JP2519480B2 - New benzylpyridinium salt - Google Patents
New benzylpyridinium saltInfo
- Publication number
- JP2519480B2 JP2519480B2 JP62255388A JP25538887A JP2519480B2 JP 2519480 B2 JP2519480 B2 JP 2519480B2 JP 62255388 A JP62255388 A JP 62255388A JP 25538887 A JP25538887 A JP 25538887A JP 2519480 B2 JP2519480 B2 JP 2519480B2
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- JP
- Japan
- Prior art keywords
- mol
- formula
- added
- chloride
- new
- 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
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- Pyridine Compounds (AREA)
- Polymerization Catalysts (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。Description: BACKGROUND OF THE INVENTION As an initiator of the cationic polymerization reaction of a monomer capable of undergoing cationic polymerization, Friedel-Crafts catalyst such as aluminum chloride, boron trifluoride diethyl ether complex, photocleavable onium Salts (sulfur, selenium, tellurium) or diallyliodonium salts, thermally cleaved aromatic or aliphatic sulfonium salts, etc. 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.
そこで本発明は、このような欠点のない熱潜在性カチ
オン重合開始剤として使用し得る新規なベンジルピリジ
ニウム塩を提供することを課題とする。Therefore, it is an object of the present invention to provide a novel benzylpyridinium salt that can be used as a thermal latent cationic polymerization initiator without such drawbacks.
本発明の開示 本発明は、式Ｉ のベンジルピリジニウム塩を提供する。DISCLOSURE OF THE INVENTION The present invention provides compounds of formula I Benzylpyridinium salt of
式中、Ｒ1,R2およびＲ3は水素、ハロゲン、アルキ
ル、アルコキシ、ニトロ、アミノ、またはヒドロキシで
ある。Wherein R 1 , R 2 and R 3 are hydrogen, halogen, alkyl, alkoxy, nitro, amino or hydroxy.
Ｒ4は水素、アルキル、シアノ、アルコキシカルボニ
ル、またはカルバモイルである。ただし、Ｒ1,R2および
Ｒ3は同時に水素を意味しない。R 4 is hydrogen, alkyl, cyano, alkoxycarbonyl, or carbamoyl. However, R 1 , R 2 and R 3 do not mean hydrogen at the same time.
ＭはAs,Sb,BまたはＰである。 M is As, Sb, B or P.
Ｘはハロゲンである。 X is halogen.
ｎはＭがＢである時は４であり、他の場合は６であ
る。n is 4 when M is B, and 6 otherwise.
式Ｉにおいて、アルキルおよびアルコキシの炭素数は
好ましくは４以下であり、Ｒ1,R2およびＲ4のうち少な
くとも一つは水素であり、残りは水素以外の基であるこ
とが好ましい。In formula I, the number of carbon atoms of alkyl and alkoxy is preferably 4 or less, at least one of R 1 , R 2 and R 4 is hydrogen, and the remainder is preferably a group other than hydrogen.
式Ｉの化合物は、式II （式中、Ｒ4は前記に同じ。）のピリジンを、式III （式中、Ｒ1,R2,R3およびＸは前記に同じ。）の置換ベ
ンジルハライドで４級化し、生成するピリジニウムハラ
イドのハライド陰イオンをMXn-イオンで交換することに
よって合成することができる。すなわち、式Ｉのピリジ
ニウム塩に対応するピリジニウムハライドに、MXn-イオ
ンのアルカリ金属塩を反応させることによって式Ｉの化
合物が得られる。The compound of formula I has the formula II (In the formula, R 4 is the same as above.) (Wherein R 1 , R 2 , R 3 and X are the same as above) are quaternized with a substituted benzyl halide and the resulting pyridinium halide can be synthesized by exchanging the halide anion with MXn − ion. it can. That is, the compound of formula I is obtained by reacting the pyridinium halide corresponding to the pyridinium salt of formula I with the alkali metal salt of MXn - ion.
式Ｉの化合物は、温度が上昇するとき開裂して対応す
るカルボニウムカチオン、式 を生じ、オレフィン類、ビニルエーテル、スチレン誘導
体、ジエン類、カルボニル化合物、環状エーテル、エポ
キシド、環状エステル、環状アミドなどのカチオン重合
し得るモノマーの重合連鎖反応を開始させる。しかし常
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、例えば一液型エポキシ樹脂の
硬化剤などその熱潜在性を利用する用途に適している。The compound of formula I is cleaved when the temperature increases to give the corresponding carbonium cation, To initiate a polymerization chain reaction of cationically polymerizable monomers such as olefins, vinyl ethers, styrene derivatives, dienes, carbonyl compounds, cyclic ethers, epoxides, cyclic esters and cyclic amides. However, it is almost inactive at room temperature, but since it functions as an initiator only after heating, it is suitable for applications such as a curing agent for a one-pack type epoxy resin that utilizes its thermal potential.
