JPH04103582A - Tetracarboxylic acid dianhydride - Google Patents
Tetracarboxylic acid dianhydrideInfo
- Publication number
- JPH04103582A JPH04103582A JP22336390A JP22336390A JPH04103582A JP H04103582 A JPH04103582 A JP H04103582A JP 22336390 A JP22336390 A JP 22336390A JP 22336390 A JP22336390 A JP 22336390A JP H04103582 A JPH04103582 A JP H04103582A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- polyimide
- added
- compound shown
- thienyl
- 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
- -1 Tetracarboxylic acid dianhydride Chemical class 0.000 title description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 abstract description 20
- 229920001721 polyimide Polymers 0.000 abstract description 20
- 239000012286 potassium permanganate Substances 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- WLPXNBYWDDYJTN-UHFFFAOYSA-N 1-bromo-2,3-dimethylbenzene Chemical group CC1=CC=CC(Br)=C1C WLPXNBYWDDYJTN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract description 2
- DANMWBNOPFBJSZ-UHFFFAOYSA-N 1-iodo-2,3-dimethylbenzene Chemical group CC1=CC=CC(I)=C1C DANMWBNOPFBJSZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000921 elemental analysis Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 125000001544 thienyl group Chemical group 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 150000001793 charged compounds Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 210000003323 beak Anatomy 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 229920001221 xylan Polymers 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000645 Hg alloy Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Plural Heterocyclic 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】
〔産業上の利用分野〕
本発明は、ポリイミド等耐熱性樹脂の原料として有用な
新規な酸二無水物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel acid dianhydride useful as a raw material for heat-resistant resins such as polyimide.
ポリイミドは種々の有機ポリマーの中でも耐熱性に優れ
ているため、宇宙、航空分野から電子通信分野まで幅広
く用いられている。特に最近では、単に耐熱性に優れて
いるだけでなく、用途に応じて種々の性能を合わせ持つ
ことが望まれている。Polyimide has excellent heat resistance among various organic polymers, so it is widely used in fields ranging from space and aviation to electronic communications. Particularly recently, it has been desired not only to have excellent heat resistance but also to have various performances depending on the application.
例えば、フレキシブルプリント基板用ベースフィルムや
ＴＡＢ （テープオートメーテツドボンディング）用キ
ャリアテープ或いは積層板用樹脂としては、熱膨張係数
、誘電率が小さく、低吸湿性であることが望まれている
。しかし、これらの性能を充分に満足するポリイミドは
現在のところ得られていない。For example, base films for flexible printed circuit boards, carrier tapes for TAB (tape automated bonding), and resins for laminates are desired to have a low coefficient of thermal expansion, a low dielectric constant, and low hygroscopicity. However, a polyimide that satisfactorily satisfies these properties has not yet been obtained.
このようなポリイミドを得るためには、ポリイミド主鎖
を出来る限り剛直にして低熱膨張性を発現させることが
必要である。既存の最も剛直な構造を持つピロメリット
酸を用いてポリイミドを合成すると、低熱膨張性を容易
に発現させることができるが、イミド基の分極が大きく
なり、低吸湿性を発現させることはできない、また、誘
電率を低くするために、フッ素を導入することが考えら
れるが、構造コストがかさむこと、酸無水物の反応性が
低下することが予想され好ましくない。In order to obtain such a polyimide, it is necessary to make the polyimide main chain as rigid as possible to exhibit low thermal expansion. When polyimide is synthesized using pyromellitic acid, which has the most rigid structure in existence, it is possible to easily develop low thermal expansion properties, but the polarization of the imide group becomes large and it is not possible to develop low hygroscopicity. Further, in order to lower the dielectric constant, it is possible to introduce fluorine, but this is not preferred because it is expected to increase the structural cost and reduce the reactivity of the acid anhydride.
本発明は、低熱膨張性、低誘電率、低吸湿性（耐水性）
などの優れた特性を有するポリイミドを合成するために
有用な新規酸二無水物を提供することを目的とする。The present invention has low thermal expansion, low dielectric constant, and low moisture absorption (water resistance).
The purpose of the present invention is to provide a novel acid dianhydride useful for synthesizing polyimides having excellent properties such as.
本発明者らは上記の問題を解決するために鋭意研究の結
果、本発明に到達したものである。The present inventors have arrived at the present invention as a result of intensive research to solve the above problems.
