JPH01216985A - Butadiyne based acid anhydride - Google Patents
Butadiyne based acid anhydrideInfo
- Publication number
- JPH01216985A JPH01216985A JP3948588A JP3948588A JPH01216985A JP H01216985 A JPH01216985 A JP H01216985A JP 3948588 A JP3948588 A JP 3948588A JP 3948588 A JP3948588 A JP 3948588A JP H01216985 A JPH01216985 A JP H01216985A
- Authority
- JP
- Japan
- Prior art keywords
- butadiyne
- formula
- acid anhydride
- group
- compound expressed
- 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.)
- Granted
Links
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical compound C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 title description 11
- 150000008065 acid anhydrides Chemical class 0.000 title description 3
- -1 nitro, amino Chemical group 0.000 claims abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 239000009719 polyimide resin Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 238000005691 oxidative coupling reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 abstract 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000003863 metallic catalyst Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- HMQFJYLWNWIYKQ-UHFFFAOYSA-N 1,4-diphenylbutadiyne Chemical group C1=CC=CC=C1C#CC#CC1=CC=CC=C1 HMQFJYLWNWIYKQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical class BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Furan Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はブタジイン系酸無水物に関するものであり、更
に詳しくは、ジアミンと反応させることにより、架橋性
及び耐熱性に優れたポリイミド樹脂を与えるブタジイン
系酸無水物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a butadiyne acid anhydride, and more particularly, to a butadiyne acid anhydride that provides a polyimide resin with excellent crosslinkability and heat resistance by reacting with a diamine. It is.
近年、固相反応による分子間架橋及び高分子単結晶の合
成は注目されており、この手法を用いて種々の高弾性率
を有する材料の開発がおこなわれている。In recent years, intermolecular crosslinking and synthesis of polymer single crystals by solid-phase reactions have attracted attention, and various materials with high elastic modulus are being developed using this method.
本発明者もまた、種々の機能性ブタジイン化合物を合成
、開発してきた。The present inventor has also synthesized and developed various functional butadiyne compounds.
〔発明が解決しようとしている問題点〕しかしながら、
これまでに合成されてきたブタジイン化合物の多くは、
ジアセチレン基の隣に−ＣＨｔ−を有する物が多く、゛
そのために得られたポリマーは、耐熱性は低い。[Problem that the invention is trying to solve] However,
Many of the butadiyne compounds that have been synthesized so far are
Many of them have -CHt- next to the diacetylene group, and therefore the resulting polymers have low heat resistance.
一方、ジアセチレン基を含有するポリイミドは架橋させ
ることにより、高耐熱性、高い寸法安定性等が期待され
、本発明者らも、いくつかのブタジイン系ポリイミドを
開発した（例えば、特願昭６１−１３０１０１号、特願
昭６１−１５８８６４号）が、架橋収率が若干低かった
り、また七ツマ−の合成が難しい等の問題があった。On the other hand, polyimides containing diacetylene groups are expected to have high heat resistance, high dimensional stability, etc. by crosslinking, and the present inventors have also developed several butadiyne-based polyimides (for example, Japanese Patent Application No. 61 No. 130101 and Japanese Patent Application No. 158864/1983), there were problems such as a slightly low crosslinking yield and difficulty in synthesizing the seven-layer compound.
そこで本発明者らは、耐熱性を落さずに、ジアセチレン
基の反応性が高いイミド閘脂の開発を行うに当り、モノ
マーとして酸無水物の分子骨格中にジアセチレン基を有
するモノマーを用いることが好ましいことを見出した。Therefore, in developing an imide resin with high reactivity of diacetylene groups without reducing heat resistance, the present inventors used monomers having diacetylene groups in the molecular skeleton of acid anhydrides as monomers. It has been found that it is preferable to use
すなわちジフェニルジアセチレン骨格は、耐熱性の面で
は好ましいが、そのジアセチレン基の反応性を高めるた
めに、電子吸引基であるカルボニル基をベンゼン環１個
当り２コ以上導入することで高反応性を有するブタジイ
ン系酸無水物が得られることを見い出した。In other words, the diphenyl diacetylene skeleton is preferable in terms of heat resistance, but in order to increase the reactivity of the diacetylene group, two or more carbonyl groups, which are electron-withdrawing groups, are introduced per benzene ring to increase the reactivity. It has been found that a butadiyne acid anhydride having the following formula can be obtained.
