JP2014210731A - Polyformyl polyphenyl derivative - Google Patents
Polyformyl polyphenyl derivative Download PDFInfo
- Publication number
- JP2014210731A JP2014210731A JP2013087965A JP2013087965A JP2014210731A JP 2014210731 A JP2014210731 A JP 2014210731A JP 2013087965 A JP2013087965 A JP 2013087965A JP 2013087965 A JP2013087965 A JP 2013087965A JP 2014210731 A JP2014210731 A JP 2014210731A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyphenyl
- derivative
- polyformyl
- formula
- 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
- 0 CCC(C)c(ccc(C(C)(C*=C)c(cccc1C)c1I)c1C)c1I Chemical compound CCC(C)c(ccc(C(C)(C*=C)c(cccc1C)c1I)c1C)c1I 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/54—Benzaldehyde
Abstract
Description
本発明はポリ（置換メチル）ポリフェニル誘導体を酸化して得られるポリホルミルポリフェニル誘導体に関するものである。 The present invention relates to a polyformyl polyphenyl derivative obtained by oxidizing a poly (substituted methyl) polyphenyl derivative.
ポリホルミルポリフェニル誘導体は、これまで様々な方法で製造されている。特許文献１では、ハロゲン化ベンズアルデヒドをピリジンと無水ニッケル化合物及び還元金属の存在下カップリング反応後、不溶解分を濾過し、更に系中に水を滴下して結晶を析出させ、濾過、乾燥する方法が提案されている。特許文献２では、ジアルコキシメチルジフェニルを酢酸溶剤中、臭素酸ナトリウムを用いて酸化し、対応するジホルミルジフェニル化合物を製造している。 Polyformyl polyphenyl derivatives have been produced by various methods so far. In Patent Document 1, a halogenated benzaldehyde is subjected to a coupling reaction in the presence of pyridine, an anhydrous nickel compound and a reducing metal, and then the insoluble matter is filtered. Water is further dropped into the system to precipitate crystals, which are filtered and dried. A method has been proposed. In Patent Document 2, dialkoxymethyldiphenyl is oxidized with sodium bromate in an acetic acid solvent to produce a corresponding diformyldiphenyl compound.
しかしながら上述のしたような方法では、使用するパラジウム、ニッケルなどの遷移金属触媒が高価であることに加え、反応終了後、残留する有害な金属化合物を処理する必要がある。さらには生成したポリホルミルポリフェニル誘導体を再結晶する工程を経るために工程が複雑化し、コストが高くなることからも、工業的に有利ではない。また臭素酸ナトリウムは加熱により、酸性度の高い臭化水素ガスを発生し、ポリホルミルジフェニル誘導体のアルデヒド基同士で副反応が起こり、高分子量化が進行する恐れがある。以上のような問題点を解決するために、金属触媒や臭素酸化物を用いず、かつ簡便に精製できるポリホルミルポリフェニル誘導体が求められている。 However, in the method as described above, the transition metal catalyst such as palladium and nickel to be used is expensive, and it is necessary to treat the remaining harmful metal compound after the reaction is completed. Furthermore, since the process of recrystallizing the produced polyformyl polyphenyl derivative is complicated, the process becomes complicated and the cost is increased, which is not industrially advantageous. In addition, sodium bromate generates hydrogen bromide gas with high acidity by heating, and side reactions occur between aldehyde groups of the polyformyldiphenyl derivative, which may lead to an increase in the molecular weight. In order to solve the above problems, there is a demand for polyformyl polyphenyl derivatives that can be easily purified without using a metal catalyst or bromine oxide.
本発明者らはこうした実情に鑑み、金属触媒や臭素酸化物を用いず、かつ簡便に精製できるポリホルミルポリフェニル誘導体を求めて鋭意検討した結果、本発明を完成させるに至った。 In view of such circumstances, the present inventors have intensively studied for a polyformyl polyphenyl derivative that can be easily purified without using a metal catalyst or bromine oxide, and as a result, the present invention has been completed.
すなわち本発明は、下記（１）〜（６）に関する。
（１）遷移金属化合物の含有率が１００ｐｐｍ以下である一般式（１）
で表されるポリホルミルポリフェニル誘導体であって、下記式（２）
で表される化合物の含有割合が高速液体クロマトグラフィーでの測定において５面積％以下であることを特徴とするポリホルミルポリフェニル誘導体。
（２）（１）に記載のポリホルミルポリフェニル誘導体のうち、アルデヒド基の縮合反応に起因するＧＰＣでの測定において、高分子量体が５面積％以下であるポリホルミルポリフェニル誘導体。
（３）一般式（２）
で表されるポリ（置換メチル）ポリフェニル誘導体と、
水および／またはアルコールと、
ヘキサメチレンテトラミンおよび／またはホルムアルデヒド−アンモニア混合物を反応させることにより得られる、（１）又は（２）に記載のポリホルミルポリフェニル誘導体。
（４）（３）に記載のポリ（置換メチル）ポリフェニル誘導体として４，４’−ジクロロメチルジフェニルを用いた、ポリホルミルジフェニル誘導体。
（５）（３）に記載のポリ（置換メチル）ポリフェニル誘導体を水およびヘキサミンと反応させて得られるポリホルミルジフェニル誘導体。
（６）（３）に記載のポリ（置換メチル）ポリフェニル誘導体をメタノールおよびヘキサミンと反応させて得られるポリホルミルジフェニル誘導体。
That is, the present invention relates to the following (1) to (6).
(1) General formula (1) in which the content of the transition metal compound is 100 ppm or less
A polyformylpolyphenyl derivative represented by the following formula (2):
A polyformyl polyphenyl derivative characterized in that the content of the compound represented by the formula is 5 area% or less as measured by high performance liquid chromatography.
(2) Among the polyformyl polyphenyl derivatives according to (1), a polyformyl polyphenyl derivative having a high molecular weight of 5 area% or less as measured by GPC resulting from a condensation reaction of an aldehyde group.
(3) General formula (2)
A poly (substituted methyl) polyphenyl derivative represented by:
With water and / or alcohol,
The polyformyl polyphenyl derivative according to (1) or (2), which is obtained by reacting hexamethylenetetramine and / or a formaldehyde-ammonia mixture.
(4) A polyformyldiphenyl derivative using 4,4′-dichloromethyldiphenyl as the poly (substituted methyl) polyphenyl derivative according to (3).
(5) A polyformyldiphenyl derivative obtained by reacting the poly (substituted methyl) polyphenyl derivative according to (3) with water and hexamine.
