JPH0742277B2 - New heterocyclic ammonium salt - Google Patents
New heterocyclic ammonium saltInfo
- Publication number
- JPH0742277B2 JPH0742277B2 JP19165989A JP19165989A JPH0742277B2 JP H0742277 B2 JPH0742277 B2 JP H0742277B2 JP 19165989 A JP19165989 A JP 19165989A JP 19165989 A JP19165989 A JP 19165989A JP H0742277 B2 JPH0742277 B2 JP H0742277B2
- Authority
- JP
- Japan
- Prior art keywords
- ammonium salt
- formula
- alkyl
- compound
- hexafluoroantimonate
- 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 - Fee Related
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 本発明の背景 これまでカチオン重合し得るモノマーのカチオン重合反
応の開始剤としては、塩化アルミニウム等のフリーデル
クラフト触媒、三フッ化ホウ素ジエチルエーテル錯体、
光で開裂するオニウム塩（イオウ、セレン、テルル）ま
たはジアリルヨードニウム塩、熱的に開裂する芳香族ま
たは脂肪族スルホニウム塩などが知られている。これら
のうち熱的に開裂してカルボニウムカチオンを生じ得る
開始剤（熱潜在性カチオン開始剤）は、例えば一液型エ
ポキシ樹脂の硬化剤として使用すると常温では反応せ
ず、120℃以上のような高温において重合反応を開始さ
せるので、ポットライフおよび貯蔵安定性を向上させる
硬化剤として注目されている。特開昭58−37003および
同58−37004参照。しかしながらスルホニウム塩型開始
剤は副生するイオウ化合物が悪臭を発し、使用面で制約
を受ける。DETAILED DESCRIPTION OF THE INVENTION As an initiator of a cationic polymerization reaction of a monomer capable of undergoing cationic polymerization, Friedel-Crafts catalyst such as aluminum chloride, boron trifluoride diethyl ether complex,
Light-cleavable onium salts (sulfur, selenium, tellurium) or diallyliodonium salts, and thermally-cleavable aromatic or aliphatic sulfonium salts are known. Of these, initiators that can be thermally cleaved to generate carbonium cations (thermal latent cation initiators) do not react at room temperature when used as a curing agent for one-pack type epoxy resins, for example, at temperatures above 120 ° C. Since it initiates the polymerization reaction at extremely high temperatures, it has been attracting attention as a curing agent that improves pot life and storage stability. See JP-A-58-37003 and JP-A-58-37004. However, with the sulfonium salt type initiator, the sulfur compound produced as a by-product gives off a bad odor, which limits its use.
本発明者らの特願昭62−255388号は、悪臭を発生しない
熱潜在性カチオン開始剤としてベンジルピリジニウム塩
型化合物を開示している。ところがこれらのベンジルピ
リジニウム塩はその分解生成物が重合物（硬化物）を着
色する欠点がある。Japanese Patent Application No. 62-255388 of the present inventors discloses a benzylpyridinium salt type compound as a heat-latent cation initiator which does not generate a malodor. However, these benzylpyridinium salts have a drawback that their decomposition products color the polymer (cured product).
さらに省資源、省エネルギーの立場より、熱開裂温度の
低い開始剤の開発が望まれる。Further, from the standpoint of resource saving and energy saving, it is desired to develop an initiator having a low thermal cleavage temperature.
本発明者らは、１位と３位にそれぞれ酸素原子および窒
素原子を有する含窒素複素環化合物の第４級アンモニウ
ムがこれらの要望を満たすことを知った。本発明の開示 本発明は、式Ｉ の複素環式アンモニウム塩を提供する。The present inventors have found that the quaternary ammonium, which is a nitrogen-containing heterocyclic compound having an oxygen atom and a nitrogen atom at the 1- and 3-positions, respectively satisfies these needs. DISCLOSURE OF THE INVENTION The present invention provides compounds of formula I A heterocyclic ammonium salt of
式中、R1,R2はヒドロキシ、アルキル、アルコキシ、ハ
ロゲン、ニトロ、シアノもしくはアルキルアミノで置換
されていることもあるフェニル基、水素、アルキル、ま
たはアルケニルを表わし、 R3,R4はアルキル、アルケニルまたはフェニル（前記の
置換基で置換されていてもよい）を表わし、 R5,R6は水素、ヒドロキシ、アルキル、アルコキシ又は
フェニル（前記の置換基で置換されていても良い）を表
わし、 ＭはAs,Sb,BまたはＰを表わし、 Ｘはハロゲンを表わし、 ｍは１ないし４の整数を表わし、 ｎはＭがＢであるときは４であり、他の場合は６であ
る。In the formula, R 1 and R 2 represent a phenyl group which may be substituted with hydroxy, alkyl, alkoxy, halogen, nitro, cyano or alkylamino, hydrogen, alkyl or alkenyl, and R 3 and R 4 represent alkyl. , Alkenyl or phenyl (which may be substituted by any of the above substituents), R 5 and R 6 each represent hydrogen, hydroxy, alkyl, alkoxy or phenyl (which may be substituted by any of the above substituents). , M represents As, Sb, B or P, X represents halogen, m represents an integer of 1 to 4, n is 4 when M is B, and 6 in other cases.