即ち、本発明は、化学構造式［１）
ができるが、イミド基の分極が比較的大きいため、低誘
電率、低吸湿性を発現することはできないこと等がわか
った。That is, although the chemical structural formula [1] can be obtained in the present invention, it has been found that because the polarization of the imide group is relatively large, it is not possible to exhibit a low dielectric constant and low hygroscopicity.
そこで本発明者らは、下記の化学構造式Ｃ１１）（ただ
し、ｎ＝１〜３の整数）
で表されるテトラカルボン酸二無水物を内容とするもの
である。Therefore, the present inventors used a tetracarboxylic dianhydride represented by the following chemical structural formula C11) (where n=an integer of 1 to 3) as content.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明者らは、テトラカルボン酸二無水物について種々
分子設計を行い、それを評価した結果、脂肪族では合成
したポリイミドの耐熱性が低下すること、主鎖が屈曲し
てしまうため低熱膨張性を発現できないこと、また、既
存のＷｉ無水物中、最も剛直な構造を持つピロメリット
酸を用いてポリイミドを合成すると、低熱膨張性を発現
することの−Ｒ−基に耐熱性を有することが期待される
剛直な構造を導入したものを用いてポリイミドを合成す
れば低熱膨張を実現することができるばかりでなく、ま
た、酸無水物の分子量が増加するために、ポリイミドの
極性部分であるイミド環の割合が小さくなり、低誘電率
、低吸湿性を実現することができると考え、鋭意検討の
結果、化学構造式［１１］の−Ｒ−基に導入するのにふ
されしい構造として、下記構造式（ＩＩＩ）
（ただし、ｎは１〜３の整数）
を見出し、上記化学構造式［１）で表される新規テトラ
カルボン酸二無水物を発明するに至った。The present inventors conducted various molecular designs for tetracarboxylic dianhydride and evaluated the results. As a result, the heat resistance of the synthesized polyimide decreases with aliphatic, and the main chain is bent, resulting in low thermal expansion. In addition, when polyimide is synthesized using pyromellitic acid, which has the most rigid structure among existing Wi anhydrides, the -R- group, which exhibits low thermal expansion, has heat resistance. If polyimide is synthesized using a polyimide with the expected rigid structure, it will not only be possible to achieve low thermal expansion, but also because the molecular weight of the acid anhydride will increase, the imide, which is the polar part of polyimide, will be synthesized. We thought that the proportion of the ring would be reduced, thereby achieving low dielectric constant and low hygroscopicity, and as a result of intensive study, we found that the structure is suitable for introduction into the -R- group of chemical structural formula [11]. The following structural formula (III) (where n is an integer of 1 to 3) was discovered, and a novel tetracarboxylic dianhydride represented by the above chemical structural formula [1] was invented.
上記化学構造式（１）で表されるテトラカルボン酸二無
水物を構造するための原料としては、下記化学構造式（
ＩＶ）
（ただし、ｎ−１〜３の整数）
で表されるビス０−キシリノチェニル、ビス０−キシリ
ノビチェニル、ビス０−キシリッターチエニルが挙げら
れ、これらは下記化学反応式（Ｖ）キシレンに金属マグ
ネシウム或いは金属リチウムを反応させ、次に
（ただし、ＸはＩ又はＢｒ、ｎは１〜３の整数）と反応
させることにより、式〔■〕の化合物を合成することが
できる。As raw materials for constructing the tetracarboxylic dianhydride represented by the above chemical structural formula (1), the following chemical structural formula (
IV) (However, an integer of n-1 to 3) The compound of formula [■] can be synthesized by reacting with metallic magnesium or metallic lithium, and then with (where X is I or Br, and n is an integer of 1 to 3).
また、下記反応式［）
（ただし、ＸばＢｒ又はＩ、 ｎば１〜３の整数、Ｍは
金属マグネシウム又は金属リチウム）て示される方法に
よって得られる。It can also be obtained by the method shown in the following reaction formula [2] (where X is Br or I, n is an integer from 1 to 3, and M is metallic magnesium or metallic lithium).
