JP2001200031A - Phenolic compound and method for producing the same - Google Patents
Phenolic compound and method for producing the sameInfo
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- JP2001200031A JP2001200031A JP2001006233A JP2001006233A JP2001200031A JP 2001200031 A JP2001200031 A JP 2001200031A JP 2001006233 A JP2001006233 A JP 2001006233A JP 2001006233 A JP2001006233 A JP 2001006233A JP 2001200031 A JP2001200031 A JP 2001200031A
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- phenolic compound
- integer
- producing
- phenol
- general formula
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エポキシ樹脂中間
体及び各種高性能高分子の原料として有用な新規フェノ
ール性化合物及びその製造方法に関するものである。TECHNICAL FIELD The present invention relates to a novel phenolic compound useful as an epoxy resin intermediate and a raw material for various high-performance polymers, and a method for producing the same.
【０００２】[0002]
【従来の技術】ビスフェノールＡに代表される多価のフ
ェノール性化合物は、種々の高性能高分子、例えばポリ
エステル、ポリカーボネート、ポリウレタン、エポキシ
樹脂等の出発原料として広く一般に使用されている。し
かしながら、用途の多様化にともない、これら高分子材
料に対して耐熱性、耐湿性、靭性等の向上が強く求めら
れている。2. Description of the Related Art Polyhydric phenolic compounds represented by bisphenol A are widely and generally used as starting materials for various high-performance polymers such as polyesters, polycarbonates, polyurethanes and epoxy resins. However, with the diversification of uses, improvement of heat resistance, moisture resistance, toughness and the like of these polymer materials is strongly demanded.
【０００３】そこで、これら物性の改良を目的に新規な
ビスフェノール化合物が提案されている（特開昭５８‐
１８３３１号公報）が、このようなビスフェノール類を
原料にして得られた高分子化合物にしても十分に満足し
得る物性を有しているわけではない。Therefore, a novel bisphenol compound has been proposed for the purpose of improving these physical properties (Japanese Patent Application Laid-Open No. 58-1983).
No. 18331) does not necessarily have sufficiently satisfactory physical properties even with a polymer compound obtained from such a bisphenol as a raw material.
【０００４】[0004]
【発明が解決しようとする課題】したがって、本発明の
目的は、耐熱性、耐湿性に優れ、かつ、耐衝撃性等の機
械的特性に優れた性能を有する高性能高分子用原料等に
有用な、特にエポキシ樹脂原料に有用な新規フェノール
性化合物及びその製造方法を提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a raw material for high-performance polymers having excellent heat resistance, moisture resistance and excellent mechanical properties such as impact resistance. In particular, it is an object of the present invention to provide a novel phenolic compound useful as an epoxy resin raw material and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、下
記一般式（１）That is, the present invention provides a compound represented by the following general formula (1):
【化４】 （但し、式中、Ｒ1、Ｒ2、Ｒ3は、水素原子又は炭素数
１〜６の炭化水素基を示し、ｎは０〜１５の整数を示
し、ｍは０〜２の整数を示す）で表されるフェノール性
化合物である。また、本発明は、エポキシ化合物製造用
の中間体である前記のフェノール性化合物である。更
に、本発明は、一般式（１）において、ｎが０の化合物
が主成分である前記のフェノール性化合物である。Embedded image (Wherein, R 1 , R 2 , and R 3 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, n represents an integer of 0 to 15, and m represents an integer of 0 to 2) ) Is a phenolic compound represented by Further, the present invention is the above-mentioned phenolic compound which is an intermediate for producing an epoxy compound. Furthermore, the present invention is the above-mentioned phenolic compound, wherein the compound of the formula (1) wherein n is 0 is a main component.
