JPH0356470A - Novel heterocyclic ammonium salt - Google Patents
Novel heterocyclic ammonium saltInfo
- Publication number
- JPH0356470A JPH0356470A JP19165989A JP19165989A JPH0356470A JP H0356470 A JPH0356470 A JP H0356470A JP 19165989 A JP19165989 A JP 19165989A JP 19165989 A JP19165989 A JP 19165989A JP H0356470 A JPH0356470 A JP H0356470A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- phenyl
- alkyl
- compound
- substituted
- 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.)
- Granted
Links
- -1 heterocyclic ammonium salt Chemical class 0.000 title claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 239000003999 initiator Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 150000001299 aldehydes Chemical class 0.000 abstract description 2
- 238000003776 cleavage reaction Methods 0.000 abstract description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 230000007017 scission Effects 0.000 abstract description 2
- 125000006193 alkinyl group Chemical group 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000010538 cationic polymerization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- RUWWNRBXWIYKAD-UHFFFAOYSA-N 1,3-oxazetidine Chemical compound C1NCO1 RUWWNRBXWIYKAD-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- UFTHEDBYLPFRDP-UHFFFAOYSA-N 5,6-dihydro-2h-oxazine Chemical compound C1CC=CNO1 UFTHEDBYLPFRDP-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 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
- 238000004134 energy conservation Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
生見里立宜量
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ξ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５８一３７００４参照．しかしながらスルホニ
ウム塩型開始剤は副生ずるイオウ化合物が悪臭を発し、
使用面で制約を受ける．
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ペンジルビリジ
ニウム塩型化合物を開示している．ところがこれらのペ
ンジルビ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．
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．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．婆ｌ通Ｂ凶糺天
本発明は、式■
（以下余白）
の複素環式アンモニウム塩を提供する．式中、Ｒ＋，Ｒ
ｚ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、
Ｒｓ，Ｒａ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、
ＲＳ，Ｒ．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
．
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、ベルヒドロー１．３−オキサジンまたはベル
ヒドロー１． ３−オキサゼビンである．
式Ｉの化合物は、例えば式■
のω−２級アξノアルカノールに、
式■
Ｒ．ＣＯＲ．
（ＩＩ）
のア−ルデヒドまたはケトンを反応させ、弐■
の複素環化合物とし、この化合物をＲ．Ｘの４級化剤に
て４級化して式■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一で交
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．
式■の化合物は、温度が上昇すると開裂し、下記反応に
よりＨＭＸｎ一を放出し、カチオン重合を開始させるこ
とができる．分解生戒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．
＋Ｒ ＩＣＯＨｔ ＋Ｈ”
＋ＭＸｎ−
しかしながら式■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
、例えばエボ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．実施例ｌ