即ち、エーテル中或いは非プロトン性溶媒中で３−ブロ
モ−Ｏ−キシレン或いは３−ヨード−〇（ただし、Ｘは
Ｂｒ又はｒ、ｎは１〜３の整数、触媒はパラジウム、パ
ラジウムと水銀の合金、又は塩化パラジウムと塩化第二
水銀の混合物）で示されるように、水、メタノール或い
は水とメタノール混合液中で３−ブロモ−０−キシレン
或いは３−ヨード−〇−キシレンと
（ただし、ＸはＢｒ又はＩ、ｎは１〜３の整数）から金
属パラジウム、パラジウムと水銀の合金、塩化パラジウ
ム或いは塩化パラジウムと塩化水銀の混合物を触媒とし
て、過酸化水素で酸化カップリングすることにより弐（
ｒＶ〕の化合物を合成することができる。That is, 3-bromo-O-xylene or 3-iodo-〇 (where X is Br or r, n is an integer from 1 to 3, and the catalyst is palladium or an alloy of palladium and mercury) in ether or an aprotic solvent. or a mixture of palladium chloride and mercuric chloride) with 3-bromo-0-xylene or 3-iodo-〇-xylene (where X is Br or I, n is an integer of 1 to 3) to 2(
rV] can be synthesized.
次に、式［ＩＶ）で表されるビス０−キシリノチェニル
、ビス０−キシリノビチェニル、ビス０キシリツターチ
エニルから式〔１〕で表されるテトラカルボン酸二無水
物への酸化、脱水反応は通常の酸化、脱水閉環手法によ
って行うことができる。例えば、過マンガン酸カリウム
法、硝酸法等によるメチル基の酸化および無水酢酸法、
加熱脱水法等による酸無水物化法が採用できる。また、
五酸化バナジウムを触媒として空気酸化により直接酸無
水物化する方法も採用可能である。Next, oxidation and dehydration reactions from bis 0-xylinochenyl, bis 0-xylinobichenyl, and bis 0-xylitarthenyl represented by formula [IV) to tetracarboxylic dianhydride represented by formula [1] can be carried out by conventional oxidation and dehydration ring closure techniques. For example, oxidation of methyl groups by potassium permanganate method, nitric acid method, acetic anhydride method, etc.
An acid anhydride method such as a heating dehydration method can be adopted. Also,
A method of directly converting the acid anhydride by air oxidation using vanadium pentoxide as a catalyst can also be adopted.
〔実施例〕
以下、実施例により本発明を更に具体的に説明するが、
本発明はこれらの実施例に限定されるものではない。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.
実施例１
２．５〜ビス（３−ｏ−キシラン）チエニルの合成
三角フラスコに３−ヨード−〇−キシレン５１゜１ｇ（
２２０鯛園ｏ１）、金属マグネシウムリボン５゜５ ｇ
（２２５ｍｍｏｌ） 、ジエチルエーテル５００ｇを
加えた。この混合物を窒素雰囲気下、室温で３時間攪拌
し、次にその反応容器を氷で冷却し、２５−ショート−
チエニル３３．６ ｇ （１００ｍｍｏｌ）をジエチル
エーテル３００ｇに溶かし、上記混合液に加え、水冷下
２時間攪拌し、その後、還流攪拌を１時間行った。反応
後、ジエチルエーテルを留去し、残りの固形分をガラス
チューブオーブンを用いて減圧蒸留をして精製し、２．
５−ビス（３−ｏ〜キシリノ）チエニルを合成した。Example 1 Synthesis of 2.5-bis(3-o-xylan)thienyl 51°1 g of 3-iodo-〇-xylene (
220 Taien o1), metal magnesium ribbon 5゜5 g
(225 mmol) and 500 g of diethyl ether were added. The mixture was stirred at room temperature under a nitrogen atmosphere for 3 hours, then the reaction vessel was cooled with ice and the 25-short-
33.6 g (100 mmol) of thienyl was dissolved in 300 g of diethyl ether, added to the above mixed solution, stirred for 2 hours under water cooling, and then stirred under reflux for 1 hour. After the reaction, diethyl ether was distilled off, and the remaining solid content was purified by vacuum distillation using a glass tube oven.2.
5-bis(3-o-xylino)thienyl was synthesized.
このものは、質量分析における分子イオンビーク（ｍ／
ｅ＝２９２）が目的成分の分子量と一致すること、そし
て下記に示すように元素分析に於いて測定値と計算値が
ほぼ一致していることから目的化合物であることが確認
された。This is the molecular ion beak (m/
e = 292) was consistent with the molecular weight of the target component, and as shown below, the measured value and calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.