(6) A polyformyldiphenyl derivative obtained by reacting the poly (substituted methyl) polyphenyl derivative according to (3) with methanol and hexamine.
金属触媒や臭素酸化物を用いず、かつ簡便に精製させて得られるポリホルミルポリフェニル誘導体であるため、安価で、残存遷移金属量の少ないエポキシ樹脂となる。 Since it is a polyformyl polyphenyl derivative obtained by simply purifying without using a metal catalyst or bromine oxide, it is an inexpensive epoxy resin with a small amount of residual transition metal.
以下、本発明を詳細に説明する。本発明によれば、金属触媒や臭素酸化物を用いず、かつ簡便に精製できるポリホルミルポリフェニル誘導体を得ることができる。 Hereinafter, the present invention will be described in detail. According to the present invention, a polyformyl polyphenyl derivative that can be easily purified without using a metal catalyst or bromine oxide can be obtained.
本発明のポリホルミルポリフェニル誘導体は、下記式（１）
で表される。尚、上記点線はフェニル基が存在していても、存在していなくてもよいことを表す。
Ｒ１として、好ましくは水素原子、炭素数１〜１０のアルキル基である。
また、置換基を有しても良いフェニル基において、置換基の具体例としては、ヒドロキシル基、炭素数１〜１０のアルキル基、アルコキシ基、カルボキシル基又はその金属塩、アルコキシカルボニル基、アルキルカルボニルアミノ基、ハロゲン原子、ニトロ基、シアノ基、アルキルカルボニル基又はフェニル基である。
The polyformyl polyphenyl derivative of the present invention has the following formula (1):
It is represented by The dotted line indicates that a phenyl group may or may not be present.
R 1 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
In the phenyl group which may have a substituent, specific examples of the substituent include a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a carboxyl group or a metal salt thereof, an alkoxycarbonyl group, an alkylcarbonyl group. An amino group, a halogen atom, a nitro group, a cyano group, an alkylcarbonyl group or a phenyl group.
本発明のポリホルミルポリフェニル誘導体における遷移金属化合物の含有量は１００ｐｐｍ以下であり、５０ｐｐｍ以下がさらに好ましく、１０ｐｐｍが特に好ましい。遷移金属化合物の含有量が１００ｐｐｍより多いと、環境汚染の原因となる可能性が有る。
また、本発明においては、前記式（１）で表されるポリフェニル誘導体において、不純物として存在し得る下記に記載の原料である前記式（２）で表される化合物の含有量が高速液体クロマトグラフィー（ＨＰＬＣ）での測定において、５面積％以下であり、３面積％以下であることが好ましい。当該式（２）で表される化合物の残存量が多いと、所望の硬化物性を得ることができなくなる恐れがあるためである。
尚、ＨＰＬＣの測定条件としては、例えば下記の条件を適用できる。
＜ＨＰＬＣ測定条件＞
（株）島津製作所 ＬＣ−２０ＡＤ
カラム： ＯＤＳ−２
使用溶剤： 水（Ａ液）−アセトニトリル（Ｂ液）
Ｂ液濃度勾配：７０％（０ｍｉｎ）−１００％（１４ｍｉｎ）−１００％（４０ｍｉｎ）
流速：１ｍｌ／ｍｉｎ．
カラム温度：４０℃
検出器：（株）島津製作所 フォトダイオードアレイ ＳＰＤ−Ｍ２０Ａ
The content of the transition metal compound in the polyformyl polyphenyl derivative of the present invention is 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 10 ppm. When there is more content of a transition metal compound than 100 ppm, it may become a cause of environmental pollution.
In the present invention, in the polyphenyl derivative represented by the formula (1), the content of the compound represented by the formula (2), which is a raw material described below that may be present as an impurity, is high-performance liquid chromatography. In the measurement by the graphic (HPLC), it is 5 area% or less, and preferably 3 area% or less. This is because if the amount of the compound represented by the formula (2) is large, the desired cured properties may not be obtained.
As the HPLC measurement conditions, for example, the following conditions can be applied.
<HPLC measurement conditions>
Shimadzu Corporation LC-20AD
Column: ODS-2
Solvent: Water (Liquid A)-Acetonitrile (Liquid B)
B liquid concentration gradient: 70% (0 min) -100% (14 min) -100% (40 min)
Flow rate: 1 ml / min.
Column temperature: 40 ° C
Detector: Shimadzu Corporation Photodiode array SPD-M20A
本発明においてアルデヒド基の縮合反応に起因するゲルパーミエーションクロマトグラフィー（ＧＰＣ）での高分子量体面積比率は、通常５．０面積％以下であり、好ましくは３．０面積％以下であり、特に好ましくは２．０面積％以下である。本発明のポリホルミルポリフェニル誘導体を製造する際、酸触媒を用いるが、これらの酸触媒（例えば、強酸である臭素酸化物）が原因でアルデヒド基が重合し、該重合物として高分子量体を含有してしまう可能性が有る。高分子量化が進行すると、溶剤への溶解性が低下し、製品の操作性が劣ることに加え、縮合して生成するエーテル基が加水分解されやすく、一定の品質を得ることができない恐れがある。 In the present invention, the high molecular weight area ratio in gel permeation chromatography (GPC) resulting from the condensation reaction of aldehyde groups is usually 5.0 area% or less, preferably 3.0 area% or less, particularly Preferably it is 2.0 area% or less. When the polyformyl polyphenyl derivative of the present invention is produced, an acid catalyst is used. The aldehyde group is polymerized due to these acid catalysts (for example, bromine oxide which is a strong acid), and a high molecular weight product is obtained as the polymer. There is a possibility of containing. As the molecular weight increases, the solubility in a solvent decreases and the operability of the product is inferior. In addition, the ether group formed by condensation is easily hydrolyzed, and there is a possibility that a certain quality cannot be obtained. .