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−’のＯＨ基の吸収が
なくなるまで続けた．
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．
ＮＭＲ：２．３ｐｐｍ （３．３Ｈ，Ｍｅ）． ３．２
ｐｐｍ （ｓ，３Ｈ，Ｍｅ），３．８−４．０ｐｐｍ
（ｍ，２Ｈ，ＣＨＩ ），４．３−４．５ｐｐｍ （ｍ
，２Ｈ，ＣＨｚ ）．５．９ｐｐｍ （ｓ，ＩＨ，ＣＨ
）．７．６ｐｐｍ （ｓ，５Ｈ，Ｐｈ）
実施例２
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ξ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
を合威した．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，ＣＨｚ ）．４．４ＰＰｍ （ｍ，ＩＨ，
ＣＨｔ ），４．５ｐｐｍ （ｍ，１Ｂ，ＣＨｚ ），
６．１ｐｐｍ （ｓ，ＩＨ，ＣＩ）＋＆Ｏｐｐｍ （ｄ
，２Ｈ，Ｐｈ）．８．４ｐｐｍ （ｄ，２Ｈ，Ｐｈ）
実施例３
二上
実施例ｌ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
を合威した．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）
，＆２ｐｐｍ （ｓ，３８，Ｍｅ）．４．０ｐｐｍ （
ｍ，２Ｈ，ＣＨ＊ ），４．４ｐｐｍ （ｍ，ＩＩ｛，
ＣＨｇ ），４．５Ｐｐｍ （ｍ，ＩＨ．ＣＨｔ ）．
６．１ｐｐｍ （ｓ，ＩＨ，ＣＨＬ８．０−８．４ｐｐ
ｍ （ｍ，４Ｈ，Ｐｈ）実施例４
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ξ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
物を合威した．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，Ｍｅ
ｎ）．３．１ｐｐｍ （ｓ，３Ｈ，Ｍｅ）．３．４ｐｐ
ｍ （ｓ，３Ｈ，Ｍｅ），３．９ ４．１ｐｐｍ （
ｍ，２Ｈ，ＣＨｚ ），４．４−４．６ｐｐｍ （ｍ
，２Ｈ，Ｃ｝ｌｘ ）．５．９ｐｐｍ （ｓ．ＩＨ，Ｃ
｝Ｉ）．７．１−７．２ｐｐｍ （ｄ．２Ｈ，Ｐｈ）．
７．５−７．６ｐｐｍ （ｄ，２Ｈ，Ｐｈ）実施例５
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
物を合威した．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，Ｍｅ
ｎ），３．１ ｐｐｍ （ｓ，３Ｈ，Ｍｅ）．３．４ｐ
ｐｍ （ｓ，３Ｈ，Ｍｅ），３．９ ４．ＩＰｐｍ
（ｍ，２Ｈ，ＣＨｚ ），４．４−４．６ｐｐｍ （ｍ
，２Ｈ，ＣＨｚ ），５．８ｐｐｍ （ｓ，ＩＨ，ＣＨ
）．７．３−７．６ｐｐｍ （ｍ．４Ｈ，Ｐｈ）
実施例６
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ξ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威した
．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，３｝１，Ｍｅ），３．３ｐｐｍ （ｓ，３Ｈ，Ｍ
ｅ），３．８ Ｐ Ｐｍ （ｍ， ２ Ｈ． ＣＨ！
） ． ４．２−４．３ Ｐｐｍ （ｍ，２Ｈ，ＣＨ
ｚ ）．４．５ｐｐｍ （ｓ，ＩＨ，ＣＨ）
実施例７
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威
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．１．１ ＰＰｍ （ｔ，３Ｈ，ＣＨ＊
Ｃ旦ｋ） ，１− ８−２．０ｐｐｍ （ｍ，２Ｈ，Ｃ
旦．−ｃＨ＊ ），３．１ｐｐｍ （ｓ，３Ｈ，Ｍｅ）
．３．５ｐｐｍ （ｓ，３Ｈ，Ｍｅ），３．８ｐｐｍ
（ｍ，２Ｈ，ＣＨｚ ），４．２−４．３ｐｐｍ （ｍ
，２Ｈ，ＣＨｚ ），４．６−４．７ｐｐｍ （ｍ，Ｉ
Ｈ，ＣＨ）[Detailed Description of the Invention] As an initiator for the cationic polymerization reaction of monomers capable of cationic polymerization, Friedel-Crafts catalysts such as aluminum ξium chloride, boron trifluoride diethyl ether complex,
Photo-cleavable onium salts (sulfur, selenium, tellurium) or diallyliodonium salts, thermally cleavable aromatic or aliphatic sulfonium salts, etc. are known. Among these, initiators that can be thermally cleaved to produce carbonium cations (thermally latent cation initiators) do not react at room temperature when used as curing agents for one-component epoxy resins, but at temperatures above 120°C. Because it initiates the polymerization reaction at high temperatures, it is attracting attention as a curing agent that improves pot life and storage stability. Japanese Patent Publication No. 58-37003
See also 58-37004. However, with sulfonium salt type initiators, the sulfur compounds produced as by-products emit a foul odor.