元素分析
計算値： Ｃ：８２．５４ Ｈ：６．８９測定イ
ーｒ： Ｃ：８２．２０ Ｈ：６．８０
実施例２
２．５−ビス（３−ｏ−キシラン）チエニルの合成
三角フラスコに３−ヨード−〇−キシレン５１゜１ｇ
（２２０１ＩＩｓｏｌ）、２８％過酸化水素水５５．０
ｇ （４５０ｓ＋ｍｏｌ） 、Ｐ ｄ Ｃ１２０，９ｇ
（５ｍ＋ｇｏ＋）、２．５−ショート−チエニル３３
．６ｇ（１００鯛園ｏ１）、メタノール４００ｇを加え
た。この混合物を加熱還流下８時間撹拌した。この混合
物を濾過して金属触媒を除去した後、濾液を留去して得
られた固形分をガラスチューブオーブンを用いて減圧蒸
留をして精製し、２，５−ビス（３−０−キシラン）チ
エニルを合成した。Elemental analysis calculated value: C: 82.54 H: 6.89 Measured value: C: 82.20 H: 6.80
Example 2 Synthesis of 2.5-bis(3-o-xylan)thienyl 51°1 g of 3-iodo-〇-xylene was placed in an Erlenmeyer flask.
(2201IIsol), 28% hydrogen peroxide solution 55.0
g (450s+mol), P d C120.9g
(5m+go+), 2.5-short-thienyl 33
．． 6 g (100 Taien o1) and 400 g of methanol were added. This mixture was stirred under heating under reflux for 8 hours. After filtering this mixture to remove the metal catalyst, the filtrate was distilled off and the solid content obtained was purified by distillation under reduced pressure using a glass tube oven. ) Thienyl was synthesized.
質量分析、元素分析の結果も実施例１と一致した。The results of mass spectrometry and elemental analysis were also consistent with Example 1.
実施例３
ビス（３−フタリンクアンヒドリド１２．５チエニルの
合成
３０フラスコに２，５−ビス（３−ｏ−キシラン）チエ
ニル８．１ｇ（６２偕層。１）、ピリジン５５０ｘｉ、
蒸留水２００〆を加えてＩ ００ ”Ｃに加熱し、過マ
ンガン酸カリウム４８．９ ｇ （３１０ｍｍｏｌ）を
少しずつ加えて３時間撹拌した０反応後、溶液を濾過し
、濾液の溶媒を留去し固形分を得た。Example 3 Synthesis of bis(3-phthalic anhydride 12.5 thienyl) 8.1 g (62 ml) of 2,5-bis(3-o-xylan) thienyl in 30 flasks, 550 xi of pyridine,
Add 200ml of distilled water and heat to I00''C, add 48.9g (310mmol) of potassium permanganate little by little and stir for 3 hours.After the reaction, the solution was filtered and the solvent of the filtrate was distilled off. A solid content was obtained.
次に、その固形分を６％水酸化ナトリウム水溶液７００
ｇ中に加えて１００℃に加熱した後、過マンガン酸カリ
ウム５８．８ ｇをゆっくり加えて２時間撹拌しながら
反応を行った０反応後、エタノールを加えて余分の過マ
ンガン酸カリウムを分解し、濾過した。濾液を冷却した
後、塩酸を加えて性成物を沈澱させた。この沈澱物を乾
燥させた後、ｌ 丁ｏｒｒ、 ２００℃で熱処理し、最
後に昇華精製して目的物のビス（３−フタリックアンヒ
ドリド）−２，５−チエニルを得た。Next, the solid content was dissolved in 6% sodium hydroxide aqueous solution 700%
After the reaction, 58.8 g of potassium permanganate was slowly added and the reaction was carried out with stirring for 2 hours.After the reaction, ethanol was added to decompose the excess potassium permanganate. , filtered. After cooling the filtrate, hydrochloric acid was added to precipitate the product. After drying this precipitate, it was heat-treated at 200° C. and finally purified by sublimation to obtain the target product, bis(3-phthalic anhydride)-2,5-thienyl.
二のものは、質量分析における分子イオンピーク（ｍ／
ｅ＝３７６）が目的成分の分子量と一致すること、そし
て下記に示すように元素分析に於いて測定値と計算値が
ほぼ一致していることから目的化合物であることがｒｔ
ｖｔｅされた。The second one is the molecular ion peak (m/
e = 376) matches the molecular weight of the target component, and as shown below, the measured value and calculated value in elemental analysis almost match, so it is confirmed that the target compound is rt.
It was vte.