【０００６】また、本発明は下記一般式（２）Further, the present invention provides the following general formula (2)
【化５】 （但し、Ｒ3は、水素原子又は炭素数１〜６の炭化水素
基を示し、ｍは０〜２の整数を示す）で表されるフェノ
ール類と下記一般式（３）Embedded image (Where R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 0 to 2) and a phenol represented by the following general formula (3)
【化６】 （但し、式中、Ｒ1、Ｒ2、Ｒ4は、水素原子又は炭素数
１〜６の炭化水素基を示す）で表される縮合剤とを、酸
触媒の存在下に、フェノール類と縮合剤とのモル比（縮
合剤／フェノール類）０．０１〜０．９の条件で反応さ
せる前記のいずれかに記載のフェノール性化合物の製造
方法である。Embedded image (Wherein, R 1 , R 2 , and R 4 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) with a phenol in the presence of an acid catalyst. The method for producing a phenolic compound according to any one of the above, wherein the reaction is carried out at a molar ratio with the condensing agent (condensing agent / phenols) of 0.01 to 0.9.
【０００７】本発明のフェノール性化合物からエポキシ
化合物を得るには、フェノール性化合物とエピクロルヒ
ドリンとを、アルカリ金属水酸化物の存在下に反応温度
６０〜１２０℃及びフェノール性化合物とエピクロルヒ
ドリンとのモル比（エピクロルヒドリン／フェノール性
化合物）０．９〜１．２の条件で反応させる方法があ
る。To obtain an epoxy compound from the phenolic compound of the present invention, the phenolic compound and epichlorohydrin are reacted at a reaction temperature of 60 to 120 ° C. in the presence of an alkali metal hydroxide and at a molar ratio of the phenolic compound to epichlorohydrin. (Epichlorohydrin / phenolic compound) There is a method of reacting under the conditions of 0.9 to 1.2.
【０００８】上記の方法で得られるエポキシ化合物は、
下記一般式（４）The epoxy compound obtained by the above method is
The following general formula (4)
【化７】 （但し、式中、Ｒ1、Ｒ2、Ｒ3は、水素原子又は炭素数
１〜６の炭化水素基を示し、ｎは０〜１５の整数を示
し、ｍは０〜２の整数を示す。また、Ｇはグリシジル基
を示す）で表される。Embedded image (Wherein, R 1 , R 2 , and R 3 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, n represents an integer of 0 to 15, and m represents an integer of 0 to 2) G represents a glycidyl group).
【０００９】上記一般式（２）で表されるフェノール類
において、Ｒ3は水素原子又は炭素数１〜６の炭化水素
基を示し、ｍは０〜２の整数を示す。一般式（２） で
示されるフェノール類の具体例としては、例えばフェノ
ール、ｏ‐クレゾール、ｍ‐クレゾール、2,6-キシレノ
ール、ｏ‐エチルフェノール、2,6-ジエチルフェノー
ル、ｏ‐フェニルフェノール等が挙げられる。In the phenols represented by the general formula (2), R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 0 to 2. Specific examples of the phenol represented by the general formula (2) include phenol, o-cresol, m-cresol, 2,6-xylenol, o-ethylphenol, 2,6-diethylphenol, o-phenylphenol and the like. Is mentioned.
【００１０】上記一般式（３）で表される縮合剤におい
て、Ｒ1、Ｒ2、Ｒ4は、水素原子又は炭素数１〜６の炭
化水素基を示す。上記一般式（３）で表される縮合剤の
具体的例としては、例えば 4,4'-ジメチロールビフェニ
ル、 4,4'-ジメトキシメチルビフェニル、 4,4'-ジエト
キシメチルビフェニル、 4,4'-ジイソプロポキシメチル
ビフェニル、4,4'-ジヒドロキシエチルビフェニル、 4,
4'-ジ（1-メトキシ-1-エチル）ビフェニル、4,4'-ジ（1
-イソプロポキシ-1-エチル）ビフェニル、4,4'-ジ（2-
ヒドロキシ-2-プロピル）ビフェニル、4,4'-ジ（2-メト
キシ-2-プロピル）ビフェニル、 4,4'-ジ（2-イソプロ
ポキシ-2-ロピル）ビフェニル等が挙げられる。In the condensing agent represented by the general formula (3), R 1 , R 2 and R 4 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the condensing agent represented by the general formula (3) include, for example, 4,4′-dimethylolbiphenyl, 4,4′-dimethoxymethylbiphenyl, 4,4′-diethoxymethylbiphenyl, 4'-diisopropoxymethylbiphenyl, 4,4'-dihydroxyethylbiphenyl, 4,
4'-di (1-methoxy-1-ethyl) biphenyl, 4,4'-di (1
-Isopropoxy-1-ethyl) biphenyl, 4,4'-di (2-
Hydroxy-2-propyl) biphenyl, 4,4′-di (2-methoxy-2-propyl) biphenyl, 4,4′-di (2-isopropoxy-2-ropyl) biphenyl and the like.
