JPH0459314B2 - - Google Patents
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- Publication number
- JPH0459314B2 JPH0459314B2 JP61131105A JP13110586A JPH0459314B2 JP H0459314 B2 JPH0459314 B2 JP H0459314B2 JP 61131105 A JP61131105 A JP 61131105A JP 13110586 A JP13110586 A JP 13110586A JP H0459314 B2 JPH0459314 B2 JP H0459314B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- curing
- compounds
- temperature
- compound represented
- 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.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 11
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 amine compounds Chemical class 0.000 description 7
- 229960004050 aminobenzoic acid Drugs 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MBDUKNCPOPMRJQ-UHFFFAOYSA-N 4-amino-2-chlorobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(Cl)=C1 MBDUKNCPOPMRJQ-UHFFFAOYSA-N 0.000 description 1
- NHFKECPTBZZFBC-UHFFFAOYSA-N 4-amino-3-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1N NHFKECPTBZZFBC-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、自己硬化型エポキシ化合物に関す
る。本発明のエポキシ化合物は、成形加工性が良
く、かつ耐熱性の優れた構造材料、炭素繊維複合
材用マトリツクス樹脂、接着剤、封止剤、粉体塗
料用樹脂として有用である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to self-curing epoxy compounds. The epoxy compound of the present invention is useful as a structural material with good moldability and excellent heat resistance, a matrix resin for carbon fiber composites, an adhesive, a sealant, and a resin for powder coatings.
従来のエポキシ化合物は、硬化剤（例えばアミ
ン化合物、カルボン酸化合物、無水カルボン酸化
合物、イミダゾール系化合物、フエノール化合物
及び三フツ化ホウ素化合物等）との反応によつて
良好な硬化物を得ることができる。
Conventional epoxy compounds can be used to obtain good cured products through reaction with curing agents (e.g., amine compounds, carboxylic acid compounds, carboxylic anhydride compounds, imidazole compounds, phenol compounds, boron trifluoride compounds, etc.). can.
しかしエポキシ化合物を構造材料、複合材用マ
トリツクス樹脂、接着剤、封止剤及び粉体塗料用
樹脂として利用するためには、上記の様な硬化剤
との混合が必要であつた。
However, in order to utilize epoxy compounds as structural materials, matrix resins for composite materials, adhesives, sealants, and resins for powder coatings, it has been necessary to mix them with the above-mentioned curing agents.
本発明者等は、硬化剤と混合することなく硬化
し、かつ保存安定性の良い自己硬化型エポキシ化
合物の合成を検討して次記一般式〔〕で示され
るエポキシ化合物が上記の目的を十分に達成する
ことを見い出し、本発明を完成するに至つた。即
ち、本発明は一般式〔〕で示される自己硬化型
エポキシ化合物を提供するものである。
The present inventors investigated the synthesis of a self-curing epoxy compound that cures without mixing with a curing agent and has good storage stability, and found that an epoxy compound represented by the following general formula [] sufficiently satisfies the above purpose. The present inventors have discovered that this can be achieved, and have completed the present invention. That is, the present invention provides a self-curing epoxy compound represented by the general formula [].
〔式中、ＲはＨ又は−CH3，ＸはＨ，−CH3，−
Ｏ−CH3又はハロゲン原子を表す〕
上記の一般式〔〕で示されるエポキシ化合物
は、次記一般式〔〕で示されるアルデヒド化合
物と次記一般式〔〕で示されるアミン化合物の
縮合反応により合成される。 [Wherein, R is H or -CH 3 , X is H, -CH 3 , -
represents O-CH 3 or a halogen atom] The epoxy compound represented by the above general formula [] is produced by the condensation reaction of an aldehyde compound represented by the following general formula [] and an amine compound represented by the following general formula []. be synthesized.
〔式中、ＲはＨ又は−CH3，ＸはＨ，−CH3，−
Ｏ−CH3又はハロゲン原子を表す〕
前記一般式〔〕で示されるアルデヒド化合物
は、ｐ−ヒドロキシベンズアルデヒド又は置換基
を有するｐ−ヒドロキシベンズアルデヒド〔例え
ばｐ−ヒドロキシベンズアルデヒド、バニリン
等〕をエポキシ化することによつて合成される。 [Wherein, R is H or -CH 3 , X is H, -CH 3 , -
represents O-CH 3 or a halogen atom] The aldehyde compound represented by the above general formula [] can be obtained by epoxidizing p-hydroxybenzaldehyde or p-hydroxybenzaldehyde having a substituent [e.g. p-hydroxybenzaldehyde, vanillin, etc.] synthesized by
前記一般式〔〕で示されるアミン化合物は、
ｐ−アミノ安息香酸又は置換基を有するｐ−アミ
ノ安息香酸〔例えばｐ−アミノ安息香酸、４−ア
ミノ−３−メチル安息香酸、４−アミノ−２−ク
ロル安息酸等〕である。 The amine compound represented by the general formula [] is
p-aminobenzoic acid or p-aminobenzoic acid having a substituent (for example, p-aminobenzoic acid, 4-amino-3-methylbenzoic acid, 4-amino-2-chlorobenzoic acid, etc.).