本発明において用いるポリ（置換メチル）ポリフェニル誘導体は下記式（２）
で表される。
The poly (substituted methyl) polyphenyl derivative used in the present invention has the following formula (2)
It is represented by
このようなポリ（置換メチル）ポリフェニルの具体例は、２，２’−ジクロロメチルジフェニル、２，２’−ジブロモメチルジフェニル、２，２’−ジメトキシメチルジフェニル、２，２’−ジメチロールジフェニル、２，４’−ジクロロメチルジフェニル、２，４’−ジブロモメチルジフェニル、２，４’−ジメトキシメチルジフェニル、２，４’−ジメチロールジフェニル、３，３’−ジクロロメチルジフェニル、３，３’−ジブロモメチルジフェニル、３，３’−ジメトキシメチルジフェニル、３，３’−ジメチロールジフェニル、４，４’−ジクロロメチルジフェニル、４，４’−ジブロモメチルジフェニル、４，４’−ジメトキシメチルジフェニル、４，４’−ジメチロールジフェニル、３，３’，４，４’−テトラクロロメチルジフェニル、３，３’，４，４’−テトラブロモメチルジフェニル、３，３’，４，４’−テトラメトキシメチルジフェニル、３，３’，４，４’−テトラメチロールジフェニル、３，３’，５，５’−テトラクロロメチルジフェニル、３，３’，５，５’−テトラブロモメチルジフェニル、３，３’，５，５’−テトラメトキシメチルジフェニル、３，３’，５，５’−テトラメチロールジフェニル、３，３’，５，５’−テトラクロロメチル−４，４’−ジヒドロキシジフェニル、３，３’，５，５’−テトラブロモメチル−４，４’−ジヒドロキシメチルジフェニル、３，３’，５，５’−テトラメトキシメチル−４，４’−ジヒドロキシジフェニル、３，３’，５，５’−テトラメチロール−４，４’−ジヒドロキシメチルジフェニル、４，４’−ジクロロメチルトリフェニル、４，４’−ジブロモメチルトリフェニル、４，４’−ジメトキシメチルトリフェニル、４，４’−ジメチロールトリフェニル、２，２’−ジクロロメチル−１，１’−ビナフチル、２，２’−ジブロモメチル−１，１’−ビナフチル、２，２’−ジメトキシメチル−１，１’−ビナフチル、２，２’−ジメチロール−１，１’−ビナフチル、などが挙げられるが、これらに限定されるものではない。特に４，４’−ジクロロメチルジフェニル、４，４’−ジブロモメチルジフェニルが好ましい。 Specific examples of such poly (substituted methyl) polyphenyl are 2,2′-dichloromethyldiphenyl, 2,2′-dibromomethyldiphenyl, 2,2′-dimethoxymethyldiphenyl, 2,2′-dimethyloldiphenyl. 2,4′-dichloromethyldiphenyl, 2,4′-dibromomethyldiphenyl, 2,4′-dimethoxymethyldiphenyl, 2,4′-dimethyloldiphenyl, 3,3′-dichloromethyldiphenyl, 3,3 ′ -Dibromomethyldiphenyl, 3,3'-dimethoxymethyldiphenyl, 3,3'-dimethyloldiphenyl, 4,4'-dichloromethyldiphenyl, 4,4'-dibromomethyldiphenyl, 4,4'-dimethoxymethyldiphenyl, 4,4'-dimethyloldiphenyl, 3,3 ', 4,4'-tetrachloromethyl Phenyl, 3,3 ′, 4,4′-tetrabromomethyldiphenyl, 3,3 ′, 4,4′-tetramethoxymethyldiphenyl, 3,3 ′, 4,4′-tetramethyloldiphenyl, 3,3 ′ , 5,5′-tetrachloromethyldiphenyl, 3,3 ′, 5,5′-tetrabromomethyldiphenyl, 3,3 ′, 5,5′-tetramethoxymethyldiphenyl, 3,3 ′, 5,5 ′ -Tetramethylol diphenyl, 3,3 ', 5,5'-tetrachloromethyl-4,4'-dihydroxydiphenyl, 3,3', 5,5'-tetrabromomethyl-4,4'-dihydroxymethyldiphenyl, 3,3 ′, 5,5′-tetramethoxymethyl-4,4′-dihydroxydiphenyl, 3,3 ′, 5,5′-tetramethylol-4,4′-dihydroxymethyldipheny 4,4′-dichloromethyltriphenyl, 4,4′-dibromomethyltriphenyl, 4,4′-dimethoxymethyltriphenyl, 4,4′-dimethyloltriphenyl, 2,2′-dichloromethyl-1 , 1′-binaphthyl, 2,2′-dibromomethyl-1,1′-binaphthyl, 2,2′-dimethoxymethyl-1,1′-binaphthyl, 2,2′-dimethylol-1,1′-binaphthyl, However, it is not limited to these. In particular, 4,4'-dichloromethyldiphenyl and 4,4'-dibromomethyldiphenyl are preferred.
本発明においてポリホルミルジフェニル誘導体を製造する試薬は、ヘキサメチレンテトラミンやホルムアルデヒド−アンモニア混合物等が例示できるがこれらに限定されるものではない。好ましくは、ヘキサメチレンテトラミンを挙げることが出来る。その添加量は例えば一般式（２）で示されるポリ（置換メチル）ポリフェニル誘導体の置換メチル基１モルに対し、０．１〜１０モルが好ましく、さらに好ましくは、０．３〜５．０モル、特に好ましくは、０．８〜２．５モルである。０．１モルより少ないと、反応の進行が悪く原料が大量に残り、１０モルより多いと、ヘキサメチレンテトラミンやホルムアルデヒド−アンモニア混合物等の精製が困難になる。 Examples of the reagent for producing the polyformyldiphenyl derivative in the present invention include, but are not limited to, hexamethylenetetramine and a formaldehyde-ammonia mixture. Preferably, hexamethylenetetramine can be mentioned. The addition amount is preferably 0.1 to 10 mol, more preferably 0.3 to 5.0, for 1 mol of the substituted methyl group of the poly (substituted methyl) polyphenyl derivative represented by the general formula (2). Mol, particularly preferably 0.8 to 2.5 mol. When the amount is less than 0.1 mol, the progress of the reaction is poor and a large amount of raw material remains. When the amount is more than 10 mol, purification of hexamethylenetetramine, formaldehyde-ammonia mixture or the like becomes difficult.