【００１１】上記フェノール類と縮合剤とを反応させる
場合の両者のモル比は、フェノール類１モルに対して縮
合剤が１モル以下でなければならず、好ましくは０．０
１〜０．９モルの範囲である。When the phenol and the condensing agent are reacted with each other, the molar ratio of the condensing agent and the phenols must be not more than 1 mol per 1 mol of the phenols, preferably 0.0
It is in the range of 1 to 0.9 mole.
【００１２】このフェノール類と縮合剤とを反応させて
フェノール性化合物を製造する反応は、酸触媒の存在下
に行う。この酸触媒としては周知の無機酸、有機酸より
適宜選択することができ、例えば塩酸、硫酸、燐酸等の
鉱酸、ギ酸、シュウ酸、トリフルオロ酢酸、ｐ-トルエ
ンスルホン酸等の有機酸、三フッ化ホウ素、塩化亜鉛、
塩化アルミニウム、塩化鉄等のルイス酸あるいは固体酸
等が挙げられる。The reaction for producing a phenolic compound by reacting a phenol with a condensing agent is carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from well-known inorganic acids and organic acids, for example, mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, and p-toluenesulfonic acid; Boron trifluoride, zinc chloride,
Examples thereof include Lewis acids such as aluminum chloride and iron chloride, and solid acids.
【００１３】この反応は、通常‐５０〜２５０℃で１〜
２０時間行われる。また、反応の際にメタノール、エタ
ノール、プロパノール、ブタノール、エチレングリコー
ル、メチルセロソルブ、エチルセロソルブ等のアルコー
ル類やベンゼン、トルエン、クロロベンゼン、ジクロロ
ベンゼン等の芳香族化合物等を溶媒として使用すること
ができる。This reaction is usually carried out at -50 to 250 ° C for 1 to 1
Performed for 20 hours. In the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve and ethyl cellosolve, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as a solvent.
【００１４】また、本発明のフェノール性化合物は、エ
ピクロルヒドリンと反応させることにより、比較的低粘
度で耐熱性、耐湿性、靭性に優れたエポキシ化合物とす
ることができる。この反応は、通常のエポキシ化反応と
同様に行うことができるが、次のような方法で行うこと
がよい。By reacting the phenolic compound of the present invention with epichlorohydrin, an epoxy compound having a relatively low viscosity and excellent heat resistance, moisture resistance and toughness can be obtained. This reaction can be carried out in the same manner as a usual epoxidation reaction, but is preferably carried out by the following method.
【００１５】上記一般式（１）で表されるフェノール性
化合物を過剰のエピクロルヒドリンに溶解した後、水酸
化ナトリウム、水酸化カリウム等のアルカリ金属水酸化
物の存在下に、５０〜１５０℃、好ましくは６０〜１２
０℃の範囲で１〜１０時間反応させる方法が挙げられ
る。この際の、エピクロルヒドリンの使用量は、フェノ
ール性化合物中の水酸基１モルに対して０．８〜２モ
ル、好ましくは０．９〜１．２モルの範囲である。反応
終了後、過剰のエピクロルヒドリンを留去し、残留物を
トルエン、メチルイソブチルケトン等の溶剤に溶解し、
濾過し、水洗して無機塩を除去し、次いで溶剤を留去す
ることにより目的のエポキシ化合物を得ることができ
る。After dissolving the phenolic compound represented by the general formula (1) in an excess of epichlorohydrin, the solution is preferably heated to 50 to 150 ° C. in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Is 60-12
A method of reacting at 0 ° C. for 1 to 10 hours is exemplified. The amount of epichlorohydrin used at this time is in the range of 0.8 to 2 mol, preferably 0.9 to 1.2 mol, per 1 mol of the hydroxyl group in the phenolic compound. After completion of the reaction, excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene and methyl isobutyl ketone.
