JP3517240B2 - New anilinium salt compound and polymerization initiator - Google Patents
New anilinium salt compound and polymerization initiatorInfo
- Publication number
- JP3517240B2 JP3517240B2 JP51500994A JP51500994A JP3517240B2 JP 3517240 B2 JP3517240 B2 JP 3517240B2 JP 51500994 A JP51500994 A JP 51500994A JP 51500994 A JP51500994 A JP 51500994A JP 3517240 B2 JP3517240 B2 JP 3517240B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- nitrogen atom
- salt compound
- alkyl group
- compound
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/18—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/16—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/12—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
- C07C225/04—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
- C07C225/06—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and acyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Polymerization Catalysts (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、新規アニリニウム塩化合物及びそれらを含
有するカチオン重合開始剤に関するものである。該重合
開始剤を含有するカチオン重合性組成物は、室温又は加
熱により短時間で重合することができ、新しい重合体の
合成や成型樹脂、注型樹脂、塗料、接着剤、インキ等の
材料として好適に用いられる。The present invention relates to novel anilinium salt compounds and cationic polymerization initiators containing them. The cationically polymerizable composition containing the polymerization initiator can be polymerized in a short time at room temperature or by heating, and is used as a material for synthesizing a new polymer, molding resin, casting resin, paint, adhesive, ink, etc. It is preferably used.
カチオン重合性化合物を重合させる開始剤として、ル
イス酸、ブレンステット酸など知られている。
一方、新しいカチオン重合開始剤として、特公昭63−
12092号、特公昭63−12093号、特公昭63−12095号、特
開平２−1470号、特開２−268173号、特開平３−17101
号、特開平１−96169号、特開平２−255646号、特開平
３−11044号、特開平３−56470号などが知られている。
また、東村等は、開始剤としてハロゲン原子を有する
化合物とアクセレーターとの組み合わせを使用してビニ
ルエーテル誘導体やスチレン誘導体等のカチオン重合性
化合物のリビングカチオン重合について報告している。
反応性の高いビニルエーテル等のモノマーを重合開始
剤として、三フッ化ホウ素エーテラートやトリメチルオ
キソニウムテトラクロロアンチモネート等のルイス酸を
使用して重合する場合は、−60℃等の低温で行う必要が
あり、また、重合開始剤の扱いには、湿気を嫌うため、
不便さがさけられない。また、これらの開始剤をエポキ
シ化合物等の硬化用触媒として使用することは、一般に
困難である。
一方、特公昭63−12092号、特公昭63−12093号、特公
昭63−12095号、特開平２−1470号、特開２−268173
号、特開平３−17101号、特開平１−96169号、特開平２
−255646号、特開平３−11044号、特開平３−56470号な
どのスルホニウム塩、ホスホニウム塩およびアンモニウ
ム塩化合物は、所謂ハンドリングが簡単に行うことがで
き、エポキシ化合物等の硬化用触媒として使用すること
は容易であるが、硬化用触媒として使用する場合には、
開始反応の際に脱離する成分による重合停止が簡単に起
こるため、架橋密度の高い、優れた物性を有する硬化物
は得られにくい。また、重合開始剤として使用する場合
は、作用温度が高いことによる連鎖移動等の原因によ
り、高分子量の重合体が得られにくいという欠点があ
る。
ハロゲン原子を有する化合物とアクセレーターとの組
み合わせを重合開始剤として使用する、所謂東村等によ
って開発されたカチオンリビング重合は、これまでにな
い画期的なものであり、反応温度も室温付近で行えるな
どの特徴を有するが、開始剤のハンドリング性に問題が
あると同時に、シクロヘキセンオキサイド等のエポキシ
化合物を重合することは困難であり、硬化用触媒として
使用することも困難である。
本発明は、前に述べた事情からみてなされたもので、
空気中、常温で極めて安定で、常温での取り扱いが簡便
であり、常温付近から100℃以下の温和な条件下で、ビ
ニルエーテルやエポキシ化合物等のカチオン重合性モノ
マーを容易に重合できる重合開始剤として作用するばか
りでなく、硬化触媒として用いた場合、常温から170℃
の比較的低い温度範囲で容易に硬化させることができ、
また開始反応の際に脱離する成分による重合停止が起こ
りにくいため、架橋密度やガラス転移温度が高い、優れ
た物性を有する硬化物を得ることができる新規アニリニ
ウム塩化合物を提供することを目的としている。As an initiator for polymerizing a cationically polymerizable compound, Lewis acid, Brensted acid and the like are known. On the other hand, as a new cationic polymerization initiator,
12092, JP-B-63-12093, JP-B-63-12095, JP-A No. 2-1470, JP-A No. 2-268173, and JP-A No. 3-17101.