元素分析
計算値： Ｃ：６３．８３ ｆｌ：２．１４測定
値： Ｃ：６３．７５ Ｈ：２．２０実施例４
ビス５．５’−（（３−オルトーキシリノ）−２−チエ
ニル〕の合成
三角フラスコに３−ヨード−〇−キシレン５１゜１ ｇ
（２２０ｗ＋ｍｏｌ） 、金属マグネシウムリボン５
゜５ ｇ （２２５ｓ＊ｏｌ） 、ジエチルエーテル４
００ｇを加えた。この混合物を窒素雰囲気下、室温で３
時間攪拌し、次にその反応容器を氷で冷却し、５５′−
ショート−２，２′−ビチェニル４１．８ｇ（１００ｍ
ｍｏｌ）をジエチルエーテル３００ｇに溶かし、上記混
合液に加え、水冷下２時間攪拌し、その後、還流攪拌を
１時間行った。反応後、ジエチルエーテルを留去し、残
りの固形分をガラスチューブオーブンを用いて減圧蒸留
をして精製し、ビス５．５’−［（３−オルトーキシリ
ノ）−２チエニル〕を合成した。Elemental analysis calculated value: C: 63.83 fl: 2.14 Measured value: C: 63.75 H: 2.20 Example 4 Synthesis of bis5.5'-((3-orthoxylino)-2-thienyl) 51゜1 g of 3-iodo-〇-xylene in an Erlenmeyer flask
(220w+mol), metal magnesium ribbon 5
゜5 g (225s*ol), diethyl ether 4
00g was added. This mixture was mixed at room temperature under a nitrogen atmosphere for 3 hours.
stir for an hour, then cool the reaction vessel with ice and
Short-2,2'-bichenyl 41.8g (100m
mol) was dissolved in 300 g of diethyl ether, added to the above mixture, stirred for 2 hours under water cooling, and then stirred under reflux for 1 hour. After the reaction, diethyl ether was distilled off, and the remaining solid content was purified by distillation under reduced pressure using a glass tube oven to synthesize bis5.5'-[(3-orthoxylino)-2thienyl].
このものは、質量分析における分子イオンピーク（ｍ／
ｅ＝３７５）が目的成分の分子量と一致すること、そし
て下記番こ示すように元素分析に於いて測定値と計算値
がほぼ一致していることから目的化合物であることが確
認された。This is the molecular ion peak (m/
e=375) was consistent with the molecular weight of the target component, and as shown in the number below, the measured value and calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.
元素分析
計算値： Ｃニア６．９６ Ｈ：５．９２測定値
： Ｃニア６．８Ｏｆ（：６．００実施例５
ビス５．５’−［（３−フタリックアンヒドリド）−２
−チエニル〕の合成
３０フラスコにビス５．５′〜〔（３−オルトキシリノ
）−２−チエニル２３．３ ｇ （６２ｍｔａ。Elemental analysis calculated value: Cnia 6.96 H: 5.92 Measured value: Cnia 6.8Of(:6.00 Example 5 Bis5.5'-[(3-phthalic anhydride)-2
Synthesis of 23.3 g (62 mta) of bis5.5' to [(3-orthoxylino)-2-thienyl] in 30 flasks.
１）、ピリジン５５０ｍ、蒸留水２００ｄを加えて１０
０℃に加熱し、過マンガン酸カリウム４８゜９ ｇ （
３１０ｓｍｏｌ）を少しずつ加えて３時間攪拌した。反
応後、溶液を濾過し、濾液の溶媒を留去し固形分を得た
。1) Add 550 m of pyridine and 200 d of distilled water to 10
Heat to 0°C and add 48°9 g of potassium permanganate (
310 smol) was added little by little and stirred for 3 hours. After the reaction, the solution was filtered, and the solvent of the filtrate was distilled off to obtain a solid content.
次に、その固形分を６％水酸化ナトリウム水溶Ｗｉ、
７５０ ｇ中に加えて１００″Ｃに加熱した後、過マン
ガン酸カリウム６０ｇをゆっくり加えて２時間撹拌しな
がら反応を行った０反応後、エタノールを加えて余分の
過マンガン酸カリウムを分解し、濾過した。濾液を冷却
した後、塩酸を加えて生成物を沈澱させた。この沈澱物
を乾燥させた後、ＩＴｏｒｒ、 ２００°Ｃで熱処理し
、最後に昇華精製して目的物のビス５．５’−（（３−
フタリックアンヒドリド）−２−チエニル〕を得た。Next, the solid content was dissolved in 6% sodium hydroxide solution Wi,
After adding 750 g of potassium permanganate and heating to 100''C, 60 g of potassium permanganate was slowly added and the reaction was carried out with stirring for 2 hours.After the reaction, ethanol was added to decompose the excess potassium permanganate. It was filtered. After cooling the filtrate, hydrochloric acid was added to precipitate the product. After drying this precipitate, it was heat-treated at I Torr and 200°C, and finally purified by sublimation to obtain the target bis5. 5'-((3-
phthalic anhydride)-2-thienyl] was obtained.