本発明のポリフェニルポリフェニル誘導体の製造において、無溶媒条件で反応させても良いが、より円滑に反応を進行させるために必要に応じて反応系に溶媒を添加することが出来る。溶媒の具体例として例えば、ギ酸、酢酸、プロピオン酸等の低級脂肪族カルボン酸や、メタノール、エタノール、プロパノール、２−プロパノール、ｔ−ブタノール等の低級脂肪族アルコールをあげることが出来る。好ましくはギ酸、酢酸、プロピオン酸等の低級脂肪族カルボン酸をあげることが出来、さらに好ましくは酢酸である。これらの溶媒は単独でも２種以上混合して用いても良い。その添加量は一般式（２）で示されるポリ（置換メチル）ポリフェニルの置換メチル基１モルに対し、通常０．１〜５０モルであり、１〜２０モルが好ましく、２〜１０モルがさらに好ましい。添加量が置換メチル基１モルに対し、０．１モルより少ないと、原料が溶解せず、撹拌ができない。５０モルより多いと、反応容器の効率が悪く工業上有利でない。 In the production of the polyphenylpolyphenyl derivative of the present invention, the reaction may be performed under solvent-free conditions, but a solvent can be added to the reaction system as necessary in order to allow the reaction to proceed more smoothly. Specific examples of the solvent include lower aliphatic carboxylic acids such as formic acid, acetic acid, and propionic acid, and lower aliphatic alcohols such as methanol, ethanol, propanol, 2-propanol, and t-butanol. Preferred examples include lower aliphatic carboxylic acids such as formic acid, acetic acid and propionic acid, and more preferred is acetic acid. These solvents may be used alone or in combination of two or more. The addition amount is usually 0.1 to 50 mol, preferably 1 to 20 mol, and preferably 2 to 10 mol based on 1 mol of the substituted methyl group of the poly (substituted methyl) polyphenyl represented by the general formula (2). Further preferred. When the addition amount is less than 0.1 mol per 1 mol of the substituted methyl group, the raw materials are not dissolved and stirring is not possible. When the amount is more than 50 mol, the efficiency of the reaction vessel is poor and it is not industrially advantageous.
本発明のポリフェニルポリフェニル誘導体の製造において、水またはアルコールを反応基質として使用する。アルコールの具体例としては、メタノール、エタノール、プロパノール、２−プロパノール、ｔ−ブタノール等が挙げられるがこれらに限定されるものではない。好ましくはメタノールを用いる。さらに、原料を均一に溶解させ、反応を円滑に進行させる点、および反応後に濾過により簡便にヘキサメチレンテトラミンやホルムアルデヒド−アンモニア混合物等を除去できる点から、水および／またはアルコールを置換メチル基の当量以上添加することが好ましい。この場合の水および／またはアルコールの仕込み量は一般式（２）で示されるポリ（置換メチル）ポリフェニルの置換メチル基に対して、通常１〜２００倍であり、５〜１００倍が好ましく、１０〜２０倍が特に好ましい。水および／またはアルコールが置換メチル基に対して１倍モルより少ないと未反応原料が残存し、２００倍モルより多いと、原料が溶解しきらないため、反応が均一に進行せず、生成物の純度が低くなる。 In the production of the polyphenylpolyphenyl derivative of the present invention, water or alcohol is used as a reaction substrate. Specific examples of the alcohol include, but are not limited to, methanol, ethanol, propanol, 2-propanol, t-butanol and the like. Preferably methanol is used. Furthermore, water and / or alcohol is equivalent to the substituted methyl group from the point that the raw materials are uniformly dissolved, the reaction proceeds smoothly, and the hexamethylenetetramine or formaldehyde-ammonia mixture can be easily removed by filtration after the reaction. It is preferable to add more. The amount of water and / or alcohol charged in this case is usually 1 to 200 times, preferably 5 to 100 times the substituted methyl group of the poly (substituted methyl) polyphenyl represented by the general formula (2), 10 to 20 times is particularly preferable. If the amount of water and / or alcohol is less than 1 mole relative to the substituted methyl group, the unreacted raw material remains, and if it is greater than 200 mole, the raw material cannot be completely dissolved, and the reaction does not proceed uniformly, resulting in a product. The purity of becomes low.
本発明の反応温度は５０〜１５０℃が好ましく、さらに好ましくは、８０〜１１０℃である。また、反応時間は１〜２４時間が好ましく、さらに好ましくは、２〜１０時間である。 50-150 degreeC of reaction temperature of this invention is preferable, More preferably, it is 80-110 degreeC. The reaction time is preferably 1 to 24 hours, more preferably 2 to 10 hours.
本発明において反応が完結しない場合、系内に酸触媒を添加し、反応を完結させる。酸触媒としては種々のものが使用できるが塩酸、硫酸、ｐ−トルエンスルホン酸、シュウ酸等の無機あるいは有機酸、三弗化ホウ素、無水塩化アルミニウム、塩化亜鉛などのルイス酸が挙げられる。添加量は一般式（２）で示されるポリ（置換メチル）ポリフェニルの置換メチル基１モルに対し、通常２０モル以下であり、１０モル以下が好ましく、５モル以下がさらに好ましい。添加量が置換メチル基の５０倍モルより多いと、アルデヒド基同士の縮合反応により高分子量化する可能性が有る。反応温度は５０〜１５０℃が好ましく、さらに好ましくは、８０〜１１０℃である。また、反応時間は１時間〜２４時間が好ましく、さらに好ましくは、２〜１０時間である。 In the present invention, when the reaction is not completed, an acid catalyst is added to the system to complete the reaction. Various acid catalysts can be used, and examples include inorganic or organic acids such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The addition amount is usually 20 mol or less, preferably 10 mol or less, more preferably 5 mol or less, per 1 mol of the substituted methyl group of the poly (substituted methyl) polyphenyl represented by the general formula (2). If the amount added is more than 50 times the molar amount of the substituted methyl group, there is a possibility that the molecular weight is increased by the condensation reaction between aldehyde groups. The reaction temperature is preferably 50 to 150 ° C, more preferably 80 to 110 ° C. The reaction time is preferably 1 to 24 hours, and more preferably 2 to 10 hours.
反応終了後、反応溶液を５０℃以下に冷却して固体として析出・単離させることにより精製することができる。析出した固体を、吸引濾過や遠心濾過等の方法により反応溶液と分離して取り出すことが出来る。この固体に温水を加えて洗浄し、乾燥させることにより、目的の生成物を得ることができる。 After completion of the reaction, the reaction solution can be purified by cooling to 50 ° C. or lower and precipitating and isolating as a solid. The precipitated solid can be separated from the reaction solution by a method such as suction filtration or centrifugal filtration. The target product can be obtained by adding warm water to the solid for washing and drying.
こうして得られた、本発明のポリホルミルポリフェニル誘導体は、下記式（１）
で表される構造をとる。
The polyformyl polyphenyl derivative of the present invention thus obtained has the following formula (1)
The structure represented by is taken.