本発明の化合物の基本骨格は、１位と３位とにそれぞれ
酸素原子および窒素原子を含む４員環ないし７員環の飽
和複素環、具体的には1,3−オキサゼチジン、オキサゾ
リジン、ペルヒドロ−1,3−オキサジンまたはペルヒド
ロ−1,3−オキサゼピンである。The basic skeleton of the compound of the present invention is a 4-membered to 7-membered saturated heterocycle containing an oxygen atom and a nitrogen atom at the 1- and 3-positions, specifically 1,3-oxazetidine, oxazolidine, and perhydro-. It is 1,3-oxazine or perhydro-1,3-oxazepine.
式Ｉの化合物は、例えば式II のω−２級アミノアルカノールに、式III R1COR2 （III） のアルデヒドまたはケトンを反応させ、式IV の複素環化合物とし、この化合物をR4Xの４級化剤にて
４級化して式Ｉの化合物に対応するアンモニウムハライ
ドとし、最後にこのハライド陰イオンをMXn-で交換する
ことによって製造することができる。すなわち式Ｉのア
ンモニウム塩に対応するアンモニウムハライドに、MXn
−イオンのアルカリ金属塩を反応させる。Compounds of formula I are for example compounds of formula II Ω-secondary aminoalkanol of formula III R 1 COR 2 (III) with an aldehyde or ketone of formula IV Which is obtained by quaternizing this compound with an R 4 X quaternizing agent to give an ammonium halide corresponding to the compound of formula I, and finally exchanging this halide anion with MXn −. be able to. That is, the ammonium halide corresponding to the ammonium salt of formula I
Reacting with alkali metal salts of ions.
式Ｉの化合物は、温度が上昇すると開裂し、下記反応に
よりHMXn-を放出し、カチオン重合を開始させることが
できる。分解生成物は悪臭を発することもなく、かつ硬
化物を着色することもないので、カチオン重合開始剤と
して既知のものよりすぐれている。The compounds of formula I are cleaved when the temperature rises, the following reaction HMXn - the release, it is possible to initiate cationic polymerization. Since the decomposition products do not give off a bad odor and do not color the cured product, they are superior to those known as cationic polymerization initiators.
しかしながら式Ｉの化合物は常温では殆ど不活性である
が、加熱して始めて開始剤としての機能を発揮するの
で、例えばエポキシ樹脂の硬化剤などその熱潜在性を利
用する用途に適している。 However, the compound of formula I is almost inactive at room temperature, but since it exhibits the function as an initiator only after heating, it is suitable for use in utilizing its thermal potential, for example, as a curing agent for epoxy resin.
実施例１ ２−フェニル−3,3−ジメチルオキサゾリジニウムヘキ
サフルオロアンチモネート ベンズアルデヒド10.6g（0.1モル）をベンゼン5gに溶解
し、２−ヒドロキシエチルメチルアミン7.5g（0.1モ
ル）を加え、還流下脱水縮合させた。反応はIRを追跡
し、3800cm-1のOH基の吸収がなくなるまで続けた。Example 1 2-Phenyl-3,3-dimethyloxazolidinium hexafluoroantimonate 10.6 g (0.1 mol) of benzaldehyde was dissolved in 5 g of benzene, 7.5 g (0.1 mol) of 2-hydroxyethylmethylamine was added, and the mixture was refluxed. Lower dehydration condensation was performed. The reaction was followed by IR and continued until there was no absorption of the OH group at 3800 cm -1 .
反応終了後ヨードメチル14.2g（0.1モル）を室温で滴下
し、２時間反応させた。その後反応混合物を水／エーテ
ルで抽出し、水層にヘキサフルオロアンチモン酸ナトリ
ウム25.9g（0.1モル）を加え、生成する白色沈澱を吸引
ロ過し、洗浄、乾燥して題記化合物を得た。After the reaction was completed, 14.2 g (0.1 mol) of iodomethyl was added dropwise at room temperature and the reaction was carried out for 2 hours. After that, the reaction mixture was extracted with water / ether, 25.9 g (0.1 mol) of sodium hexafluoroantimonate was added to the aqueous layer, and a white precipitate formed was suction filtered, washed and dried to obtain the title compound.