更に、凝集性の向上、置換基の種類等、耐熱性、反応性
に係わる因子及び合成のしやすさ、原料等の製造コスト
面を鋭意検討の結果、本発明に到達した。Furthermore, the present invention was achieved as a result of intensive studies on improvements in cohesiveness, types of substituents, heat resistance, factors related to reactivity, ease of synthesis, manufacturing costs such as raw materials, etc.
すなわち本発明は、
ＯＵ
（ここで、Ｒ，Ｒ’ は水素原子、ハロゲン原子、ニト
ロ基、アミノ基、エーテル結合を有する基、又は１価の
有機基を示す。）を有するブタジイン系酸無水物を提供
するものである。That is, the present invention provides a butadiyne acid anhydride having OU (where R and R' represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a group having an ether bond, or a monovalent organic group). It provides:
本発明において、Ｒ，Ｒ”は、水素原子、ハロゲン原子
、ニトロ基、アミノ基、エーテル結合を有する基、（例
えば、アルコキシル基）、又は１価の有機基を示す。そ
の】価の有機基の具体例としては、ＣＨｉ、Ｃ２Ｈ４，
Ｃ：ＩＨ？、ＣａＨｑ、ＣｓＨ＋＋。In the present invention, R and R'' represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a group having an ether bond (for example, an alkoxyl group), or a monovalent organic group. Specific examples include CHi, C2H4,
C: IH? , CaHq, CsH++.
これらのＲ，Ｒ・ のうち、ジアセチレン基の反応性を
高めるためには水素原子が好ましく、成形性を向上させ
るためにはＣＨ３が好ましい。Among these R and R., a hydrogen atom is preferable in order to improve the reactivity of the diacetylene group, and CH3 is preferable in order to improve moldability.
本発明のブタジイン系酸無水物の合成方法としては、Ｒ
，Ｒ’ が等しい時、
金属触媒と酸素ガスを用いて酸化カッブリソゲさせるこ
とにより合成できる。（グレイサア カンプリング）
一方、ＲとＲ′が等しくない時、
ン化してから、酢酸銅のような金属触媒を用いて、！１
応させることにより、合成できる。The method for synthesizing the butadiyne acid anhydride of the present invention includes R
, R' are equal, it can be synthesized by oxidation carboxylation using a metal catalyst and oxygen gas. (Greisa Campling) On the other hand, when R and R' are not equal, after conversion, using a metal catalyst such as copper acetate,! 1 can be synthesized by reacting.
上記合成例において、酸化カップリング反応の触媒とし
ては、銅、マンガン、コバルト塩を用いることができ、
必要に応じて、３級アミン、オキシム等の助触媒を共存
させてもよい。触媒としてはＣｕＣ１，ＣｕＣ１，ｔ
、Ｃｕ Ｉｚ 、Ｃｕ （００ＣＣ）Ｉｚ）ｚ、 Ｍｎ
Ｃ１２，Ｍｎ ｃｏｄ、 ＣＯＣｌｘなどを用いる
ことができる。In the above synthesis example, copper, manganese, and cobalt salts can be used as catalysts for the oxidative coupling reaction,
If necessary, a co-catalyst such as a tertiary amine or oxime may be present. As a catalyst, CuC1, CuC1,t
, Cu Iz , Cu (00CC)Iz)z, Mn
C12, Mn cod, COClx, etc. can be used.
上記合成例の酸化カップリング反応において用いる金属
触媒のモル数は、基質に対し、０．０１当量から１当量
、酸素の流量は、１０−１０００ｍｇ／ｍｉｎが好まし
い。この反応に用いる溶媒としては、例えばピリジン、
アセトン、メタノール等があげられ、他の第二の溶媒を
共存させてもよい。The number of moles of the metal catalyst used in the oxidative coupling reaction of the above synthesis example is preferably 0.01 to 1 equivalent relative to the substrate, and the flow rate of oxygen is preferably 10 to 1000 mg/min. Examples of solvents used in this reaction include pyridine,
Examples include acetone and methanol, and other second solvents may also be present.
反応時間、温度については制限はないが、好ましくは反
応時間は１０分から１２時間、反応温度は−２０℃から
１００℃の間である。There are no restrictions on reaction time and temperature, but preferably the reaction time is 10 minutes to 12 hours and the reaction temperature is between -20°C and 100°C.