実施例１ １−（４−メトキシベンジル）−４−シアノピリジニウ
ムヘキサフルオロアンチモネート ４−メトキシベンジルクロライド14.094g（0.09モ
ル）と４−シアノピリジン3.123g（0.03モル）とをメタ
ノール40mlに溶解し、40℃で３日間かきまぜた。反応終
了後溶媒を減圧留去し、残渣へ水−エーテルを加え、未
反応原料をエーテル層へ抽出し、塩化物を含む水層へヘ
キサフルオロアンチモン酸ナトリウム7.764g（0.03モ
ル）を加え、生成する沈澱を吸引ロ過し、洗浄、乾燥し
て題記化合物を得た。Example 1 1- (4-methoxybenzyl) -4-cyanopyridinium hexafluoroantimonate 4-methoxybenzyl chloride 14.094 g (0.09 mol) and 4-cyanopyridine 3.123 g (0.03 mol) were dissolved in 40 ml of methanol, Stir at 40 ° C for 3 days. After completion of the reaction, the solvent was distilled off under reduced pressure, water-ether was added to the residue, the unreacted raw materials were extracted into the ether layer, and sodium hexafluoroantimonate (7.764 g, 0.03 mol) was added to the aqueous layer containing chloride to produce the product. The precipitate was filtered with suction, washed and dried to obtain the title compound.
m.p.152-154℃1 H-NMRによるスペクトル δ 3.84（s,3H,CH3）,6.14（s,2H,CH2）,7.07-7.04
（d,2H,Ph）,7.62-7.65（d,2H,Ph）,8.75（s,2H,Py）,
9.52-9.54（d,2H,Py） 実施例２ １−（４−メチルベンジル）−４−シアノピリジニウム
ヘキサフルオロアンチモネート ４−メチルベンジルクロライド12.654g（0.09モル）
と４−シアノピリジン3.123g（0.03モル）をメタノール
40mlに溶解し、40℃で３日間かきまぜた。反応終了後溶
媒を減圧留去し、残渣へ水−エーテルを加え、未反応原
料をエーテル層へ抽出し、塩化物を含む水層へヘキサフ
ルオロアンチモン酸ナトリウム7.764g（0.03モル）を加
え、生成する沈澱を吸引ロ過し、洗浄、乾燥して題記化
合物を得た。mp152-154 ℃ 1 H-NMR spectrum δ 3.84 (s, 3H, CH 3 ), 6.14 (s, 2H, CH 2 ), 7.07-7.04
(D, 2H, Ph), 7.62-7.65 (d, 2H, Ph), 8.75 (s, 2H, Py),
9.52-9.54 (d, 2H, Py) Example 2 1- (4-methylbenzyl) -4-cyanopyridinium hexafluoroantimonate 4-methylbenzyl chloride 12.654 g (0.09 mol)
And 4-cyanopyridine 3.123 g (0.03 mol) in methanol
It was dissolved in 40 ml and stirred at 40 ° C. for 3 days. After completion of the reaction, the solvent was distilled off under reduced pressure, water-ether was added to the residue, the unreacted raw materials were extracted into the ether layer, and sodium hexafluoroantimonate (7.764 g, 0.03 mol) was added to the aqueous layer containing chloride to produce the product. The precipitate was filtered with suction, washed and dried to obtain the title compound.
m.p.169.5-171℃ 実施例３ １−（４−ｔ−ブチルベンジル）−４−シアノピリジニ
ウムヘキサフルオロアンチモネート ４−ｔ−ブチルベンジルクロライド16.443g（0.09モ
ル）と４−シアノピリジン3.123g（0.03モル）をメタノ
ール40mlに溶解し、40℃で３日間かきまぜた。反応終了
後溶媒を減圧留去し、残渣へ水−エーテルを加え、未反
応原料をエーテル層へ抽出し、塩化物を含む水層へヘキ
サフルオロアンチモン酸ナトリウム7.764g（0.03モル）
を加え、生成する沈澱を吸引ロ過し、洗浄、乾燥して題
記化合物を得た。mp169.5-171 ° C Example 3 1- (4-t-butylbenzyl) -4-cyanopyridinium hexafluoroantimonate 4-t-butylbenzyl chloride 16.443 g (0.09 mol) and 4-cyanopyridine 3.123 g (0.03) (Mol) was dissolved in 40 ml of methanol and stirred at 40 ° C. for 3 days. After completion of the reaction, the solvent was distilled off under reduced pressure, water-ether was added to the residue, unreacted raw materials were extracted into an ether layer, and sodium hexafluoroantimonate was added to the chloride-containing aqueous layer 7.764 g (0.03 mol).