本発明のポリホルミルポリフェニル誘導体は、液晶化合物の中間体、液晶ポリマーの原料または、樹脂の原料等に極めて有用である。
具体的には、硬化剤ないしエポキシ樹脂の原料として使用することが可能である。
The polyformyl polyphenyl derivative of the present invention is extremely useful as an intermediate of a liquid crystal compound, a raw material of a liquid crystal polymer, a raw material of a resin, or the like.
Specifically, it can be used as a raw material for a curing agent or an epoxy resin.
以下、本発明を合成例、実施例により更に詳細に説明する。尚、本発明はこれら合成例、実施例に限定されるものではない。また、本発明の生成物は以下の方法で同定した。なお、合成例、実施例において特に断りがない限り「部」は重量部を、「％」は重量％をそれぞれ意味する。
（１）液体クロマトグラフィー（ＨＰＬＣ）法
ＨＰＬＣの各種条件
ＨＰＬＣモデル：（株）島津製作所 ＬＣ−２０ＡＤ
カラム： ＯＤＳ−２
使用溶剤： 水（Ａ液）−アセトニトリル（Ｂ液）
Ｂ液濃度勾配：７０％（０ｍｉｎ）−１００％（１４ｍｉｎ）−１００％（４０ｍｉｎ）
流速：１ｍｌ／ｍｉｎ．
カラム温度：４０℃
検出器：（株）島津製作所 フォトダイオードアレイ ＳＰＤ−Ｍ２０Ａ
（２）１Ｈ−ＮＭＲ
１Ｈ−ＮＭＲの各種条件
ＮＭＲモデル： 日本電子（株）ＪＮＭ−ＥＣＳ４００
溶媒：ＣＤＣｌ３
濃度：１００ｍｇ／０．５ｍＬ
周波数領域：４００ＭＨｚ
パルス間隔： ３．１ｕｓ
積算回数：８回
測定温度：９．４Ｔ
（３）ＧＣ−ＭＳ
ＧＣ−ＭＳモデル：Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ ６８９０Ｎ
カラム：ＨＰ−５ＭＳ
キャリア：ヘリウム
流速：１ｍＬ／ｍｉｎ
カラム温度：５０℃（２ｍｉｎ）−１０℃／ｍｉｎ−３００℃（１３ｍｉｎ）
インジェクション：オートインジェクター
１μＬ，ｓｐｌｉｔ ３０：１，３００℃
イオン化：ＥＩ
（４）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）
メーカー：島津製作所
カラム：ガードカラム ＳＨＯＤＥＸ ＧＰＣ ＫＦ−８０２．５（２本） ＫＦ−８０２ ＫＦ−８０３
流速：１．０ｍｌ／ｍｉｎ．
カラム温度：４０℃
使用溶剤：ＴＨＦ（テトラヒドロフラン）
検出器：ＲＩ（示差屈折検出器）
Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. The product of the present invention was identified by the following method. In the synthesis examples and examples, “part” means part by weight and “%” means weight% unless otherwise specified.
(1) Various conditions of liquid chromatography (HPLC) HPLC method HPLC model: Shimadzu Corporation LC-20AD
Column: ODS-2
Solvent: Water (Liquid A)-Acetonitrile (Liquid B)
B liquid concentration gradient: 70% (0 min) -100% (14 min) -100% (40 min)
Flow rate: 1 ml / min.
Column temperature: 40 ° C
Detector: Shimadzu Corporation Photodiode array SPD-M20A
(2) 1 H-NMR
Various conditions of 1 H-NMR NMR model: JEOL Ltd. JNM-ECS400
Solvent: CDCl 3
Concentration: 100 mg / 0.5 mL
Frequency domain: 400MHz
Pulse interval: 3.1us
Integration count: 8 times Measurement temperature: 9.4T
(3) GC-MS
GC-MS model: Agilent Technologies 6890N
Column: HP-5MS
Carrier: Helium flow rate: 1 mL / min
Column temperature: 50 ° C. (2 min) −10 ° C./min−300° C. (13 min)
Injection: Autoinjector 1 μL, split 30: 1, 300 ° C.
Ionization: EI
(4) Gel permeation chromatography (GPC)
Manufacturer: Shimadzu Corporation Column: Guard column SHODEX GPC KF-802.5 (2) KF-802 KF-803
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
実施例１
温度計、冷却管、撹拌器を取り付けたフラスコに窒素ガスパージを施しながら４，４’−ジクロロメチルジフェニル１２５部、ヘキサメチレンテトラミン２８０部、５０重量％酢酸水溶液６４９部を仕込み、撹拌下で９５℃まで昇温し、１０時間反応させた。撹拌中結晶が析出し始めたがそのまま撹拌を続けた。反応終了後、室温まで冷却して、吸引濾過にて固形分を回収した。さらに固形分に温水を加え、室温で撹拌し、吸引濾過して固形分を回収する工程を４回行った。得られた固形分をオーブン内、７０℃にて終夜乾燥し、純度９７％の４，４’−ジホルミルジフェニル１０５部を得た。本化合物はＨＰＬＣ（下記チャート１）、１Ｈ−ＮＭＲ（下記チャート２）、ＧＣ−ＭＳ（下記チャート３）を用いて同定を行った。ＨＰＬＣの結果、上記式（２）で表される化合物の含有量が１．０面積％以下であり、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）での高分子量体面積比率は、１．５面積％であった。
チャート１：
A flask equipped with a thermometer, a condenser, and a stirrer was charged with 125 parts of 4,4′-dichloromethyldiphenyl, 280 parts of hexamethylenetetramine, and 649 parts of a 50 wt% aqueous acetic acid solution while purging with nitrogen gas. The mixture was heated up to react for 10 hours. While stirring, crystals started to precipitate, but stirring was continued as it was. After completion of the reaction, the reaction mixture was cooled to room temperature and the solid content was collected by suction filtration. Furthermore, the process of adding warm water to solid content, stirring at room temperature, and carrying out suction filtration and collect | recovering solid content was performed 4 times. The obtained solid content was dried in an oven at 70 ° C. overnight to obtain 105 parts of 4,4′-diformyldiphenyl having a purity of 97%. This compound was identified using HPLC (Chart 1 below), 1 H-NMR (Chart 2 below), and GC-MS (Chart 3 below). As a result of HPLC, the content of the compound represented by the above formula (2) is 1.0 area% or less, and the high molecular weight area ratio in gel permeation chromatography (GPC) is 1.5 area%. there were.