のエチニル水素をハロゲン化するときには、常法に従っ
て、次亜塩素酸アルカリ塩、次亜臭素酸アルカリ塩と核
酸無水物と反応させればよい。When halogenating ethynyl hydrogen, an alkali hypochlorite salt, an alkali hypobromite salt and a nucleic acid anhydride may be reacted according to a conventional method.
ニドワード・ティー・サボーリンらの方法（ジャーナル
・オブ・オーガニック・ケミストリー、第４８巻、第５
１３５頁、１９８３年）を用いて合成できる。The method of Nidward T. Sabourin et al. (Journal of Organic Chemistry, Vol. 48, No. 5)
135, 1983).
このようにして合成されたブタジイン系酸無水物は、極
めて純度が高く、重合度が高いポリイミドを与えうる原
料モノマーとして使用しうる。すなわち、遊離のカルボ
ン酸成分がほとんどなく、その純度は、９８％以上、さ
らに、再結晶、蒸留、昇華等の精製法を用いることによ
り、はぼ１００％にまで高めることができる。これらの
純度決定に、は、ＩＲ，ＮＭＲ，元素分析、マススペク
トル、液体クロマト法、ガスクロマド法、滴定法などを
用いることができる。The butadiyne acid anhydride synthesized in this manner has extremely high purity and can be used as a raw material monomer capable of producing polyimide with a high degree of polymerization. That is, there is almost no free carboxylic acid component, and its purity is 98% or more, and can be further increased to nearly 100% by using purification methods such as recrystallization, distillation, and sublimation. To determine their purity, IR, NMR, elemental analysis, mass spectrometry, liquid chromatography, gas chromatography, titration, etc. can be used.
本発明のブタジイン系酸無水物は、ジアセチレン基によ
る高反応性、高架橋収率、そしてすぐれた耐熱性を有す
るポリイミド樹脂の原料モノマーとなる。得られるポリ
イミド樹脂は、精密機器、電気・電子分野、自動車用の
特殊樹脂として極めて有用である。The butadiyne acid anhydride of the present invention serves as a raw material monomer for a polyimide resin having high reactivity due to diacetylene groups, high crosslinking yield, and excellent heat resistance. The obtained polyimide resin is extremely useful as a special resin for precision instruments, electric/electronic fields, and automobiles.
以下、本発明の実施例を挙げるが、本発明が、以下の実
施例に限定されるものではない。Examples of the present invention will be described below, but the present invention is not limited to the following examples.
〔実施例１〕
ジャーナル オプ オーガニック ケミストリー第４８
巻 第５１３５頁 １９８３年に記載されている方１７
２ ｇ （１，０モル）、塩化銅（１） ９．９ｇ
（０゜１モル）を、ピリジン３００ ｄ 、アセトン７
００−の混合溶媒に溶かし、この溶液に酸素ガスを激し
く導入しながら、３０℃で、８時間反応させた。反応後
、反応物を大量の水中に注ぎ、析出した目的物（白色固
体）を吸引ろ過にて単離した。得られた目的物の収率は
、定量的であった。[Example 1] Journal Op Organic Chemistry No. 48
Volume No. 5135 Those listed in 1983 17
2 g (1.0 mol), copper chloride (1) 9.9 g
(0°1 mol), 300 d of pyridine, 7 d of acetone
00-, and reacted at 30° C. for 8 hours while vigorously introducing oxygen gas into the solution. After the reaction, the reaction product was poured into a large amount of water, and the precipitated target product (white solid) was isolated by suction filtration. The yield of the target product obtained was quantitative.
ＩＲ（ヌジョール、 ｃｍ−’） ３０５６．１８７６
、１７９５’Ｈ−ＮＭＲ（δ、ｄ６ −アセトン）
８．０（Ｓ、 ３Ｈ）合成した酸無水物は、エーテ
ルより繰り返し再結晶した。その再結晶品は、水酸化ナ
トリウム水溶液を用いた滴定で、酸成分は実質的に認め
られなかった。又、硝酸銀による滴定によって、エチニ
ル水素の存在は、認められず、元素分析においても、炭
素、水素量は、計算値（理論値）の０．０２％以内にお
さまっていた。又、’Ｈ−ＮＭＲ，′３Ｃ−ＮＭＲにお
いて、目的物以外のピークは認められず、液体クロマト
グラフ、薄膜クロマトグラフによる分析でも実質的に単
一成分であることが確認された。IR (nujol, cm-') 3056.1876
, 1795'H-NMR (δ, d6-acetone)
8.0 (S, 3H) The synthesized acid anhydride was repeatedly recrystallized from ether. The recrystallized product was titrated using an aqueous sodium hydroxide solution, and substantially no acid component was detected. Furthermore, the presence of ethynyl hydrogen was not detected by titration with silver nitrate, and elemental analysis showed that the amounts of carbon and hydrogen were within 0.02% of the calculated value (theoretical value). Further, in 'H-NMR and '3C-NMR, no peaks other than the target compound were observed, and analysis by liquid chromatography and thin film chromatography confirmed that it was substantially a single component.