The resulting precipitate was suction filtered, washed and dried to give the title compound.
m.p.120-124℃ 実施例４ １−（４−ｔ−ブチルベンジル）−４−シアノピリジニ
ウムヘキサフルオロフォスフェート 実施例３において、ヘキサフルオロアンチモン酸ナト
リウムの代わりにヘキサフルオロリン酸ナトリウム3.52
7g（0.021モル）を使用し、題記化合物を得た。m.p.188
-191℃ 実施例５ １−（４−ｔ−ブチルベンジル）−４−シアノピリジニ
ウムテトラフルオロボレート 実施例３において、ヘキサフルオロアンチモン酸ナト
リウムの代わりにテトラフルオロホウ酸ナトリウム2.30
6g（0.021モル）を使用し、題記化合物を得た。m.p.215
-218℃ 実施例６ １−（４−クロロベンジル）−４−シアノピリジニウム
ヘキサフルオロアンチモネート ４−クロロベンジルクロライド14.493g（0.09モル）
と４−シアノピリジン3.123g（0.03モル）をメタノール
40mlに溶解し、40℃で３日間かきまぜた。反応終了後溶
媒を減圧留去し、残渣へ水−エーテルを加え、未反応原
料をエーテル層へ抽出し、塩化物を含む水層へヘキサフ
ルオロアンチモン酸ナトリウム7.764g（0.03モル）を加
え、生成する沈澱を吸引ロ過し、洗浄、乾燥して題記化
合物を得た。mp120-124 ° C. Example 4 1- (4-t-butylbenzyl) -4-cyanopyridinium hexafluorophosphate In Example 3, sodium hexafluorophosphate 3.52 was used instead of sodium hexafluoroantimonate.
Using 7 g (0.021 mol), the title compound was obtained. mp188
-191 ° C Example 5 1- (4-t-butylbenzyl) -4-cyanopyridinium tetrafluoroborate In Example 3, sodium tetrafluoroborate 2.30 was used instead of sodium hexafluoroantimonate.
Using 6 g (0.021 mol), the title compound was obtained. mp215
-218 ° C Example 6 1- (4-chlorobenzyl) -4-cyanopyridinium hexafluoroantimonate 4-chlorobenzyl chloride 14.493 g (0.09 mol)
And 4-cyanopyridine 3.123 g (0.03 mol) in methanol
It was dissolved in 40 ml and stirred at 40 ° C. for 3 days. After completion of the reaction, the solvent was distilled off under reduced pressure, water-ether was added to the residue, the unreacted raw materials were extracted into the ether layer, and sodium hexafluoroantimonate (7.764 g, 0.03 mol) was added to the aqueous layer containing chloride to produce the product. The precipitate was filtered with suction, washed and dried to obtain the title compound.
m.p.150-151℃ 実施例７ １−（４−ニトロベンジル）−４−シアノピリジニウム
ヘキサフルオロアンチモネート ４−ニトロベンジルクロライド15.442g（0.09モル）
と４−シアノピリジン3.123g（0.03モル）をメタノール
40mlに溶解し、40℃で３日間かきまぜた。反応終了後溶
媒を減圧留去し、残渣へ水−エーテルを加え、未反応原
料をエーテル層へ抽出し、塩化物を含む水層へヘキサフ
ルオロアンチモン酸ナトリウム7.764g（0.03モル）を加
え、生成する沈澱を吸引ロ過し、洗浄、乾燥して題記化
合物を得た。mp150-151 ° C. Example 7 1- (4-Nitrobenzyl) -4-cyanopyridinium hexafluoroantimonate 4-nitrobenzyl chloride 15.442 g (0.09 mol)
And 4-cyanopyridine 3.123 g (0.03 mol) in methanol
It was dissolved in 40 ml and stirred at 40 ° C. for 3 days. After completion of the reaction, the solvent was distilled off under reduced pressure, water-ether was added to the residue, the unreacted raw materials were extracted into the ether layer, and sodium hexafluoroantimonate (7.764 g, 0.03 mol) was added to the aqueous layer containing chloride to produce the product. The precipitate was filtered with suction, washed and dried to obtain the title compound.