NMR:2.3ppm（S,3H,Me）,3.2ppm（s,3H,Me）,3.8−4.0pp
m（m,2H,CH2）,4.3−4.5ppm（m,2H,CH2）,5.9ppm（s,1
H,CH）,7.6ppm（s,5H,Ph） 実施例２ ２−（４−ニトロフェニル）−3,3−ジメチルオキサゾ
リジニウムヘキサフルオロアンチモネート 実施例１と同様の方法で、４−ニトロベンズアルデヒ
ド、ヒドロキシエチルメチルアミン、ヨードメチル、及
びヘキサフルオロアンチモン酸ナトリウムより表記化合
物を合成した。得られた化合物のNMRスペクトルは以下
のとおりであった。NMR: 2.3 ppm (S, 3H, Me), 3.2 ppm (s, 3H, Me), 3.8-4.0 pp
m (m, 2H, CH 2 ), 4.3-4.5ppm (m, 2H, CH 2), 5.9ppm (s, 1
H, CH), 7.6 ppm (s, 5H, Ph) Example 2 2- (4-Nitrophenyl) -3,3-dimethyloxazolidinium hexafluoroantimonate In the same manner as in Example 1, 4- The title compound was synthesized from nitrobenzaldehyde, hydroxyethylmethylamine, iodomethyl, and sodium hexafluoroantimonate. The NMR spectrum of the obtained compound was as follows.
2.7ppm（s,3H,Me）,3.2ppm（s,3H,Me）,4.0ppm（m,2H,C
H2）,4.4ppm（m,1H,CH2）,4.5ppm（m,1H,CH2）,6.1ppm
（s,1H,CH）,8.0ppm（d,2H,Ph）,8.4ppm（d,2H,Ph） 実施例３ ２−（２−ニトロフェニル）−3,3−ジメチルオキサゾ
リジニウムヘキサフルオロアンチモネート 実施例１と同様の方法で、２−ニトロベンズアルデヒ
ド、ヒドロキシエチルメチルアミン、ヨードメチル、及
びヘキサフルオロアンチモン酸ナトリウムより表記化合
物を合成した。得られた化合物のNMRスペクトルは以下
のとおりであった。2.7ppm (s, 3H, Me), 3.2ppm (s, 3H, Me), 4.0ppm (m, 2H, C
H 2 ), 4.4ppm (m, 1H, CH 2 ), 4.5ppm (m, 1H, CH 2 ), 6.1ppm
(S, 1H, CH), 8.0ppm (d, 2H, Ph), 8.4ppm (d, 2H, Ph) Example 3 2- (2-Nitrophenyl) -3,3-dimethyloxazolidinium hexafluoro Antimonate In the same manner as in Example 1, the title compound was synthesized from 2-nitrobenzaldehyde, hydroxyethylmethylamine, iodomethyl, and sodium hexafluoroantimonate. The NMR spectrum of the obtained compound was as follows.
2.7ppm（s,3H,Me）,3.2ppm（s,3H,Me）,4.0ppm（m,2H,C
H2）,4.4ppm（m,1H,CH2）,4.5ppm（m,1H,CH2）,6.1ppm
（s,1H,CH）,8.0−8.4ppm（m,4H,Ph） 実施例４ ２−（４−メトキシフェニル）−3,3−ジメチルオキサ
ゾリジニウムヘキサフルオロアンチモネート 実施例１と同様の方法で、４−メトキシベンズアルデヒ
ド、ヒドロキシエチルメチルアミン、ヨードメチル、及
びヘキサフルオロアンチモン酸ナトリウムより表記化合
物を合成した。得られた化合物のNMRスペクトルは以下
のとおりであった。2.7ppm (s, 3H, Me), 3.2ppm (s, 3H, Me), 4.0ppm (m, 2H, C
H 2 ), 4.4ppm (m, 1H, CH 2 ), 4.5ppm (m, 1H, CH 2 ), 6.1ppm
(S, 1H, CH), 8.0-8.4ppm (m, 4H, Ph) Example 4 2- (4-methoxyphenyl) -3,3-dimethyloxazolidinium hexafluoroantimonate Similar to Example 1. By a method, the title compound was synthesized from 4-methoxybenzaldehyde, hydroxyethylmethylamine, iodomethyl, and sodium hexafluoroantimonate. The NMR spectrum of the obtained compound was as follows.