The desired epoxy compound can be obtained by filtering, washing with water to remove inorganic salts, and then distilling off the solvent.
【００１６】[0016]
【発明の実施の形態】以下、実施例により本発明をさら
に具体的に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically by way of examples.
【００１７】実施例１ ５００ｍｌの４口フラスコに、フェノール１１２．８ｇ
（１．２モル）、 4,4'-ジ（2-ヒドロキシ-2-プロピ
ル）ビフェニル２７ｇ（０．１モル）、ベンゼン３００
ｍｌを加え、溶解した後、約５℃に冷却し、濃塩酸１０
０ｍｌを加え、攪拌下１５時間反応させた。反応後、油
水分離し得られた油相を炭酸ソーダ水溶液で中和した。
その後、油相よりベンゼンを留去し、さらに水蒸気蒸溜
により大半の過剰のフェノールを除いて固体（樹脂）を
得た。得られた樹脂をベンゼンにて再結晶し白色の結晶
を得た。得られた樹脂結晶のＮＭＲ測定結果を表ｌに示
す。さらに、質量分析、元素分析よりこの生成物は、下
記式で表されるビスフェノール化合物と確認した。Example 1 In a 500 ml four-necked flask, 112.8 g of phenol was added.
(1.2 mol), 4,4'-di (2-hydroxy-2-propyl) biphenyl 27 g (0.1 mol), benzene 300
After adding and dissolving the mixture, the mixture was cooled to about 5 ° C and concentrated hydrochloric acid was added.
0 ml was added, and the mixture was reacted for 15 hours with stirring. After the reaction, the oil phase obtained by oil-water separation was neutralized with an aqueous sodium carbonate solution.
Thereafter, benzene was distilled off from the oil phase, and most of the excess phenol was removed by steam distillation to obtain a solid (resin). The obtained resin was recrystallized from benzene to obtain white crystals. Table 1 shows the NMR measurement results of the obtained resin crystals. Further, this product was confirmed to be a bisphenol compound represented by the following formula by mass spectrometry and elemental analysis.
【００１８】[0018]
【化８】 Embedded image
【００１９】[0019]
【表１】 [Table 1]
【００２０】実施例２ 実施例ｌで得た樹脂５５ｇをエピクロルヒドリン３３０
ｇに溶解し、さらにベンジルトリエチルアンモニウムク
ロライド０．２ｇを加え、減圧下（約１５０ｍｍＨ
ｇ）、４８％水酸化ナトリウム水溶液２２．３ｇを３時
間かけて滴下した。この間、生成する水はエピクロルヒ
ドリンとの共沸により系外に除き、溜出したエピクロル
ヒドリンは系内に戻した。滴下終了後、さらに３０分間
反応を継続した。その後、濾過により生成した塩を除
き、さらに水洗したのちエピクロルヒドリンを留去し、
エポキシ樹脂６６．７ｇを得た。エポキシ当量は２９１
であり、軟化点は６２℃であった。得られた樹脂のＧＰ
Ｃチャートを図１に示す。本樹脂を用い、フェノールノ
ボラック樹脂（荒川化学工業社製タマノル７５８）を硬
化剤として成形（１６０℃、３分）し、硬化試験片を得
た。試験片は１８０℃にて１２時間ポストキュアを行っ
た後、種々の物性試験に供した。結果を表２に示す。Example 2 55 g of the resin obtained in Example 1 was used for epichlorohydrin 330.
g of benzyltriethylammonium chloride, and 0.2 g of benzyltriethylammonium chloride was added thereto.
g) and 22.3 g of a 48% aqueous sodium hydroxide solution were added dropwise over 3 hours. During this time, generated water was removed from the system by azeotropic distillation with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was continued for another 30 minutes. Thereafter, salts produced by filtration were removed, and after further washing with water, epichlorohydrin was distilled off.