There are restrictions on usage. Japanese Patent Application No. 62-255388 by the present inventors discloses a penzylpyridinium salt type compound as a heat-latent cationic initiator that does not generate a bad odor. However, these pendylpyridinium salts have the disadvantage that their decomposition products color the polymer (cured product). Furthermore, from the standpoint of resource and energy conservation, it is desirable to develop an initiator with a low thermal cleavage temperature. The inventors have determined that the 1st and 3rd place
It was found that quaternary ammonium, a nitrogen-containing heterocyclic compound having oxygen and nitrogen atoms at the respective positions, satisfies these needs. The present invention provides a heterocyclic ammonium salt of the formula (hereinafter referred to as the blank). In the formula, R+, R
z represents a phenyl group, hydrogen, alkyl or alkenyl which may be substituted with hydroxy, alkyl, alkoxy, halogen, nitro, cyano or alkylamino; Rs, Ra represent alkyl, alkenyl or phenyl (the above substituents ), and RS, R. is hydrogen, hydroxy, alkyl, alkoxy or phenyl (optionally substituted with the above substituents)
, M represents As, Sb, B or P, X represents halogen, m represents an integer from 1 to 4, n is 4 when M is B, and 6 in other cases. be. The basic skeleton of the compound of the present invention is a 4- to 7-membered saturated heterocyclic ring containing an oxygen atom and a nitrogen atom at the 1st and 3rd positions, respectively, specifically 1,3-oxazetidine, oxazolidine, and berhydro-1. .3-Oxazine or Berhydro1. It is 3-oxazevin. The compound of formula I can be, for example, an ω-secondary anoξnoalkanol of formula (1), a compound of formula (1) R. COR. (II) is reacted with the aldehyde or ketone to form the heterocyclic compound (II), and this compound is converted into R. It can be produced by quaternizing X with a quaternizing agent to form an ammonium halide corresponding to the compound of formula (1), and finally exchanging this halide anion with MXn. That is, an ammonium halide corresponding to the ammonium salt of formula I is reacted with an alkali metal salt of MXn- ion. The compound of formula (1) cleaves when the temperature rises, releases HMXn through the reaction described below, and can initiate cationic polymerization. Decomposition products do not emit bad odors and do not color the cured product, so they are superior to known cationic polymerization initiators. +R ICOHt +H" +MXn- However, although the compound of formula (■) is almost inactive at room temperature, it only exhibits its function as an initiator when heated, so it can be used in applications that utilize its thermal latent properties, such as as a curing agent for epoxy resins. Example 1 10.6 g (0.1 mol) of benzaldehyde is dissolved in 5 g of benzene and 7.2 g of 2-hydroxyethylmethylamine is dissolved.
5 g (0.1 mol) was added and dehydration condensation was carried out under reflux. The reaction was followed by IR and continued until the absorption of the OH group at 3800 cm-' disappeared. After the reaction was completed, 14.2 g (0.1 mol) of iodomethyl was added dropwise at room temperature, and the mixture was allowed to react for 2 hours. Thereafter, the reaction mixture was extracted with water/ether, 25.9 g (0.1 mol) of sodium hexafluoroantimonate was added to the aqueous layer, and the white precipitate formed was filtered under suction, washed, and dried to obtain the title compound. Ta. NMR: 2.3ppm (3.3H, Me). 3.2
ppm (s,3H,Me), 3.8-4.0ppm
(m, 2H, CHI), 4.3-4.5ppm (m
, 2H, CHz). 5.9ppm (s, IH, CH
). 7.6 ppm (s, 5H, Ph) Example 2 In the same manner as in Example 1, the title compound was synthesized from 4-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, CHz). 4.4PPm (m, IH,
CHt), 4.5ppm (m, 1B, CHz),
6.1ppm (s, IH, CI) + & Oppm (d
, 2H, Ph). 8.4 ppm (d, 2H, Ph) Example 3 The title compound was synthesized from 2-nitrobenzaldehyde, hydroxyethylmethylamine, iodomethyl, and sodium hexafluoroantimonate in the same manner as in Example 1 above. The NMR spectrum of the obtained compound was as follows. 2.7ppm (s, 3H, Me)
, &2ppm (s, 38, Me). 4.0ppm (
m,2H,CH*),4.4ppm (m,II{,
CHg), 4.5Ppm (m, IH.CHt).