JP-A-1-96169, JP-A-2-255646, JP-A-3-11044, and JP-A-3-56470 are known. Higashimura et al. Have reported living cationic polymerization of cationically polymerizable compounds such as vinyl ether derivatives and styrene derivatives using a combination of a compound having a halogen atom as an initiator and an accelerator. When a highly reactive monomer such as vinyl ether is used as a polymerization initiator and a Lewis acid such as boron trifluoride etherate or trimethyloxonium tetrachloroantimonate is used for polymerization, it is necessary to perform the reaction at a low temperature such as −60 ° C. Yes, and because the polymerization initiator does not like moisture,
I can't avoid the inconvenience. Further, it is generally difficult to use these initiators as a curing catalyst for epoxy compounds and the like. On the other hand, JP-B-63-12092, JP-B-63-12093, JP-B-63-12095, JP-A-2-1470 and JP-A-2-268173.
JP-A-3-17101, JP-A-1-96169, and JP-A-2
-255646, JP-A-3-11044, JP-A-3-56470 and the like, sulfonium salt, phosphonium salt and ammonium salt compounds, so-called handling can be easily performed, and used as a curing catalyst for epoxy compounds and the like. It is easy to do, but when used as a curing catalyst,
Since the termination of the polymerization is easily caused by the component released during the initiation reaction, it is difficult to obtain a cured product having a high crosslink density and excellent physical properties. Further, when it is used as a polymerization initiator, there is a drawback that it is difficult to obtain a polymer having a high molecular weight due to a cause such as chain transfer due to a high action temperature. Cationic living polymerization developed by so-called Higashimura et al., Which uses a combination of a compound having a halogen atom and an accelerator as a polymerization initiator, is epoch-making, and the reaction temperature can be around room temperature. However, it is difficult to polymerize an epoxy compound such as cyclohexene oxide, and it is difficult to use it as a curing catalyst. The present invention has been made in view of the circumstances described above,
As a polymerization initiator that is extremely stable in the air at room temperature, is easy to handle at room temperature, and can easily polymerize cationically polymerizable monomers such as vinyl ether and epoxy compounds under mild conditions from around room temperature to 100 ° C or less. Not only does it work, but when used as a curing catalyst, room temperature to 170 ° C
Can be easily cured in the relatively low temperature range of
Further, since it is difficult for polymerization termination due to a component to be eliminated during the initiation reaction to occur, the crosslink density and the glass transition temperature are high, and it is an object to provide a novel anilinium salt compound capable of obtaining a cured product having excellent physical properties. There is.