66.7 g of an epoxy resin was obtained. Epoxy equivalent is 291
And the softening point was 62 ° C. GP of the obtained resin
The C chart is shown in FIG. Using this resin, a phenol novolak resin (Tamanol 758, manufactured by Arakawa Chemical Industry Co., Ltd.) was molded (160 ° C., 3 minutes) as a curing agent to obtain a cured test piece. The test pieces were subjected to post-curing at 180 ° C. for 12 hours and then subjected to various physical property tests. Table 2 shows the results.
【００２１】比較例２ ｏ-クレゾールノボラック型エポキシ樹脂を使用し、実
施例２と同様に種々の物性試験に供した。結果を表２に
示す。Comparative Example 2 An o-cresol novolak type epoxy resin was used and subjected to various physical property tests in the same manner as in Example 2. Table 2 shows the results.
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【発明の効果】本発明により得られるフェノール性化合
物を出発原料とすることにより、高性能なエポキシ樹脂
を得ることができ、さらにはポリエステル、ポリカーボ
ネート等の高分子材料の開発が期待できる。By using the phenolic compound obtained by the present invention as a starting material, a high-performance epoxy resin can be obtained, and furthermore, development of a polymer material such as polyester and polycarbonate can be expected.
【図１】 実施例２で得られたエポキシ化合物のＧＰＣ
チャートFIG. 1 GPC of the epoxy compound obtained in Example 2
chart
Claims (4)
１〜６の炭化水素基を示し、ｎは０〜１５の整数を示
し、ｍは０〜２の整数を示す）で表されるフェノール性
化合物。[Claim 1] The following general formula (1) (Wherein, R 1 , R 2 , and R 3 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, n represents an integer of 0 to 15, and m represents an integer of 0 to 2) The phenolic compound represented by).
製造用の中間体である請求項１記載のフェノール性化合
物。2. The phenolic compound according to claim 1, wherein the phenolic compound is an intermediate for producing an epoxy compound.
が主成分である請求項１記載のフェノール性化合物。3. The phenolic compound according to claim 1, wherein a compound in which n is 0 in the general formula (1) is a main component.
基を示し、ｍは０〜２の整数を示す）で表されるフェノ
ール類と下記一般式（３） 【化３】 （但し、式中、Ｒ1、Ｒ2、Ｒ4は、水素原子又は炭素数
１〜６の炭化水素基を示す）で表される縮合剤とを、酸
触媒の存在下に、フェノール類と縮合剤とのモル比（縮
合剤／フェノール類）０．０１〜０．９の条件で反応さ
せることを特徴とする請求項１〜３のいずれかに記載の
フェノール性化合物の製造方法。4. The following general formula (2): (Where R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 0 to 2) and a phenol represented by the following general formula (3): (Wherein, R 1 , R 2 , and R 4 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) with a phenol in the presence of an acid catalyst. The method for producing a phenolic compound according to any one of claims 1 to 3, wherein the reaction is carried out at a molar ratio with the condensing agent (condensing agent / phenols) of 0.01 to 0.9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001006233A JP3403178B2 (en) | 2001-01-15 | 2001-01-15 | Phenolic compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001006233A JP3403178B2 (en) | 2001-01-15 | 2001-01-15 | Phenolic compound and method for producing the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24597898A Division JP3165678B2 (en) | 1991-10-30 | 1998-08-31 | Method for producing epoxy compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001200031A true JP2001200031A (en) | 2001-07-24 |
| JP3403178B2 JP3403178B2 (en) | 2003-05-06 |
Family
ID=18874150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001006233A Expired - Lifetime JP3403178B2 (en) | 2001-01-15 | 2001-01-15 | Phenolic compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3403178B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257120A (en) * | 2005-03-15 | 2006-09-28 | Asahi Organic Chem Ind Co Ltd | Manufacturing method of novolak resin |
-
2001
- 2001-01-15 JP JP2001006233A patent/JP3403178B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257120A (en) * | 2005-03-15 | 2006-09-28 | Asahi Organic Chem Ind Co Ltd | Manufacturing method of novolak resin |
| JP4653527B2 (en) * | 2005-03-15 | 2011-03-16 | 旭有機材工業株式会社 | Method for producing novolac resin |
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| Publication number | Publication date |
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| JP3403178B2 (en) | 2003-05-06 |
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