m.p.167-168℃m.p.167-168 ℃
───────────────────────────────────────────────────── 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 Ｃ０８Ｆ 4/00 ＭＦＪ Ｃ０８Ｆ 4/00 ＭＦＪ 4/06 ＭＥＨ 4/06 ＭＥＨ Ｃ０８Ｇ 59/50 ＮＪＡ Ｃ０８Ｇ 59/50 ＮＪＡ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location C08F 4/00 MFJ C08F 4/00 MFJ 4/06 MEH 4/06 MEH C08G 59/50 NJA C08G 59 / 50 NJA
Claims (1)
アルコキシ、ニトロ、アミノ、またはヒドロキシであ
り、Ｒ4は水素、アルキル、シアノ、アルコキシカルボ
ニル、またはカルバモイルであり（ただし、Ｒ1,R2およ
びＲ3は同時に水素を意味しない。）、 ＭはAs,Sb,BまたはＰであり、 Ｘはハロゲンであり、 ｎはＭがＢである時は４であり、他の場合は６である。1. A formula Benzylpyridinium salt of. In the formula, R 1 , R 2 and R 3 are hydrogen, halogen, alkyl,
Alkoxy, nitro, amino, or hydroxy, R 4 is hydrogen, alkyl, cyano, alkoxycarbonyl, or carbamoyl (provided that R 1 , R 2 and R 3 do not mean hydrogen at the same time), and M is As. , Sb, B or P, X is halogen, n is 4 when M is B, and 6 otherwise.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62255388A JP2519480B2 (en) | 1987-10-09 | 1987-10-09 | New benzylpyridinium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62255388A JP2519480B2 (en) | 1987-10-09 | 1987-10-09 | New benzylpyridinium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0196169A JPH0196169A (en) | 1989-04-14 |
| JP2519480B2 true JP2519480B2 (en) | 1996-07-31 |
Family
ID=17278067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62255388A Expired - Fee Related JP2519480B2 (en) | 1987-10-09 | 1987-10-09 | New benzylpyridinium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2519480B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7329480B2 (en) | 2002-08-30 | 2008-02-12 | Toyo Gosei Co., Ltd. | Radiation-sensitive negative-type resist composition for pattern formation method |
| WO2009101758A1 (en) | 2008-02-14 | 2009-08-20 | Daicel Chemical Industries, Ltd. | Curable resin composition for nanoimprint |
| WO2009110162A1 (en) | 2008-03-03 | 2009-09-11 | ダイセル化学工業株式会社 | Process for production of nanostructures |
| WO2011040531A1 (en) | 2009-10-01 | 2011-04-07 | 日立化成工業株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| WO2011132702A1 (en) | 2010-04-22 | 2011-10-27 | 日立化成工業株式会社 | Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device |
| WO2014136900A1 (en) | 2013-03-08 | 2014-09-12 | 日立化成株式会社 | Ionic-compound-containing treatment solution, organic electronic element, and method for manufacturing organic electronic element |
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|---|---|---|---|---|
| JPH09227470A (en) * | 1996-02-16 | 1997-09-02 | Nippon Paint Co Ltd | Synthesis of quaternary ammonium salt |
| CN1057402C (en) * | 1996-03-01 | 2000-10-11 | 台湾通用器材股份有限公司 | Method for packing semiconductor |
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-
1987
- 1987-10-09 JP JP62255388A patent/JP2519480B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| J.CHEM.SOC.PERKIN TRANS.2=1984 * |
| J.MED.CHEM=1969 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7329480B2 (en) | 2002-08-30 | 2008-02-12 | Toyo Gosei Co., Ltd. | Radiation-sensitive negative-type resist composition for pattern formation method |
| WO2009101758A1 (en) | 2008-02-14 | 2009-08-20 | Daicel Chemical Industries, Ltd. | Curable resin composition for nanoimprint |
| WO2009110162A1 (en) | 2008-03-03 | 2009-09-11 | ダイセル化学工業株式会社 | Process for production of nanostructures |
| WO2011040531A1 (en) | 2009-10-01 | 2011-04-07 | 日立化成工業株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| WO2011132702A1 (en) | 2010-04-22 | 2011-10-27 | 日立化成工業株式会社 | Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device |
| US10566105B2 (en) | 2010-04-22 | 2020-02-18 | Hitachi Chemical Company, Ltd. | Method for producing charge transport film |
| WO2014136900A1 (en) | 2013-03-08 | 2014-09-12 | 日立化成株式会社 | Ionic-compound-containing treatment solution, organic electronic element, and method for manufacturing organic electronic element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0196169A (en) | 1989-04-14 |
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