2.6ppm（s,3H,MeO）,3.1ppm（s,3H,Me）,3.4ppm（s,3H,
Me）,3.9−4.1ppm（m,2H,CH2）,4.4−4.6ppm（m,2H,C
H2）,5.9ppm（s,1H,CH）,7.1−7.2ppm（d,2H,Ph）,7.5
−7.6ppm（d,2H,Ph） 実施例５ ２−（２−メトキシフェニル）−3,3−ジメチルオキサ
ゾリジニウムヘキサフルオロアンチモネート 実施例１と同様の方法で、２−メトキシベンズアルデヒ
ド、ヒドロキシエチルメチルアミン、ヨードメチル、及
びヘキサフルオロアンチモン酸ナトリウムより表記化合
物を合成した。得られた化合物のNMRスペクトルは以下
のとおりであった。2.6ppm (s, 3H, MeO), 3.1ppm (s, 3H, Me), 3.4ppm (s, 3H,
Me), 3.9-4.1ppm (m, 2H , CH 2), 4.4-4.6ppm (m, 2H, C
H 2 ), 5.9ppm (s, 1H, CH), 7.1-7.2ppm (d, 2H, Ph), 7.5
-7.6 ppm (d, 2H, Ph) Example 5 2- (2-Methoxyphenyl) -3,3-dimethyloxazolidinium hexafluoroantimonate In the same manner as in Example 1, 2-methoxybenzaldehyde and hydroxy were used. The title compound was synthesized from ethylmethylamine, iodomethyl, and sodium hexafluoroantimonate. The NMR spectrum of the obtained compound was as follows.
2.6ppm（s,3H,MeO）,3.1ppm（s,3H,Me）,3.4ppm（s,3H,
Me）,3.9−4.1ppm（m,2H,CH2）,4.4−4.6ppm（m,2H,C
H2）,5.8ppm（s,1H,CH）,7.3−7.6ppm（m,4H,Ph） 実施例６ ２−（ｔ−ブチル）−3.3−ジメチルオキサゾリジニウ
ムヘキサフルオロアンチモネート 実施例１と同様の方法で、ビバルアルデヒド、ヒドロキ
シエチルメチルアミン、ヨードメチル、及びヘキサフル
オロアンチモン酸ナトリウムより表記化合物を合成し
た。得られた化合物のNMRスペクトルは以下のとおりで
あった。2.6ppm (s, 3H, MeO), 3.1ppm (s, 3H, Me), 3.4ppm (s, 3H,
Me), 3.9-4.1ppm (m, 2H , CH 2), 4.4-4.6ppm (m, 2H, C
H 2 ), 5.8 ppm (s, 1H, CH), 7.3-7.6 ppm (m, 4H, Ph) Example 6 2- (t-butyl) -3.3-dimethyloxazolidinium hexafluoroantimonate Example 1 The title compound was synthesized from bivalaldehyde, hydroxyethylmethylamine, iodomethyl, and sodium hexafluoroantimonate in the same manner as in. The NMR spectrum of the obtained compound was as follows.
1.1ppm（s,9H,t−Bu）,3.1ppm（s,3H,Me）,3.3ppm（s,3
H,Me）,3.8ppm（m,2H,CH2）,4.2−4.3ppm（m,2H,CH2）,
4.5ppm（s,1H,CH） 実施例７ ２−エチル−3,3−ジメチルオキサゾリジニウムヘキサ
フルオロアンチモネート 実施例１と同様の方法で、プロピオンアルデヒド、ヒド
ロキシエチルメチルアミン、ヨードメチル、及びヘキサ
フルオロアンチモン酸ナトリウムより表記化合物を合成
した。得られた化合物のNMRスペクトルは以下のとおり
であった。1.1ppm (s, 9H, t-Bu), 3.1ppm (s, 3H, Me), 3.3ppm (s, 3
H, Me), 3.8ppm (m , 2H, CH 2), 4.2-4.3ppm (m, 2H, CH 2),
4.5 ppm (s, 1H, CH) Example 7 2-Ethyl-3,3-dimethyloxazolidinium hexafluoroantimonate In the same manner as in Example 1, propionaldehyde, hydroxyethylmethylamine, iodomethyl, and hexa The title compound was synthesized from sodium fluoroantimonate. The NMR spectrum of the obtained compound was as follows.