Chart 1:
実施例２
原料の仕込み量を４，４’−ジクロロメチルジフェニル２００部、ヘキサメチレンテトラミン３３６部、５０％酢酸水溶液９６０部を仕込み、撹拌下で９５℃まで昇温し、１０時間反応させた。続いて反応系内に３５％塩酸を８３部加え、撹拌を続けた。反応終了後、室温まで冷却して、吸引濾過にて固形分を回収した。さらに固形分に温水を加え、室温で撹拌し、吸引濾過して固形分を回収する工程を４回行い得られた固形分を、オーブン内、７０℃にて終夜乾燥し、純度９７％の４，４’−ジホルミルジフェニル１５８部を得た。ＨＰＬＣの結果、上記式（２）で表される化合物の含有量が１．０面積％以下であり、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）での高分子量体面積比率は、２．０面積％であった。
Example 2
The raw material was charged in 200 parts of 4,4′-dichloromethyldiphenyl, 336 parts of hexamethylenetetramine, and 960 parts of 50% acetic acid aqueous solution, heated to 95 ° C. with stirring, and reacted for 10 hours. Subsequently, 83 parts of 35% hydrochloric acid was added to the reaction system, and stirring was continued. After completion of the reaction, the reaction mixture was cooled to room temperature and the solid content was collected by suction filtration. Further, warm water was added to the solid content, stirred at room temperature, and suction filtered to collect the solid content four times. The solid content obtained was dried in an oven at 70 ° C. overnight, and the purity was 97%. 158 parts of 4'-diformyldiphenyl were obtained. As a result of HPLC, the content of the compound represented by the above formula (2) is 1.0 area% or less, and the high molecular weight area ratio in gel permeation chromatography (GPC) is 2.0 area%. there were.
実施例３
原料の仕込み量を４，４’−ジクロロメチルジフェニル２５０部、ヘキサメチレンテトラミン３８８部、５０％酢酸メタノール溶液８４１部を仕込み、撹拌下で９５℃まで昇温し、１０時間反応させた。撹拌中結晶が析出し始めたがそのまま撹拌を続けた。反応終了後、室温まで冷却して、吸引濾過にて固形分を回収した。さらに固形分に温水を加え、室温で撹拌し、吸引濾過して固形分を回収する工程を４回行った。得られた固形分をオーブン内、７０℃にて終夜乾燥し、純度７５％の４，４’−ジホルミルジフェニル１９６部を得た。ＨＰＬＣの結果、上記式（２）で表される化合物の含有量が１．０面積％以下であり、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）での高分子量体面積比率は、２．０面積％であった。
Example 3
The raw material was charged in 250 parts of 4,4′-dichloromethyldiphenyl, 388 parts of hexamethylenetetramine, and 841 parts of a 50% methanol solution in acetic acid. The temperature was raised to 95 ° C. with stirring and the reaction was carried out for 10 hours. While stirring, crystals started to precipitate, but stirring was continued as it was. After completion of the reaction, the reaction mixture was cooled to room temperature and the solid content was collected by suction filtration. Furthermore, the process of adding warm water to solid content, stirring at room temperature, and carrying out suction filtration and collect | recovering solid content was performed 4 times. The obtained solid content was dried in an oven at 70 ° C. overnight to obtain 196 parts of 4,4′-diformyldiphenyl having a purity of 75%. As a result of HPLC, the content of the compound represented by the above formula (2) is 1.0 area% or less, and the high molecular weight area ratio in gel permeation chromatography (GPC) is 2.0 area%. there were.
参考例１
本発明で得られたポリホルミルポリフェニル誘導体をフェノール樹脂原料として用い、エポキシ樹脂、エポキシ樹脂組成物、および硬化物を得た例を示す。尚、水酸基当量、エポキシ当量、軟化点、ＩＣＩ粘度は以下の条件で測定した。
・水酸基当量
ＪＩＳ Ｋ−７２３６に記載された方法で測定し、単位はｇ／ｅｑ．である。
・エポキシ当量
ＪＩＳ Ｋ−７２３６に記載された方法で測定し、単位はｇ／ｅｑ．である。
・軟化点
ＪＩＳ Ｋ−７２３４に準拠した方法で測定。
・ＩＣＩ粘度
ＪＩＳ Ｋ−７１１７−２に準拠した方法で測定
攪拌機、還流冷却管、攪拌装置を備えたフラスコに、窒素パージを施しながら実施例１で得られた４，４’−ジホルミルジフェニル１０５部、フェノール７０６部、ｐ−トルエンスルホン酸１１．７部を加え、１００℃に昇温し、そのままの温度を保ち８時間反応を行った。反応終了後、ＭＩＢＫを３００部加え、水層が中性になるまで水洗を行った。得られた有機層をロータリーエバポレーターで１８０℃で減圧下、過剰のフェノールを留去することでフェノール樹脂２５２部を得た。得られたフェノール樹脂は赤色固形であり、水酸基当量は１４５ｇ／ｅｑ．、軟化点は１３０℃であった。
攪拌機、還流冷却管、攪拌装置を備えたフラスコに、窒素パージを施しながら得られたフェノール樹脂２５３部、エピクロロヒドリン９６６部、メタノール６３部、水９．７部を加え、７５℃にまで昇温した。次いでフレーク状の水酸化ナトリウム７２部を９０分かけて分割添加した後、さらに７５℃で７５分間反応を行った。反応終了後水洗を行い、有機層からロータリーエバポレーターを用いて１４０℃で減圧下、過剰のエピクロロヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン６６５部を加え溶解し、７５℃にまで昇温した。攪拌下でメタノール７．９部、３０％水酸化ナトリウム水溶液２３部を加え、１時間反応を行った後、洗浄水が中性になるまで有機層を水洗し得られた有機層からロータリーエバポレーターを用いて１８０℃で減圧下にメチルイソブチルケトン等の溶剤を留去することで本発明のエポキシ樹脂を３２１部得た。得られたエポキシ樹脂は黄色固形であり、エポキシ当量は２１１ｇ／ｅｑ．、軟化点は９９℃、１５０℃における粘度は２．７６Ｐａ・ｓであった。
Reference example 1
The example which obtained the epoxy resin, the epoxy resin composition, and hardened | cured material using the polyformyl polyphenyl derivative obtained by this invention as a phenol resin raw material is shown. The hydroxyl equivalent, epoxy equivalent, softening point, and ICI viscosity were measured under the following conditions.
-Hydroxyl equivalent: Measured by the method described in JIS K-7236, the unit is g / eq. It is.
-Epoxy equivalent Measured by the method described in JIS K-7236, the unit is g / eq. It is.
