyl skeleton, which exhibits a liquid crystal.
【００１７】[0017]
【実施例】以下に実施例を掲げて本発明をより一層明ら
かにする。EXAMPLES The present invention will be further clarified with reference to the following examples.
【００１８】実施例１ 等モルのＢＨＢとＨＤＩとをジメチルホルムアミド中、
１００〜１３０℃で３時間攪拌した。反応終了後、生成
したポリマーをエーテル又はメタノール中で沈殿させて
本発明のポリウレタンを得た。収率８３％。Example 1 Equimolar amounts of BHB and HDI in dimethylformamide,
It stirred at 100-130 degreeC for 3 hours. After completion of the reaction, the produced polymer was precipitated in ether or methanol to obtain the polyurethane of the present invention. Yield 83%.
【００１９】実施例２ ＨＤＩの代りにＴＤＩを用い、実施例１と同様にして本
発明のポリウレタンを得た。収率８０％。Example 2 The polyurethane of the present invention was obtained in the same manner as in Example 1 except that TDI was used instead of HDI. Yield 80%.
【００２０】実施例１及び実施例２で得られたポリウレ
タンは、下記表１に示す範囲において液晶性を示した。The polyurethanes obtained in Examples 1 and 2 exhibited liquid crystallinity in the ranges shown in Table 1 below.
【００２１】[0021]
【表１】 [Table 1]
【００２２】実施例３ ポリテトラメチレングリコール（分子量８７６，保土谷
化学（株）製，以下「ＰＴＧ」という）０．８７６ｇ、
ＢＨＢ０．２１４ｇ及びＨＤＩ０．３３６ｇをジメチル
ホルムアミド５０ｍｌに溶解し、１００〜１３０℃で３
時間加熱攪拌して反応させた後、０．０１ｇのＨＤＩを
更に加えた。反応系はゲル状となり、更に１３０℃で５
時間加熱し、反応を完結させた。生成物をメタノール中
に加え、十分攪拌し、生じた沈殿を集めて乾燥させ、本
発明のポリウレタンを得た。Example 3 0.876 g of polytetramethylene glycol (molecular weight 876, Hodogaya Chemical Co., Ltd., hereinafter referred to as "PTG"),
BHB (0.214 g) and HDI (0.336 g) were dissolved in dimethylformamide (50 ml), and the mixture was mixed at 100 to 130 ° C for 3 times.
After heating and stirring for a reaction time, 0.01 g of HDI was further added. The reaction system becomes a gel, and at 5 ℃ at 5 ℃
Heated for hours to complete the reaction. The product was added to methanol and stirred sufficiently, and the resulting precipitate was collected and dried to obtain the polyurethane of the present invention.
【００２３】該ポリウレタン物性は、以下の通りであ
る。The physical properties of the polyurethane are as follows.
【００２４】ＩＲ（フィルム）；３３５０ｃｍ-1（−Ｎ
Ｈ−），１６９０ｃｍ-1（Ｃ＝Ｏ） 〔η〕（３０℃，ジメチルホルムアミド）＝０．３１。IR (film); 3350 cm -1 (-N
H-), 1690 cm -1 (C = O) [η] (30 ° C, dimethylformamide) = 0.31.
【００２５】実施例４ ３，３´−ジメチルジフェニル−４，４´−ジイソシア
ナート０．５２９ｇ、ＢＰ０．２１４ｇ及びＰＴＧ０．
８７６ｇを１０ｍｌ三つ口フラスコに入れ、窒素ガス気
流中で１００℃に加熱攪拌した。反応系は、直ぐに透明
均一になり、その後粘度が上昇し、最後に白濁した塊に
なった。これを１３０℃で一昼夜放置し、反応を完結さ
せた。生成物をジメチルホルムアミドに溶解し、テトラ
ヒドロフランから再沈殿し、本発明のポリウレタンを得
た。Example 4 0.529 g of 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 0.214 g of BP and PTG0.
876 g was put into a 10 ml three-necked flask, and heated and stirred at 100 ° C. in a nitrogen gas stream. The reaction system immediately became transparent and uniform, then the viscosity increased, and finally became a cloudy lump. This was left overnight at 130 ° C. to complete the reaction. The product was dissolved in dimethylformamide and reprecipitated from tetrahydrofuran to obtain the polyurethane of the present invention.
【００２６】該ポリウレタン物性は、以下の通りであ
る。The physical properties of the polyurethane are as follows.
【００２７】ＩＲ（フィルム）；３３５０ｃｍ-1（−Ｎ
Ｈ−），１７１０ｃｍ-1（Ｃ＝Ｏ） 〔η〕（３０℃，ジメチルホルムアミド）＝０．８５。
上記実施例１〜４で得られた各ポリウレタンを２５０℃
のホットプレートに置いたガラス板上に載せると、白濁
した流動性のある状態になった。その上からもう一枚ガ
ラスを載せて製膜したところ、少し弾性のある強い膜を
得ることができた。IR (film); 3350 cm -1 (-N
H−), 1710 cm −1 (C═O) [η] (30 ° C., dimethylformamide) = 0.85.
Each polyurethane obtained in the above Examples 1 to 4
When placed on the glass plate placed on the hot plate of No. 3, it became cloudy and fluid. When another glass was placed on top of this to form a film, a strong film with a little elasticity could be obtained.
Claims (2)
０００００の範囲にあるポリウレタン類。1. A general formula: And has a molecular weight of 5,000 to 2
Polyurethanes in the range of 00000.
０００００の範囲にあるポリウレタン類。2. A general formula: And has a molecular weight of 5,000 to 2
Polyurethanes in the range of 00000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4195135A JPH0641263A (en) | 1992-07-22 | 1992-07-22 | Liquid crystal polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4195135A JPH0641263A (en) | 1992-07-22 | 1992-07-22 | Liquid crystal polyurethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0641263A true JPH0641263A (en) | 1994-02-15 |
Family
ID=16336052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4195135A Pending JPH0641263A (en) | 1992-07-22 | 1992-07-22 | Liquid crystal polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0641263A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329749A (en) * | 1993-05-19 | 1994-11-29 | Osaka Gas Co Ltd | Liquid crystal polyurethane |
| KR20200061970A (en) * | 2018-11-26 | 2020-06-03 | 한국생산기술연구원 | Composition for forming polyurethane-based film, Polyurethane-based film formed from the composition, Articles comprising the polyurethane-based film |
-
1992
- 1992-07-22 JP JP4195135A patent/JPH0641263A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329749A (en) * | 1993-05-19 | 1994-11-29 | Osaka Gas Co Ltd | Liquid crystal polyurethane |
| KR20200061970A (en) * | 2018-11-26 | 2020-06-03 | 한국생산기술연구원 | Composition for forming polyurethane-based film, Polyurethane-based film formed from the composition, Articles comprising the polyurethane-based film |
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