エポキシ化反応及び縮合反応は、すでに公知で
ある。例えば、
エポキシ化反応：ヘンリー リー等著ハンドブ
ツクオブエポキシレジンズ（Handbook of
Epoxy Resins）、第２章1967年米国マクグロウー
ヒルブツクカンパニー刊に、に開示されている。 Epoxidation reactions and condensation reactions are already known. For example, epoxidation reaction: Handbook of Epoxy Resins by Henry Lee et al.
Epoxy Resins), Chapter 2, published by McGraw-Hill Book Company, USA, 1967.
縮合反応：新実験化学講座14〔有機化合物の合
成と反応（）〕、ｐ−1410又はL.Strze lecki，
L.Liebert，ブレテインソシエヘミ−フランス
（Bulletin de la Societe Chmique de France），
605〜608（1973）等に開示されている。 Condensation reaction: New experimental chemistry course 14 [Synthesis and reaction of organic compounds ()], p-1410 or L.Strze lecki,
L. Liebert, Bulletin de la Societe Chmique de France,
605-608 (1973), etc.
詳しくは、例えば、
エポキシ化方法には、(1)アルカリを用いて付加
反応と脱ハロゲン化水素反応とを一挙に行なわせ
る一段法と、(2)第四級アンモニウム塩等の触媒を
使用して、まず50〜150℃の温度で付加反応を行
なわせ、次いでアルカリで35〜80℃の温度で脱ハ
ロゲン化水素反応を行なわせる二段法とがある
が、収率および製品の品質等の点からして後者の
二段法が好ましい。 In detail, for example, the epoxidation method includes (1) a one-step method in which an alkali is used to perform the addition reaction and dehydrohalogenation reaction at once, and (2) a catalyst such as a quaternary ammonium salt is used. There is a two-step method in which an addition reaction is first carried out at a temperature of 50 to 150°C, and then a dehydrohalogenation reaction is carried out with an alkali at a temperature of 35 to 80°C. From this point of view, the latter two-stage method is preferable.
反応は、一段法では、例えば過剰量のエピロヒ
ドリンに溶解した原料に、100〜150℃の温度でア
ルカリの水溶液を徐々に0.5〜２時間かけて、か
つ、反応系内の水はエピハロヒドリンと共沸させ
て系外へ除去しつつ滴下を行うことにより行われ
る。 The reaction can be carried out in a one-step method, for example, by gradually adding an aqueous alkali solution to the raw material dissolved in an excess amount of epihalohydrin at a temperature of 100 to 150°C for 0.5 to 2 hours, and the water in the reaction system is azeotropic with the epihalohydrin. This is carried out by dropping the liquid while removing it from the system.
二段法では、原料および過剰量のエピハロヒド
リンを第四級アンモニウム塩等の触媒存在下で１
〜４時間、エピハロヒドリンを還流させて付加反
応を行つた後、40〜70℃まで反応系の温度を下
げ、生成水がエピハロヒドリンと共沸する減圧下
（150mmHg〜400mmHg）でアルカリの水溶液を滴
下して閉環反応を行う。 In the two-step process, raw materials and an excess amount of epihalohydrin are treated in the presence of a catalyst such as a quaternary ammonium salt.
After carrying out the addition reaction by refluxing the epihalohydrin for ~4 hours, the temperature of the reaction system was lowered to 40 to 70°C, and an aqueous alkali solution was added dropwise under reduced pressure (150 mmHg to 400 mmHg) so that the produced water was azeotropic with the epihalohydrin. to perform the ring-closing reaction.
生成物は、副生する食塩を別し、反応溶液の
水洗をくり返し、過剰のエピハロヒドリンを揮発
させることによつて得られる。 The product is obtained by separating the by-produced common salt, repeatedly washing the reaction solution with water, and volatilizing excess epihalohydrin.
又、縮合反応方法は、化合物〔〕と化合物
〔〕の同モル量をメタノール、エタノール、ア
セトン又はテトラヒドロフランなどの溶媒中又は
酸触媒（例えばｐ−トルエンスルホン酸、ベンゼ
ンスルホン酸等）を加えてベンゼン、トルエン、
キシレン、クロロホルム及びジクロルエタン等の
溶媒中で撹拌しつつ脱水縮合する。 In addition, the condensation reaction method involves mixing the same molar amounts of compound [] and compound [] in a solvent such as methanol, ethanol, acetone, or tetrahydrofuran, or by adding an acid catalyst (e.g., p-toluenesulfonic acid, benzenesulfonic acid, etc.) to react with benzene. ,toluene,
Dehydration condensation is carried out with stirring in a solvent such as xylene, chloroform and dichloroethane.