-Softening point Measured by a method based on JIS K-7234.
-ICI viscosity 4,4'-diformyldiphenyl 105 obtained in Example 1 while performing nitrogen purging on a flask equipped with a measuring stirrer, a reflux condenser, and a stirrer in accordance with JIS K-7117-2. Part, 706 parts of phenol and 11.7 parts of p-toluenesulfonic acid were added, the temperature was raised to 100 ° C., and the reaction was carried out for 8 hours while maintaining the temperature as it was. After completion of the reaction, 300 parts of MIBK was added and washed with water until the aqueous layer became neutral. Excess phenol was distilled off under reduced pressure at 180 ° C. using a rotary evaporator to obtain 252 parts of a phenol resin. The obtained phenol resin was red solid, and the hydroxyl equivalent was 145 g / eq. The softening point was 130 ° C.
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, add 253 parts of a phenol resin, 966 parts of epichlorohydrin, 63 parts of methanol, and 9.7 parts of water obtained while performing a nitrogen purge. The temperature rose. Next, after 72 parts of flaky sodium hydroxide were added in portions over 90 minutes, the reaction was further carried out at 75 ° C. for 75 minutes. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 140 ° C. using a rotary evaporator. To the residue, 665 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 7.9 parts of methanol and 23 parts of 30% aqueous sodium hydroxide solution were added and reacted for 1 hour. Then, the organic layer was washed with water until the washing water became neutral. 321 parts of the epoxy resin of the present invention was obtained by distilling off a solvent such as methyl isobutyl ketone at 180 ° C. under reduced pressure. The obtained epoxy resin was a yellow solid, and the epoxy equivalent was 211 g / eq. The softening point was 99 ° C. and the viscosity at 150 ° C. was 2.76 Pa · s.
各種成分を表１の割合（部）で配合し、ミキシングロールで混練、タブレット化後、トランスファー成形で樹脂成形体を調製し、１６０℃で２時間、更に１８０℃
で８時間加熱を行い、本発明のエポキシ樹脂組成物の硬化物を得た。これら硬化物の物性を以下の条件で測定した結果を表１
に示した。
・ＤＭＡ
動的粘弾性測定器：ＴＡ−ｉｎｓｔｒｕｍｅｎｔｓ製ＤＭＡ−２９８０
昇温速度：２℃／分
・ＴＭＡ
ＴＭＡ熱機械測定装置：真空理工（株）製ＴＭ−７０００
昇温速度：２℃／ｍｉｎ．
・ピール強度
ＪＩＳＫ−６９１１に準拠
・吸水湿性
直径５ｃｍ×厚み４ｍｍの円盤状の試験片を１００℃―浸水、８５℃―８５％、１２１℃―１００％
の各条件下、２４時間煮沸した後の重量増加率（％）
・硬化収縮
ＪＩＳＫ−６９１１（成型収縮率）に準拠
・誘電性
Ｋ６９９１に準拠して１ＧＨｚにおいて測定
・熱伝導
熱伝導率測定装置：Ａｎｔｅｒ社製Ｕｎｉｔｈｅｒｍ２０２２
ＡＳＴＭＥ−１５３０に準拠
硬化剤：フェノールノボラック（明和化成工業株式会社製 Ｈ−１）
触媒：トリフェニルホスフィン（純正化学株式会社製）
Various components are blended in the proportions (parts) shown in Table 1, kneaded with a mixing roll, converted into a tablet, and then a resin molded product is prepared by transfer molding.
Was heated for 8 hours to obtain a cured product of the epoxy resin composition of the present invention. The results of measuring the physical properties of these cured products under the following conditions are shown in Table 1.
It was shown to.
・ DMA
Dynamic viscoelasticity measuring device: DMA-2980 manufactured by TA-instruments
Temperature increase rate: 2 ° C / min.TMA
TMA thermomechanical measuring device: TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C./min.
・ Peel strength compliant with JISK-6911 ・ Water-absorbent diameter 5cm x thickness 4mm disc-shaped test piece is 100 ℃ -water immersion, 85 ℃ -85%, 121 ℃ -100%
Weight increase rate after boiling for 24 hours under each condition of (%)
・ Conforms to curing shrinkage JISK-6911 (molding shrinkage) ・ Measures at 1 GHz according to dielectric K6991 ・ Heat conduction thermal conductivity measuring device: Uniter 2022 manufactured by Anter
Compliant with ASTME-1530
Catalyst: Triphenylphosphine (Pure Chemical Co., Ltd.)
以上の結果から、本発明で得られたポリホルミルポリフェニル誘導体を用いて合成したエポキシ樹脂は高い耐熱性を有する硬化物を与えることができ、特にＩＣ封止材料、積層材料、電気絶縁材料等などの電気・電子分野に有用である。
From the above results, the epoxy resin synthesized using the polyformyl polyphenyl derivative obtained in the present invention can give a cured product having high heat resistance, particularly IC sealing material, laminated material, electrical insulating material, etc. It is useful in the electric / electronic field.
Claims (6)
で表されるポリホルミルポリフェニル誘導体であって、下記式（２）
で表される化合物の含有割合が高速液体クロマトグラフィーでの測定において５面積％以下であることを特徴とするポリホルミルポリフェニル誘導体。 General formula (1) in which the content of the transition metal compound is 100 ppm or less
A polyformylpolyphenyl derivative represented by the following formula (2):
A polyformyl polyphenyl derivative characterized in that the content of the compound represented by the formula is 5 area% or less as measured by high performance liquid chromatography.