1.1ppm（t,3H,CH2−CH3）,1.8−2.0ppm（m,2H,CH2−C
H3）,3.1ppm（s,3H,Me）,3.5ppm（s,3H,Me）,3.8ppm
（m,2H,CH2）,4.2−4.3ppm（m,2H,CH2）,4.6−4.7ppm
（m,1H,CH） 1.1ppm (t, 3H, CH 2 -CH 3), 1.8-2.0ppm (m, 2H, CH 2 -C
H 3 ), 3.1ppm (s, 3H, Me), 3.5ppm (s, 3H, Me), 3.8ppm
(M, 2H, CH 2) , 4.2-4.3ppm (m, 2H, CH 2), 4.6-4.7ppm
(M, 1H, CH)
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０８Ｇ 59/68 ＮＫＭ 73/00 ＮＴＢ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location // C08G 59/68 NKM 73/00 NTB
Claims (1)
ロゲン、ニトロ、シアノもしくはアルキルアミノで置換
されていることもあるフェニル基、水素、アルキル、ま
たはアルケニルを表わし、 R3,R4はアルキル、アルケニルまたはフェニル（前記の
置換基で置換されていてもよい）を表わし、 R5,R6は水素、ヒドロキシ、アルキル、アルコキシ又は
フェニル（前記の置換基で置換されていても良い）を表
わし、 ＭはAs,Sb,BまたはＰを表わし、 Ｘはハロゲンを表わし、 ｍは１ないし４の整数を表わし、 ｎはＭがＢであるときは４であり、他の場合は６であ
る。1. A formula Heterocyclic ammonium salt of. In the formula, R 1 and R 2 represent a phenyl group which may be substituted with hydroxy, alkyl, alkoxy, halogen, nitro, cyano or alkylamino, hydrogen, alkyl or alkenyl, and R 3 and R 4 represent alkyl. , Alkenyl or phenyl (which may be substituted by any of the above substituents), R 5 and R 6 each represent hydrogen, hydroxy, alkyl, alkoxy or phenyl (which may be substituted by any of the above substituents). , M represents As, Sb, B or P, X represents halogen, m represents an integer of 1 to 4, n is 4 when M is B, and 6 in other cases.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19165989A JPH0742277B2 (en) | 1989-07-24 | 1989-07-24 | New heterocyclic ammonium salt |
| AU56126/90A AU627316B2 (en) | 1989-06-05 | 1990-05-31 | Antimony, arsenic, boron and phosphorous halide salts of quaternary ammonium compounds |
| CA002018173A CA2018173C (en) | 1989-06-05 | 1990-06-04 | Heat-latent, cationic polymerization initiator and resin compositions containing the same |
| KR1019900008291A KR0157622B1 (en) | 1989-06-05 | 1990-06-05 | A latent type cationic polymerization initiator and a resin composition containing the same |
| EP95100720A EP0651002A3 (en) | 1989-06-05 | 1990-06-05 | Latent heat initiator of cationic polymerization and resinous compositions containing it. |
| DE69030600T DE69030600T2 (en) | 1989-06-05 | 1990-06-05 | Heat latent, cationic polymerization initiator and resin compositions containing the same |
| EP90110649A EP0401770B1 (en) | 1989-06-05 | 1990-06-05 | Heat-latent, cationic polymerization initiator and resin composition containing the same |
| AU17227/92A AU640085B2 (en) | 1989-06-05 | 1992-05-28 | Antimony, arsenic, boron and phosphorous halide salts of oxazolidinium compounds and resin compositions containing the same |
| AU17228/92A AU640086B2 (en) | 1989-06-05 | 1992-05-28 | Antimony, arsenic, boron and phosphorous halide salts of pyridinium compounds and resin compositions containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19165989A JPH0742277B2 (en) | 1989-07-24 | 1989-07-24 | New heterocyclic ammonium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0356470A JPH0356470A (en) | 1991-03-12 |
| JPH0742277B2 true JPH0742277B2 (en) | 1995-05-10 |
Family
ID=16278326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19165989A Expired - Fee Related JPH0742277B2 (en) | 1989-06-05 | 1989-07-24 | New heterocyclic ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742277B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5402279B2 (en) | 2008-06-27 | 2014-01-29 | 株式会社リコー | Electrophotographic photoreceptor, method for producing the same, and image forming apparatus using the same |
| JP5553198B2 (en) | 2008-11-26 | 2014-07-16 | 株式会社リコー | Electrophotographic photoreceptor, image forming apparatus using the same, and process cartridge for image forming apparatus |
-
1989
- 1989-07-24 JP JP19165989A patent/JPH0742277B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0356470A (en) | 1991-03-12 |
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