上記の方法で合成される本発明の自己硬化型エ
ポキシ化合物〔〕は、室温では結晶質であり、
硬化触媒を加えることなく溶融温度まで加熱する
だけで硬化反応が進み30分〜60分で完全に硬化す
る。また室温状態では、ほとんど硬化反応が起ら
ず長期の保存が可能である。 The self-curing epoxy compound of the present invention synthesized by the above method is crystalline at room temperature,
The curing reaction proceeds simply by heating to the melting temperature without adding a curing catalyst, and it is completely cured in 30 to 60 minutes. Further, at room temperature, almost no curing reaction occurs and long-term storage is possible.
さらに本発明の自己硬化型エポキシ化合物に
は、必要に応じて可塑型、有機溶剤、反応性希釈
剤、増量剤、充てん剤、補強剤、顔料、難燃化
剤、増粘剤及び可撓性付与剤等の種々の添加剤を
配合することができる。 Furthermore, the self-curing epoxy compound of the present invention may optionally contain a plasticizer, an organic solvent, a reactive diluent, an extender, a filler, a reinforcing agent, a pigment, a flame retardant, a thickener, and a flexibilizer. Various additives such as imparting agents can be blended.
以下に実施例をあげてさらに具体的な説明をす
るが、これらの実施例は例示であり、本発明は実
施例によつて制限されるものでない。
A more specific explanation will be given below with reference to Examples, but these Examples are merely illustrative and the present invention is not limited by the Examples.
グリシジルエーテルの製造例
例 １
温度計、冷却器、撹拌装置を装備した500mlの
四つ口フラスコ内に、ｐ−ヒドロキシベンズアル
デヒド30ｇ、エピクロルヒドリン364ｇ、塩化テ
トラエチルアンモニウム0.6ｇを仕込み、油浴中
でエピクロルヒドリンを２時間還流させて付加反
応を行つた。Example of production of glycidyl ether 1 In a 500 ml four-necked flask equipped with a thermometer, condenser, and stirrer, 30 g of p-hydroxybenzaldehyde, 364 g of epichlorohydrin, and 0.6 g of tetraethylammonium chloride were charged, and the epichlorohydrin was heated in an oil bath. The mixture was refluxed for 2 hours to carry out the addition reaction.
その後、反応器の温度を60℃迄下げ、水分離器
および滴下装置をとりつけ、50％水酸化ナトリウ
ム水溶液21.6ｇを滴下装置より１時間滴下した。 Thereafter, the temperature of the reactor was lowered to 60°C, a water separator and a dropping device were attached, and 21.6 g of a 50% aqueous sodium hydroxide solution was added dropwise from the dropping device for 1 hour.
この間、反応系の温度が50〜70℃を維持する様
に減圧度を調整しながら生成水および添加水をエ
ピクロルヒドリンとともに共沸除去し、共沸物よ
り水を分離したエピクロルヒドリンは連続的に反
応系内に戻した。 During this time, the produced water and added water are azeotropically removed together with epichlorohydrin while adjusting the degree of vacuum so that the temperature of the reaction system is maintained at 50 to 70°C. I put it back inside.
滴下終了後、更に２時間反応を断続し、系内の
水を完全に除去して閉環反応を完結させた。次い
で系を室温まで冷却した後、副生する食塩を別
し、液を水洗した後、過剰のエピクロルヒドリ
ンを減圧下気発させて乾燥し次式で示される暗赤
色の液体39ｇ（収率89％）を得た。 After the dropwise addition was completed, the reaction was continued for another 2 hours to completely remove the water in the system and complete the ring-closing reaction. Next, the system was cooled to room temperature, the by-product salt was separated, the liquid was washed with water, and the excess epichlorohydrin was evaporated under reduced pressure and dried to obtain 39 g of a dark red liquid (yield: 89%) represented by the following formula. ) was obtained.
例 ２
ｐ−ヒドロキシベンズアルデヒドの代りにバニ
リンを用いた以外は、例１と同じ操作を行ない次
式で示されるグリシジルエーテルを得た。 Example 2 A glycidyl ether represented by the following formula was obtained by carrying out the same operation as in Example 1, except that vanillin was used instead of p-hydroxybenzaldehyde.