で表されるポリ（置換メチル）ポリフェニル誘導体と、
水および／またはアルコールと、
ヘキサメチレンテトラミンおよび／またはホルムアルデヒド−アンモニア混合物等を反応させることにより得られる、請求項１又は請求項２のいずれか一項に記載のポリホルミルポリフェニル誘導体。 General formula (2)
A poly (substituted methyl) polyphenyl derivative represented by:
With water and / or alcohol,
The polyformyl polyphenyl derivative according to claim 1, which is obtained by reacting hexamethylenetetramine and / or a formaldehyde-ammonia mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013087965A JP2014210731A (en) | 2013-04-19 | 2013-04-19 | Polyformyl polyphenyl derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013087965A JP2014210731A (en) | 2013-04-19 | 2013-04-19 | Polyformyl polyphenyl derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2014210731A true JP2014210731A (en) | 2014-11-13 |
Family
ID=51930779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013087965A Pending JP2014210731A (en) | 2013-04-19 | 2013-04-19 | Polyformyl polyphenyl derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2014210731A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02252724A (en) * | 1989-03-28 | 1990-10-11 | Dainippon Ink & Chem Inc | Novel epoxy resin composition |
| JPH07330645A (en) * | 1994-04-13 | 1995-12-19 | Nippon Kayaku Co Ltd | Compound of polyphenols, epoxy resin, epoxy resin composition and cured material thereof |
| JPH11276193A (en) * | 1998-03-30 | 1999-10-12 | Tanabe Seiyaku Co Ltd | Production of optically active biaryl derivative |
| JP2001199910A (en) * | 2000-01-18 | 2001-07-24 | Tosoh Corp | Method for producing aromatic compound |
| JP2009132707A (en) * | 2007-11-09 | 2009-06-18 | Kwansei Gakuin | Hexahydroxydiphenoyl compound |
| CN101781197A (en) * | 2010-03-16 | 2010-07-21 | 中山大学 | Preparation method of chiral binaphthyl dicarboxylic acid |
-
2013
- 2013-04-19 JP JP2013087965A patent/JP2014210731A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02252724A (en) * | 1989-03-28 | 1990-10-11 | Dainippon Ink & Chem Inc | Novel epoxy resin composition |
| JPH07330645A (en) * | 1994-04-13 | 1995-12-19 | Nippon Kayaku Co Ltd | Compound of polyphenols, epoxy resin, epoxy resin composition and cured material thereof |
| JPH11276193A (en) * | 1998-03-30 | 1999-10-12 | Tanabe Seiyaku Co Ltd | Production of optically active biaryl derivative |
| JP2001199910A (en) * | 2000-01-18 | 2001-07-24 | Tosoh Corp | Method for producing aromatic compound |
| JP2009132707A (en) * | 2007-11-09 | 2009-06-18 | Kwansei Gakuin | Hexahydroxydiphenoyl compound |
| CN101781197A (en) * | 2010-03-16 | 2010-07-21 | 中山大学 | Preparation method of chiral binaphthyl dicarboxylic acid |
Non-Patent Citations (7)
| Title |
|---|
| BACON, R. G. R.; LINDSAY, W. S.: "Cyclizations with hydrazine. I. Preparation of phenanthrene compounds and of pyrene from aldehydes.", JOURNAL OF THE CHEMICAL SOCIETY, JPN6016041521, 1958, pages 1375-81 * |
| BAEK, JEONG JU ET AL.: "SYNTHESIS AND ELECTRO-OPTICAL PROPERTIES OF BLUE EMITTING POLY(BP-alt-BCV) CONJUGATED POLYMERS", JOURNAL OF NONLINEAR OPTICAL PHYSICS & MATERIALS, vol. 14, no. 4, JPN6017017527, 2005, pages 535 - 543 * |
| GROSS, JENS ET AL.: "Concave hydrocarbons", CHEMISTRY - A EUROPEAN JOURNAL, vol. 2, no. 12, JPN6016023011, 1996, pages 1585 - 1595 * |
| GROSS, JENS; HARDER, GABRIELE; SIEPEN, ASTRID; HARREN, JOERG;: "Concave hydrocarbons", CHEMISTRY - A EUROPEAN JOURNAL, vol. 2(12), JPN6016023011, 1996, pages 1585-1595 * |
| HE, YAN ET AL.: "Synthesis and luminescent properties of novel Cu(II), Zn(II) polymeric complexes based on 1,10-phena", J. CHEM. SCI., vol. 121, no. 4, JPN6017017528, 2009, pages 407 - 412 * |
| KOZAKOVA, MICHALA ET AL.: "Synehtsis of Rigid Polyaromatic Dialdehydes", SYNTHETIC COMMUNICATIONS, vol. 35, no. 2, JPN6017017531, 2005, pages 161 - 167 * |
| 第４版 実験化学講座１ 基本操作Ｉ, JPN6016023012, 5 November 1990 (1990-11-05), pages 61 - 163 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2955169B1 (en) | Novel allyl compound and method for producing the same | |
| JP5870997B2 (en) | Polybenzoxazole resin and precursor thereof | |
| CN113396137A (en) | Method for producing 1,1, 1-trifluoro-2, 2-bisarylethane, and 1,1, 1-trifluoro-2, 2-bisarylethane | |
| JP2013087173A (en) | Novel epoxy compound and method for producing the same | |
| JP2020502310A (en) | Curable compound | |
| KR20160008529A (en) | Method for producing biphenyl-skeleton-containing epoxy resin | |
| JP2014210731A (en) | Polyformyl polyphenyl derivative | |
| WO2016006649A1 (en) | Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof | |
| WO2006085630A1 (en) | Process for producing aromatic dicarboxylic acid | |
| JP2012111926A (en) | Diepoxy compound, composition comprising the compound, and cured product obtained by curing the composition | |
| JP7113665B2 (en) | Composition and method for producing the same | |
| JP2009209117A (en) | Epoxy compound, method for producing the same, epoxy resin composition and cured product thereof | |
| JP3128162B2 (en) | Aromatic dinitro compound, aromatic diamino compound and method for producing them | |
| JP2004238437A (en) | Naphthol-based phenolic resin and method for producing the same | |
| JP2009107991A (en) | New hydroxymethyl-substituted or alkoxymethyl-substituted bisphenol compound | |
| JP3282330B2 (en) | Polyhydric phenolic compound and method for producing polyhydric phenolic compound | |
| JP3132783B2 (en) | Aromatic dinitro compound, aromatic diamino compound and method for producing them | |
| JP6341933B2 (en) | Phenolic resins, epoxy resins, epoxy resin compositions and cured products thereof | |
| TWI374868B (en) | Method for producing 1,4-bis(dichloromethyl)tetrafluorobenzene | |
| JPWO2011037073A1 (en) | Method for producing trans cyclic polyphenol compound | |
| JP2011246440A (en) | Diepoxy compound, method for preparing the same, and cured product obtained by curing the compound | |
| TW202342642A (en) | Maleimide compound, maleamic acid compound, curable composition, cured product, electronic device, method of producing maleimide compound and method of producing maleamic acid compound | |
| JP2023154930A (en) | Novel thermally conductive compounds | |
| WO2023167177A1 (en) | Polyether ketone ketone and method for producing same | |
| JP2002241495A (en) | New 1,3-benzoxazine monomer bearing propargyl ether group and polybenzoxazine obtained by polymerizing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20151009 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160609 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160617 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160803 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161031 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161213 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170518 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20171106 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20180507 |