このものは、質量分析における分子イオンビーク（ｍ／
ｅ−４５８）が目的成分の分子量と一致すること、そし
て下記に示すように元素分析に於いて測定値と計算値が
ほぼ一致していることがら目的化合物であることが確認
された。This is the molecular ion beak (m/
It was confirmed that e-458) was the target compound because its molecular weight matched the molecular weight of the target component, and as shown below, the measured value and calculated value in elemental analysis almost matched.
元素分析
計算値： Ｃ：６２．８８ Ｈ：２．２０ｓ定４
ｒｉ： Ｃ：６２．９０ Ｈ：２．２４実施例６
ビス２．５’−（３−オルトーキシリノ）−５゜２’
：５’、２’−ターチェニルの合成三角フラスコに３
−ヨード−〇−キシレン５１゜１ ｇ （２２０ｓｍｏ
ｌ） 、金属マグネシウムリボン５６５ｇ Ｃ２２５ｍ
ｗａｏｌ）、ジエチルエーテル５００ｇを加えた。この
混合物を窒素雰囲気下、室温で３時間攪拌し、次にその
反応容器を氷で冷却し、２゜５＃−ショート−５，２’
：５’、２”−ターチェニル５．０ ｇ （１００
ｓ＊ｏｌ）をジェチ７１／ ｘ −７−ル３００ｇに溶
かし、上記混合液に加え、水冷下２時間攪拌し、その後
、還流攪拌を１時間行った。Elemental analysis calculated value: C: 62.88 H: 2.20s constant 4
ri: C: 62.90 H: 2.24 Example 6 Bis2.5'-(3-orthoxylino)-5°2'
: Synthesis of 5',2'-terchenyl Place 3 in an Erlenmeyer flask.
-Iodo-〇-xylene 51゜1 g (220smo
l) , metal magnesium ribbon 565g C225m
waol) and 500 g of diethyl ether were added. The mixture was stirred at room temperature under a nitrogen atmosphere for 3 hours, then the reaction vessel was cooled with ice and heated to 2°5#-short-5,2'.
:5',2''-terchenyl 5.0 g (100
s*ol) was dissolved in 300 g of Jetyl 71/x-7-ol, added to the above mixed solution, stirred for 2 hours under water cooling, and then stirred under reflux for 1 hour.
反応後、ジエチルエーテルを留去し、残りの固形分をガ
ラスチューブオーブンを用いて減圧蒸留をして精製し、
ビス２．５’−（３−オルトーキシリノ）−５，２’
：５’、２”−ターチェニルを合成した。After the reaction, diethyl ether was distilled off, and the remaining solid content was purified by vacuum distillation using a glass tube oven.
Bis2,5'-(3-orthoxylino)-5,2'
:5',2''-terchenyl was synthesized.
このものは、質量分析における分子イオンビーク（ｍ／
ｅ＝４５７）が目的成分の分子量と一致すること、そし
て下記に示すように元素分析に於いて測定値と計算値が
ほぼ一致していることから目的化合物であることが確認
された。This is the molecular ion beak (m/
e = 457) was consistent with the molecular weight of the target component, and as shown below, the measured value and calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.
元素分析
計算値： Ｃニア３．６４ Ｈ：５．３０測定値
： Ｃニア３．７０ Ｈ：５．２０実施例７
ビス２．５’−（３−フタリックアンヒドリド）−５，
２’ ：５’、２’−ターチェニル〕の合成
３０フラスコにビス２．５’−（３−オルトーキシリノ
）−５，２’：５’ ２’−ターチェニル２８．３
ｇ （６２ｍｍｏｌ） 、ピリジン５５０ｄ、蒸留水２
００ｄを加えて１００°Ｃに加熱し、過マンガン酸カリ
ウム４８．９ ｇ （３１（１＋＋＋ｏｌ）を少しずつ
加えて３時間攪拌した。反応後、溶液を濾過し、濾液の
溶媒を留去し固形分を得た。Elemental analysis calculated value: C near 3.64 H: 5.30 Measured value: C near 3.70 H: 5.20 Example 7 Bis 2.5'-(3-phthalic anhydride)-5,
Synthesis of 2':5',2'-terchenyl] Bis2.5'-(3-orthoxylino)-5,2':5'2'-terchenyl28.3 was added to 30 flasks.
g (62 mmol), pyridine 550 d, distilled water 2
00d was added and heated to 100°C, and 48.9 g of potassium permanganate (31 (1 +++ ol) was added little by little and stirred for 3 hours. After the reaction, the solution was filtered, and the solvent of the filtrate was distilled off to obtain a solid. I got my share.
次に、その固形分を６％水酸化ナトリウム水溶液７５０
ｇ中に加えて１００°Ｃに加熱した後、過マンガン酸カ
リウム６０ｇをゆっくり加えて２時間撹拌しながら反応
を行った。反応後、エタノールを加えて余分の過マンガ
ン酸カリウムを分解し、濾過した。濾液を冷却した後、
塩酸を加えて性成物を沈澱させた。この沈澱物を乾燥さ
セた後、ＩＴｏｒｒ、２００°Ｃで熱処理し、最後に昇
華精製して目的物のビス２．５’−（３−フタリックア
ンヒドリド）−５，２’ ：５’、２’−ターチェニ
ルを得た。Next, the solid content was dissolved in 6% sodium hydroxide aqueous solution 750
After heating to 100°C, 60g of potassium permanganate was slowly added and the reaction was carried out with stirring for 2 hours. After the reaction, ethanol was added to decompose excess potassium permanganate, and the mixture was filtered. After cooling the filtrate,
Hydrochloric acid was added to precipitate the product. After drying this precipitate, it was heat-treated at ITorr and 200°C, and finally purified by sublimation to obtain the target bis-2.5'-(3-phthalic anhydride)-5,2':5' , 2'-terchenyl was obtained.
このものは、質量分析における分子イオンビーク（ｍ／
ｅ＝５４１）が目的成分の分子量と一致すること、そし
て下記に示すように元素分析に於いて測定値と計算値が
ほぼ一致していることから目的化合物であることが確認
された。This is the molecular ion beak (m/
e = 541) corresponds to the molecular weight of the target component, and as shown below, the measured value and calculated value in elemental analysis almost matched, so it was confirmed that it was the target compound.
元素分析
計算値： Ｃ：６２．２１ Ｈ：２．２４測定値
： Ｃ：６２．３０ Ｈ：２．４０参考例
ボリイミＦ′共重合体膜の製造
３０フラスコにパラフェニレンジアミン１２．４ｇ （
１１５ｍ５ｏｌ） 、ジメチル７ ｆ ７Ｌ／ムアミト
（以下ＤＭＦと略する）２００ｇをとり、攪拌しながら
実施例３で合成したビス（３−フタリックアンヒト！Ｊ
Ｆ） −２，５−−ｆ−ｘニル４１．４ ｇ （１１
０１ｏ１）を徐々に加え３０分撹拌した。次に、５ｍ。Elemental analysis calculated value: C: 62.21 H: 2.24 Measured value: C: 62.30 H: 2.40 Reference example Production of Boliimi F' copolymer membrane 12.4 g of paraphenylene diamine was placed in 30 flasks (
115 m5 ol), 200 g of dimethyl 7 f 7 L/muamito (hereinafter abbreviated as DMF) was taken, and while stirring, the bis(3-phthalic anhydride!J) synthesized in Example 3 was added.
F) -2,5--f-xyl 41.4 g (11
01o1) was gradually added and stirred for 30 minutes. Next, 5m.
１の８重量％ビス（３−フタリックアンヒドリド）−２
，５−チエニルのＤＭＦ溶液を徐々に添加することによ
り、ポリアミック酸溶液を得た。8% by weight of 1 bis(3-phthalic anhydride)-2
, 5-thienyl in DMF was gradually added to obtain a polyamic acid solution.
理論量より過剰の無水酢酸と触媒量の３級アミンをポリ
アミック酸溶液と混合した後で、ガラス板上に流延塗布
し、約８０°Ｃにて約９０秒間乾燥後、ポリアミック酸
塗膜をガラス板より剥し、その塗膜を支持枠に固定し、
その後約１００″Ｃで約９０秒間加熱後、延伸した６次
いで、約２５０ ’Ｃで約３０秒間、約３００°Ｃで約
３０秒間、約４゜ＯｏＣで約３０秒間、約４５０°Ｃで
約２分間加熱し、約２５ミクロンのポリイミド共重合体
膜を得た。After mixing acetic anhydride in excess of the theoretical amount and a catalytic amount of tertiary amine with a polyamic acid solution, it was cast onto a glass plate, dried at about 80°C for about 90 seconds, and then a polyamic acid coating was formed. Peel it off from the glass plate, fix the coating to the support frame,
Then, after heating at about 100'C for about 90 seconds, the 6 was stretched. Heating was performed for 2 minutes to obtain a polyimide copolymer film of about 25 microns.
得られたポリイミド共重合体膜の物性を第１表に示す。Table 1 shows the physical properties of the polyimide copolymer film obtained.
比較参考例
ポリイミド共重合体膜の製造
３０フラスコに、ジアミノジフェニルエーテル２６．０
ｇ （１３０ｖｓｏｌ）、ＤＭＦ２００ｇをトリ、攪拌
しなからピロメリット酸二無水物２７．０ ｇ（１２４
Ｉｌｓｏｌ）を徐々に加え、次に、６ｍｏｌの７重量％
のピロメリット酸二無水物のＤＭＦ溶液を徐々に添加す
ることにより、ポリアミック酸溶液を得た。Comparative Reference Example Production of polyimide copolymer membrane 26.0 diaminodiphenyl ether was added to 30 flasks.
g (130 vsol), 200 g of DMF, stirred, and pyromellitic dianhydride 27.0 g (124
Ilsol) was gradually added, then 7% by weight of 6 mol
A polyamic acid solution was obtained by gradually adding a DMF solution of pyromellitic dianhydride.
そして、参考例と同様の方法でポリイミド共重合体膜を
得た。Then, a polyimide copolymer film was obtained in the same manner as in the reference example.
得られたポリイミド共重合体膜の物性を第１表に示す。Table 1 shows the physical properties of the polyimide copolymer film obtained.
第 １ 表
（１） Ｔｈｅｒｖａｌ Ｍｅｃｈａｎｉｃａｌ Ａｎ
ａｌｙｓｉｓにより測定した１００〜２００℃の熱膨張
係数
（２） ＡＳＴＭ Ｄ−１５０により測定（３） ＡＳ
ＴＭ Ｄ−５７０により測定〔作用・効果〕
軟土の通り、本発明によれば、低熱膨張性、低誘電率及
び低吸湿性のポリイミドを提供するためのテトラカルボ
ン酸二無水物が提供される。Table 1 (1) Thermal Mechanical An
Thermal expansion coefficient from 100 to 200°C measured by lysis (2) Measured by ASTM D-150 (3) AS
Measured by TM D-570 [Function/Effect] According to the soft soil, the present invention provides a tetracarboxylic dianhydride for providing a polyimide with low thermal expansion, low dielectric constant, and low hygroscopicity. .
Claims (1)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22336390A JP2933695B2 (en) | 1990-08-24 | 1990-08-24 | Tetracarboxylic dianhydride |
| EP91114177A EP0477539B1 (en) | 1990-08-24 | 1991-08-23 | Tetracarboxylic acid dianhydrides |
| US07/749,342 US5122617A (en) | 1990-08-24 | 1991-08-23 | Tetracarboxylic acid dianhydrides |
| DE69114430T DE69114430T2 (en) | 1990-08-24 | 1991-08-23 | Tetracarboxylic dianhydrides. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22336390A JP2933695B2 (en) | 1990-08-24 | 1990-08-24 | Tetracarboxylic dianhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04103582A true JPH04103582A (en) | 1992-04-06 |
| JP2933695B2 JP2933695B2 (en) | 1999-08-16 |
Family
ID=16796978
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22336390A Expired - Fee Related JP2933695B2 (en) | 1990-08-24 | 1990-08-24 | Tetracarboxylic dianhydride |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104236214A (en) * | 2013-06-07 | 2014-12-24 | 三菱电机株式会社 | insulating box body, refrigerator, and device provided with insulating box body |
| CN115558412A (en) * | 2022-10-12 | 2023-01-03 | 深圳市华之美科技有限公司 | Polyimide composite material and preparation method and application thereof |
-
1990
- 1990-08-24 JP JP22336390A patent/JP2933695B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104236214A (en) * | 2013-06-07 | 2014-12-24 | 三菱电机株式会社 | insulating box body, refrigerator, and device provided with insulating box body |
| CN104236214B (en) * | 2013-06-07 | 2018-10-09 | 三菱电机株式会社 | Heat insulating box, refrigerator and the equipment with heat insulating box |
| CN115558412A (en) * | 2022-10-12 | 2023-01-03 | 深圳市华之美科技有限公司 | Polyimide composite material and preparation method and application thereof |
| CN115558412B (en) * | 2022-10-12 | 2023-06-09 | 深圳市华之美科技有限公司 | Polyimide composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2933695B2 (en) | 1999-08-16 |
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