実施例 １
温度計、冷却器、撹拌装置を装備した500ml四
ツ口フラスコにメタノール300mlと例１で合成し
たグリシジルエーテル23.2ｇを入れ完全に溶解さ
せた。次にｐ−アミノ安息香酸17.9ｇを加え40℃
で４時間撹拌しつつ反応させた。出析した沈殿物
を過、メタノール洗浄を行い乾燥して次式で示
される化合物28.4ｇ（収率＝73.4％）を得た。 Example 1 300 ml of methanol and 23.2 g of the glycidyl ether synthesized in Example 1 were placed in a 500 ml four-necked flask equipped with a thermometer, a condenser, and a stirrer and completely dissolved. Next, 17.9 g of p-aminobenzoic acid was added and heated to 40°C.
The mixture was reacted with stirring for 4 hours. The precipitate was filtered, washed with methanol, and dried to obtain 28.4 g of a compound represented by the following formula (yield: 73.4%).
この化合物のホツトプレートによる溶融温度は
193℃であり、NMRスペクトル（第１図）に示
すようにグリシジル基及びカルボキシル基が確認
された。また、10℃／分の加熱速度のDSC測定
より195℃付近から発熱が観察されこの温度より
硬化反応が進むことが確認された。なお、NMR
スペクトルの基準物質にはヘキサメチルジシロキ
サン（HADSO）を用いた。 The melting temperature of this compound on a hot plate is
The temperature was 193°C, and glycidyl groups and carboxyl groups were confirmed as shown in the NMR spectrum (Figure 1). Further, through DSC measurement at a heating rate of 10°C/min, heat generation was observed at around 195°C, confirming that the curing reaction progressed from this temperature. In addition, NMR
Hexamethyldisiloxane (HADSO) was used as the reference substance for the spectrum.
実施例 ２
例２で合成したグリシジルエーテル10.0ｇとｐ
−アミノ安息香酸６、７ｇを用いた以外は実施例
１と同じ操作を行い、次式の化合物を得た。Example 2 10.0 g of glycidyl ether synthesized in Example 2 and p
The same operation as in Example 1 was performed except that 6 or 7 g of -aminobenzoic acid was used to obtain a compound of the following formula.
溶融温度は220℃であり、NMRスペクトル
（第２図）よりグリシジル基及びカルボキシル基
を確認した。DSC測定より223℃付近から硬化発
熱が観察された。 The melting temperature was 220°C, and glycidyl groups and carboxyl groups were confirmed from the NMR spectrum (Figure 2). Curing heat generation was observed from around 223°C by DSC measurement.
実施例 ３
例１で合成したグリシジルエーテル11.8ｇと４
−アミノ−３−メチル安息香酸10.0ｇを用いた以
外は実施例１と同じ操作を行い、次式の化合物を
得た。Example 3 11.8 g of glycidyl ether synthesized in Example 1 and 4
The same operation as in Example 1 was performed except that 10.0 g of -amino-3-methylbenzoic acid was used to obtain a compound of the following formula.
溶融温度は206℃であり、NMRスペクトル
（第３図）よりグリシジル基及びカルボキシル基
を確認した。第４図のDSC測定より208℃付近か
ら硬化発熱が観察された。 The melting temperature was 206°C, and glycidyl groups and carboxyl groups were confirmed from the NMR spectrum (Figure 3). According to the DSC measurement shown in FIG. 4, curing heat generation was observed at around 208°C.
第１〜３図はそれぞれ実施例１〜３で得られた
化合物のNMRスペクトル（溶媒DMSO）を示す
図である。第４図は実施例１〜３で得られた化合
物のDSC測定結果について温度軸をそろえて、
それぞれのパターン（１：実施例１、２：実施例
２、３：実施例３）を示した図である。
1 to 3 are diagrams showing NMR spectra (solvent: DMSO) of the compounds obtained in Examples 1 to 3, respectively. Figure 4 shows the DSC measurement results of the compounds obtained in Examples 1 to 3 with the temperature axes aligned.
It is a figure showing each pattern (1: Example 1, 2: Example 2, 3: Example 3).
Claims (1)
OCH3又はハロゲン原子を表す〕 で示されるエポキシ化合物。[Claims] 1. General formula [Wherein, R is H or -CH 3 , X is H, -CH 3 , -
represents OCH 3 or a halogen atom] An epoxy compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61131105A JPS62289572A (en) | 1986-06-07 | 1986-06-07 | Self-curing epoxy compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61131105A JPS62289572A (en) | 1986-06-07 | 1986-06-07 | Self-curing epoxy compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62289572A JPS62289572A (en) | 1987-12-16 |
| JPH0459314B2 true JPH0459314B2 (en) | 1992-09-21 |
Family
ID=15050093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61131105A Granted JPS62289572A (en) | 1986-06-07 | 1986-06-07 | Self-curing epoxy compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62289572A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020225884A1 (en) * | 2019-05-08 | 2020-11-12 | 昭和電工マテリアルズ株式会社 | Resin particle mixture |
-
1986
- 1986-06-07 JP JP61131105A patent/JPS62289572A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62289572A (en) | 1987-12-16 |
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