Claims (1)
基、アミノ基、エーテル結合を有する基、又は１価の有
機基を示す。）を有するブタジイン系酸無水物。[Claims] The structural formula is ▲a mathematical formula, a chemical formula, a table, etc.▼ (where R and R' are a hydrogen atom, a halogen atom, a nitro group, an amino group, a group having an ether bond, or a monovalent butadiyne acid anhydride having an organic group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3948588A JPH01216985A (en) | 1988-02-24 | 1988-02-24 | Butadiyne based acid anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3948588A JPH01216985A (en) | 1988-02-24 | 1988-02-24 | Butadiyne based acid anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01216985A true JPH01216985A (en) | 1989-08-30 |
| JPH0552831B2 JPH0552831B2 (en) | 1993-08-06 |
Family
ID=12554360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3948588A Granted JPH01216985A (en) | 1988-02-24 | 1988-02-24 | Butadiyne based acid anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01216985A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0381327A (en) * | 1989-08-24 | 1991-04-05 | Asahi Chem Ind Co Ltd | Diacetylenic polyamic acid, derivative thereof, and polyimide |
| US8263732B2 (en) | 2006-03-16 | 2012-09-11 | Jnc Corporation | Photo-alignment film and liquid crystal display element |
-
1988
- 1988-02-24 JP JP3948588A patent/JPH01216985A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0381327A (en) * | 1989-08-24 | 1991-04-05 | Asahi Chem Ind Co Ltd | Diacetylenic polyamic acid, derivative thereof, and polyimide |
| US8263732B2 (en) | 2006-03-16 | 2012-09-11 | Jnc Corporation | Photo-alignment film and liquid crystal display element |
| JP2014024846A (en) * | 2006-03-16 | 2014-02-06 | Jnc Corp | Optical alignment film, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0552831B2 (en) | 1993-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH01216985A (en) | Butadiyne based acid anhydride | |
| JP3171635B2 (en) | Synthetic method of citraconic imide | |
| JPH05222024A (en) | Production of biphenyltetracarboxylic acid dianhydride | |
| JPS63275541A (en) | Diacetylene compound | |
| WO1991004996A1 (en) | Preparation of open chain poly(reissert compounds) | |
| JP3384895B2 (en) | Method for producing polyamide resin | |
| JPH01186852A (en) | Amide group-containing diphenyldiacetylene | |
| WO2023176687A1 (en) | Biphenanthrene compound or alkali metal salt thereof | |
| CN116396196B (en) | Method for preparing amido isothiocyanate/amido thiourea compound in one pot | |
| JPS62255456A (en) | Production of diethylformamide | |
| CN116947734A (en) | Synthesis method of N-substituted phthalimide compound | |
| JPH06321836A (en) | Method for purifying 9,9-bis(4-hydroxyphenyl)fluorene | |
| JPH0575742B2 (en) | ||
| JPS6122034A (en) | Preparation of tetramethylbiphenyl | |
| JPH01106852A (en) | Diacetylene amide containing double bond | |
| JPS62149650A (en) | Production of aromatic bisaniline | |
| SU572456A1 (en) | Pyrazole derivatives as monomers for synthesis of metal-containing polymers | |
| JPS62288629A (en) | Polyamide containing diacetylene group and non-aromatic group | |
| JPS62267251A (en) | Diacetylene compound having amino group | |
| JPS62288628A (en) | Aromatic polyamide containing diacetylene group | |
| JPS61229863A (en) | Production of aromatic bismaleimide | |
| JPS62267248A (en) | Amino group-containing diacetylene compound | |
| JPS62258351A (en) | Production of tetraethylurea | |
| JPH06279421A (en) | New triazole compound, intermediate therefor and its synthesis | |
| JPH04103579A (en) | Tetracarboxylic acid dianhydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |