JPS60156692A - 3,4-epoxy-tricyclo(5,2,1,02,6)decane-8,9-dicarboxylic acid anhydride - Google Patents
3,4-epoxy-tricyclo(5,2,1,02,6)decane-8,9-dicarboxylic acid anhydrideInfo
- Publication number
- JPS60156692A JPS60156692A JP59011405A JP1140584A JPS60156692A JP S60156692 A JPS60156692 A JP S60156692A JP 59011405 A JP59011405 A JP 59011405A JP 1140584 A JP1140584 A JP 1140584A JP S60156692 A JPS60156692 A JP S60156692A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- epoxy
- tricyclo
- decane
- dicarboxylic acid
- 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
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyethers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、構造式〔１〕で、表される
３、４−エボキシートリシク、口（５，２，１゜９２．
８）デカン−８，９−ジカルボン酸無水物以下Ｅ−ＴＣ
ＤＡと略称する）に関するものである０本発明の化合物
は、新規化合物であり分子内に反応性に富むエポキシ基
と酸無水物基を同時に有している事を特徴としており、
耐熱性に有利なトリジクワデカン骨格を有する為エポキ
シ樹脂、エポキシ硬化剤、ポリエステル樹脂その他新し
い型の多官能性モイマーとして新轡な性能が期待される
。更に農医薬の新規な中間体としての用途にも興味かも
、たれる。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a 3,4-epoxytrisic compound (5,2,1°92.
8) Decane-8,9-dicarboxylic anhydride below E-TC
The compound of the present invention is a novel compound and is characterized by having both a highly reactive epoxy group and an acid anhydride group in the molecule.
Because it has a tridiquadecane skeleton that is advantageous for heat resistance, it is expected to have new performance as an epoxy resin, epoxy curing agent, polyester resin, and other new types of multifunctional moisturizers. Furthermore, there may be interest in its use as a new intermediate for agricultural medicines.
本化合物の利用法としては
１）単独重合によるポリエステル樹脂とする方法２）エ
ポキシ基を先に重合させて酸無水物基を持った高分子を
作り、これを利用す、る方法３）酸無水−基号使った重
合を先に行い、エポキシ基を持った高分子を作り、これ
を利用する方法
等が考えられる。Methods of using this compound include 1) producing a polyester resin through homopolymerization; 2) polymerizing epoxy groups first to create a polymer with acid anhydride groups; and 3) using acid anhydride. - A possible method would be to first perform polymerization using a group name to create a polymer with epoxy groups, and then utilize this.
何れの方法で得られる高分子も架゛橋密度の高いものが
期待される。Polymers obtained by either method are expected to have a high crosslink density.
本化合物の製造り法は、次頁のスキームで示される。The method for producing this compound is shown in the scheme on the next page.
即ち、出発物質であるジシクロペンタジェン（以下ＤＣ
ＰＤと略称する）からトリシクロ（５゜２．１．０２１
８）アセ−３−エン−８，９−ジカールボン酸（以下Ｔ
ＣＤＣと略称する）を得る方法は、本発明者らが既に特
許出願している。（特願昭５７−１９０４２９）
のｉ遣方法は酸素酸化、金属酸化物酸化、過酸化声楽酸
化、有機過酸化物酸化その他の方法、が適用出来る。然
し、これらの中では目的物の収率の点から有機過酸化物
酸化が好ましい。That is, the starting material dicyclopentadiene (hereinafter DC
(abbreviated as PD) to tricyclo(5゜2.1.021
8) Ace-3-ene-8,9-dicarboxylic acid (hereinafter referred to as T
The present inventors have already filed a patent application for a method for obtaining CDC (abbreviated as CDC). (Japanese Patent Application No. 57-190429) Oxygen oxidation, metal oxide oxidation, peroxide vocal oxidation, organic peroxide oxidation and other methods can be applied. However, among these, organic peroxide oxidation is preferred from the viewpoint of yield of the target product.
有機過酸化物としては、過安惹香酸、メタクロロ過安息
香酸、過ギ酸、過酢酸、トリフルオロ過酢酸等が挙げら
れるが、実用的には過酢−が好ましい。Examples of the organic peroxide include perbenzoic acid, metachloroperbenzoic acid, performic acid, peracetic acid, trifluoroperacetic acid, etc., but peracetic acid is practically preferred.
有機過酸化物としては、過安息香酸、メタクロロ過安□
恵香酸、遇ギ酸、過酢酸、トリフルオロ過酢酸等が挙げ
られるが、実用的には過酢酸が好ましい。Examples of organic peroxides include perbenzoic acid and metachloroperbenzoic acid□
Ezoic acid, formic acid, peracetic acid, trifluoroperacetic acid, etc. may be mentioned, but peracetic acid is practically preferred.
更に、Ｅ−ＴＣＤＣのエポキサイド環がジオールに水和
開裂する事を抑制する為にリン酸水素二ナトリウムのよ
うな塩基を共存させる事により・Ｅ−ＴＣＤＣの収率は
向上する。又反応温度は５０℃以下で行うのが好ましい
。Furthermore, the yield of E-TCDC is improved by coexisting a base such as disodium hydrogen phosphate in order to suppress the hydration cleavage of the epoxide ring of E-TCDC to diol. Further, the reaction temperature is preferably 50°C or lower.
Ｅ−ＴＣＤＣの脱水反応には、種々の脱水剤が使われる
。例えば、低級脂肪酸の酸無水物或いは酸塩化物、塩化
ホスホリル□、ハロギ酸エステル等が挙げられる。これ
らの中でも特に低級脂肪酸の酸無水物が好ましく、具体
的には無水酢酸、無水ブロピオレ酸、無水コハク酸等が
実用的である。Various dehydrating agents are used in the dehydration reaction of E-TCDC. Examples include acid anhydrides or acid chlorides of lower fatty acids, phosphoryl chloride, haloformic acid esters, and the like. Among these, acid anhydrides of lower fatty acids are particularly preferred, and specifically acetic anhydride, propioleic anhydride, succinic anhydride, etc. are practical.
脱氷剤は、Ｅ−ＴＣ’ＤＣに対し過剰量加え、還流温度
で３０分程度反応させる事により反応は終了する。The deicing agent is added in an excess amount to E-TC'DC, and the reaction is completed at reflux temperature for about 30 minutes.
反応後、Ｅ−ＴＣＤＣの精製は、反応液を濃縮して得ら
れる粗結晶をベンゼンから再結晶する事により純白の結
晶が得□られる。After the reaction, E-TCDC is purified by concentrating the reaction solution and recrystallizing the obtained crude crystals from benzene to obtain pure white crystals.
以下実施例によって本発明を説明するが、本発明はこれ
らによって何等制限されるものではない。The present invention will be explained below with reference to Examples, but the present invention is not limited by these in any way.
実施例
一ジオキサン６０’ｇＪ！Ｊン酸水素二ナトリウム５ｇ
を２００ ｍ ｌ四日反応フラスコに仕込みマグネチッ
クスタラーで攪拌しながら、５〜１０℃で４０％過酢酸
２８．５ｇ （０，１５Ｍｏｌ）を３０分で滴下した。Example 1 Dioxane 60'gJ! Disodium hydrogen phosphate 5g
was charged into a 200 ml four-day reaction flask, and while stirring with a magnetic stirrer, 28.5 g (0.15 Mol) of 40% peracetic acid was added dropwise over 30 minutes at 5 to 10°C.
滴下後徐々に室温に戻しながら更に４時間攪拌した。反
応後、反応液を５０℃以下で減圧濃縮し粗結晶を得た。After the dropwise addition, the mixture was stirred for an additional 4 hours while gradually returning to room temperature. After the reaction, the reaction solution was concentrated under reduced pressure at 50° C. or lower to obtain crude crystals.
この結晶に水′３０ｇを加え、しばらく攪拌後濾過によ
り結晶を分離した。更に６０℃で４時間減圧乾燥し白色
結晶１８゜９ｇを得た。この結晶をジメチ□ルホルムア
マイドに溶解しガスクロマトグラフィーによる分析の結
果は、原料ＴＣＤＣとは異なる単一ピークであった。こ
の結晶について、以下の分析を行った。30 g of water was added to the crystals, and after stirring for a while, the crystals were separated by filtration. It was further dried under reduced pressure at 60°C for 4 hours to obtain 18.9g of white crystals. The crystals were dissolved in dimethyl□formamide and analyzed by gas chromatography, which revealed a single peak different from that of the raw material TCDC. The following analysis was performed on this crystal.
マススペクトル〔ビス（トリメチルシリル）アセトアマ
イドでシリル化して測定した）（ｍ／ｅ（５４）〕
３６７ （Ｍ−１５） （５３）、２６１ （４０）
、１４７ （１００）
融点
１９１〜１９３℃
１７４．２３１．１７３．９６１．６０．３５７．５８
．７８６．４６．９２１．４４．２６７．４４．１０４
．４３．７７９．４３．２９２．４１．５”５８．３７
．３８７．２７．５２赤外スペクトル
３１７０．２９３０．１７２０〜１７００．１２２０．
９２０．８３５ （ａｎ−’）元素分析
ＣＩ２ Ｈ１４０５＝２３８．２４として以上より本化
合物は３．４−エポキシ−トリシクロ（５，２，１，０
”）”）デカン−８，９−ジカルボン酸（Ｅ−ＴＣＤＣ
）である事が判明した。・このＥ−ＴＣＤＣｌｏｇ、無
水酢酸５０ｇを１００℃で１５分間加熱攪拌した。反応
後反応液を濃縮して粗結晶を得°た。Mass spectrum [measured by silylation with bis(trimethylsilyl)acetamide] (m/e(54)) 367 (M-15) (53), 261 (40)
, 147 (100) Melting point 191-193°C 174.231.173.961.60.357.58
．． 786.46.921.44.267.44.104
．． 43.779.43.292.41.5”58.37
．． 387.27.52 Infrared spectrum 3170.2930.1720-1700.1220.
920.835 (an-') Elemental analysis CI2 H1405 = 238.24 From the above, this compound is 3,4-epoxy-tricyclo(5,2,1,0
")") Decane-8,9-dicarboxylic acid (E-TCDC
) was found to be. - This E-TCDClog and 50 g of acetic anhydride were heated and stirred at 100° C. for 15 minutes. After the reaction, the reaction solution was concentrated to obtain crude crystals.
この粗結晶をベンゼンで再結晶すると白色結晶７．２ｇ
が得られた。この結晶についての分析の結果は以下の通
りあった。When this crude crystal is recrystallized with benzene, 7.2 g of white crystals are obtained.
was gotten. The results of analysis of this crystal were as follows.
マススペクトル（ｍ／ｅ （％）〕
２２０ （Ｍ ）（０，２） 、２０２ （３） 、１
９２ （３） 、１７６ （２） 、１７４ （５）
、１４８（１０） 、８１ （１００） 、６６ （１
００）
融点
１９５〜１９７℃
１３Ｃ−ＮＭＲ（Ｐ、Ｐ、Ｍ）
１７３．４４７．１７３．９３Ｂ、６９．３１２．５８
．８９８．４６，３６７．４５．６３６．４３．８８１
．４３．７３５．４３．１９８．４３，０５２、３７．
８８４．２７．８９
赤外スペクトル
２９５０〜２９００．１７７５、１２３０．１０９５．
９２５ （ａｍ−１）
元素分析
Ｃ璽２装置２０４＝２２０．７３とじて以上より本化合
物は、構造式〔１〕で示される３、４−エポキシ−トリ
シクロ（５，２，Ｌ、０２．８〕デカン−８，９−ジカ
ルボン酸無水物である事が判明した。Mass spectrum (m/e (%)) 220 (M) (0,2), 202 (3), 1
92 (3), 176 (2), 174 (5)
, 148 (10) , 81 (100) , 66 (1
00) Melting point 195-197°C 13C-NMR (P, P, M) 173.447.173.93B, 69.312.58
．． 898.46, 367.45.636.43.881
．． 43.735.43.198.43,052, 37.
884.27.89 Infrared spectrum 2950-2900.1775, 1230.1095.
925 (am-1) Elemental Analysis C2 Apparatus 204 = 220.73 From the above, this compound is 3,4-epoxy-tricyclo(5,2,L,02.8 ] It turned out to be decane-8,9-dicarboxylic anhydride.
特許出願人 日産化学工業株式会社Patent applicant: Nissan Chemical Industries, Ltd.
Claims (1)
．８）デカン−８，９−ジカルボン酸無水物[Scope of Claims] , 3,4-epoxy-tricyclo(5,2,1°02
．． 8) Decane-8,9-dicarboxylic anhydride
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59011405A JPS60156692A (en) | 1984-01-25 | 1984-01-25 | 3,4-epoxy-tricyclo(5,2,1,02,6)decane-8,9-dicarboxylic acid anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59011405A JPS60156692A (en) | 1984-01-25 | 1984-01-25 | 3,4-epoxy-tricyclo(5,2,1,02,6)decane-8,9-dicarboxylic acid anhydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60156692A true JPS60156692A (en) | 1985-08-16 |
Family
ID=11777107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59011405A Pending JPS60156692A (en) | 1984-01-25 | 1984-01-25 | 3,4-epoxy-tricyclo(5,2,1,02,6)decane-8,9-dicarboxylic acid anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60156692A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012147939A1 (en) * | 2011-04-28 | 2012-11-01 | 日産化学工業株式会社 | Polyimide precursor modified with dicarboxylic acid anhydride, and imidized polyimide and liquid crystal alignment treatment agent comprising same |
-
1984
- 1984-01-25 JP JP59011405A patent/JPS60156692A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012147939A1 (en) * | 2011-04-28 | 2012-11-01 | 日産化学工業株式会社 | Polyimide precursor modified with dicarboxylic acid anhydride, and imidized polyimide and liquid crystal alignment treatment agent comprising same |
| CN103502311A (en) * | 2011-04-28 | 2014-01-08 | 日产化学工业株式会社 | Polyimide precursor modified with dicarboxylic acid anhydride, and imidized polyimide and liquid crystal alignment treatment agent comprising same |
| KR20140026431A (en) * | 2011-04-28 | 2014-03-05 | 닛산 가가쿠 고교 가부시키 가이샤 | Polyimide precursor modified with dicarboxylic acid anhydride, and imidized polyimide and liquid crystal alignment treatment agent comprising same |
| CN105037722A (en) * | 2011-04-28 | 2015-11-11 | 日产化学工业株式会社 | Polyimide precursor modified with dicarboxylic acid anhydride, imidized polyimide and liquid crystal aligning agent using it |
| US9447240B2 (en) | 2011-04-28 | 2016-09-20 | Nissan Chemical Industries, Ltd. | Polyimide precursor modified with dicarboxylic acid anhydride, imidized polyimide and liquid crystal aligning agent using it |
| JP2016210784A (en) * | 2011-04-28 | 2016-12-15 | 日産化学工業株式会社 | Novel dicarboxylic acid anhydride, and method for producing the same |
| JP6060899B2 (en) * | 2011-04-28 | 2017-01-18 | 日産化学工業株式会社 | Polyimide precursor modified with dicarboxylic acid anhydride, imidized polyimide and liquid crystal aligning agent using the same |
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