6.1ppm (s, IH, CHL8.0-8.4pp
m (m,4H,Ph) Example 4 In the same manner as in Example 1, 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,Me
n). 3.1ppm (s, 3H, Me). 3.4pp
m (s, 3H, Me), 3.9 4.1 ppm (
m, 2H, CHz), 4.4-4.6ppm (m
,2H,C}lx). 5.9ppm (s.IH,C
}I). 7.1-7.2ppm (d.2H, Ph).
7.5-7.6ppm (d,2H,Ph) Example 5 The title compound was synthesized from 2-methoxybenzaldehyde, hydroxyethylmethylamine, iodomethyl, and sodium hexafluoroantimonate in the same manner as in Example 1. did. The NMR spectrum of the obtained compound was as follows. 2.6ppm (s,3H,Me
n), 3.1 ppm (s, 3H, Me). 3.4p
pm (s, 3H, Me), 3.9 4. IPpm
(m, 2H, CHz), 4.4-4.6ppm (m
, 2H, CHz), 5.8ppm (s, IH, CH
). 7.3-7.6ppm (m.4H, Ph) Example 6 In the same manner as in Example 1, the title compound was synthesized from bivalaldehyde, hydroxyethylmethylamine, iodomethyl, and sodium hexafluoroantimonate. It was intimidating. The NMR spectrum of the obtained compound was as follows. 1.1ppm (s, 9H, t-Bu). 3.1ppm
(s,3}1,Me),3.3ppm (s,3H,M
e), 3.8 P Pm (m, 2 H. CH!
)． 4.2-4.3 Ppm (m, 2H, CH
z). 4.5 ppm (s, IH, CH) Example 7 In the same manner as in Example 1, the title compound was synthesized from propionaldehyde, hydroxyethylmethylamine, iodomethyl, and sodium hexafluoroantimonate. The NMR spectrum of the obtained compound was as follows. 1.1 PPm (t, 3H, CH*
C) ,1-8-2.0ppm (m,2H,C
Dan. -cH*), 3.1ppm (s,3H,Me)
．． 3.5ppm (s, 3H, Me), 3.8ppm
(m, 2H, CHz), 4.2-4.3ppm (m
, 2H, CHz), 4.6-4.7ppm (m, I
H, CH)
Claims (1)
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、 Ｒ＿３、Ｒ＿４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、 Ｒ＿５、Ｒ＿６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
。[Claims] A heterocyclic ammonium salt of the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. In the formula, R_1, R_2 represent a phenyl group, hydrogen, alkyl, or alkenyl which may be substituted with hydroxy, alkyl, alkoxy, halogen, nitro, cyano or alkylamino, and R_3, R_4 represent alkyl, alkenyl or phenyl. (which may be substituted with the above substituents), R_5 and R_6 represent hydrogen, hydroxy, alkyl, alkoxy or phenyl (which may be substituted with the above substituents), M is As, Sb , B or P, X represents halogen, m represents an integer from 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 |
| DE69030600T DE69030600T2 (en) | 1989-06-05 | 1990-06-05 | Heat latent, cationic polymerization initiator and resin compositions containing the same |
| EP95100720A EP0651002A3 (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 |
| KR1019900008291A KR0157622B1 (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 true JPH0356470A (en) | 1991-03-12 |
| JPH0742277B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8178266B2 (en) | 2008-06-27 | 2012-05-15 | Ricoh Company, Ltd. | Electrophotographic photoreceptor, image forming apparatus using the electrophotographic photoreceptor, and method of producing electrophotographic photoreceptor |
| US8568945B2 (en) | 2008-11-26 | 2013-10-29 | Ricoh Company, Ltd. | Electrophotographic photoreceptor, and image forming apparatus and process cartridge therefor using the photoreceptor |
-
1989
- 1989-07-24 JP JP19165989A patent/JPH0742277B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8178266B2 (en) | 2008-06-27 | 2012-05-15 | Ricoh Company, Ltd. | Electrophotographic photoreceptor, image forming apparatus using the electrophotographic photoreceptor, and method of producing electrophotographic photoreceptor |
| US8568945B2 (en) | 2008-11-26 | 2013-10-29 | Ricoh Company, Ltd. | Electrophotographic photoreceptor, and image forming apparatus and process cartridge therefor using the photoreceptor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0742277B2 (en) | 1995-05-10 |
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