本発明者らは、前記目的を達成するため、鋭意検討し
たところ、特定のアニリニウム塩化合物を重合開始剤と
して用いることで、常温付近から100℃以下の温和な条
件下で簡便にカチオン重合性化合物を重合させることが
でき、又、硬化用触媒として用いることで、常温から17
0℃の比較的低い温度範囲で容易に硬化させることがで
き、架橋密度やガラス転移温度が高い、優れた物性を有
する硬化物を与えることを見出した。
即ち、本発明は、一般式（Ｉ）で表されるアニリニウ
ム塩化合物及び該化合物の少なくとも一種を含有するこ
とを特徴とするカチオン重合開始剤である。
〔式中、R1は、水素原子、アルキル基、窒素原子から数
えてβ位の炭素が不飽和結合でアルキル基、窒素原子の
α位の炭素にエステル基又はカルボニル基を有するアル
キル基、芳香環に置換基を有してもよいベンジル基、α
−フェニルベンジル基、α−ナフチルメチル基及びβ−
ナフチルメチル基からなる群から選ばれる１種を表し、
R2は、アルキル基又は窒素原子のα、β又はγ位の炭素
に置換基を有するアルキル基を表し、R3、窒素原子の
α、β又はγ位の炭素に置換基を有するアルキル基を表
し、R4R5は、それぞれ水素原子、ハロゲン原子、アルコ
キシ基、ニトロ基、シアノ基又はアルカノイル基のいず
れかの基を表し、R4とR5とは、一体となって芳香環を形
成してもよく、Ｘは、非求核性の対アニオン残基を表
す〕
以下、本発明を詳細に説明する。
（アニリニウム塩化合物）
本発明に使用されるアニリニウム塩化合物は、上記一
般式（Ｉ）で表されるが、一般式（Ｉ）において、
R1は、水素原子、メチル、エチル、ｎ−プロピル、イ
ソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｎ
−ペンチル、イソペンチル、シクロペンチル、ｎ−ヘキ
シル、イソヘキシル、シクロヘキシル、ｎ−オクチル、
デシル、ドデシル、オクタデシル等のアルキル基、シン
ナミル、クロチル、アリル、プロパルギル、２−メチル
−１−プロペニル、３−メチル−２−ブテニル、１−メ
チル−２−ブテニル、２−ブチニル等の窒素原子から数
えてβ位の炭素が不飽和結合であるアルキル基、メトキ
シカルボニルメチル、エトキシカルボニルメチル、２−
エチルヘキシルオキシカルボニルメチル、ステアリルオ
キシカルボニルメチル、α−メトキシカルボニルベンジ
ル、１−メトキシカルボニルエチル、１−エトキシカル
ボニルエチル、１−シクロヘキシルオキシカルボニルエ
チル、１−ドデシルオキシカカルボニルエチル、１−メ
トキシカルボニルプロピル、１−エトキシカルボニルプ
ロピル、１−オクチルオキシカルボニルプロピル、フェ
ノキシカルボニルメチル、１−フェノキシカルボニルエ
チル、１−フェノキカルボニルプロピル、２−アクリロ
イルオキシエトキシカルボニルメチル、アセチルメチ
ル、フェナシル、α−ベンゾイルベンゾイル、スチリル
カルボニルメチル、１−ベンゾイルエチル、１−ベンゾ
イルプロピル等の窒素原子のα位の炭素にエステル基又
はカルボニル基を有するアルキル基、芳香環に、メチ
ル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチ
ル、イソブチル、ｎ−ペンチル、イソペンチル、シクロ
ペンチル、ｎ−ヘキシル、イソヘキシル、シクロヘキシ
ル、オクチル、デシル、ドデシル、オクタデシル等のア
ルキル基、F,Cl,Br等のハロゲン原子、メトキシ基、エ
トキシ基、プロポキシ基、イソプロポキシ基等のアルコ
キシ基、置換基を有していても良いフェノキシ基、シア
ノ基、ニトロ基、アセトキシ基、メトキシカルボニル
基、エトキシカルボニル基、ベンゾイルオキシ基、フェ
ノキシカルボニル基、アセチル基、プロピオニルオキシ
基等のアルカノイル基、置換基を有していてもよいベン
ゾイル基等の置換基を有してもよいベンジル基、α−フ
ェニルベンジル基、α−フェニルベンジル基、α−ナフ
チルメチル基及びβ−ナフチルメチル基からなる群より
選ばれた一種である。
R2は、メチル、エチル、ｎ−プロピル、イソプロピ
ル、ｎ−ブチル、イソブチル、ｔ−ブチル、ｎ−ペンチ
ル、イソペンチル、シクロペンチル、ｎ−ヘキシル、イ
ソヘキシル、シクロヘキシル、オクチル、デシル、ドデ
シル、オクタデシル等のアルキル基、または、水酸基、
置換基を有していてもよいフェニル基、Ｆ、Cl、Br等の
ハロゲン原子、メトキシ基、エトキシ基、ブトキシ基等
のアルコキシ基、置換基を有していてもよいフェノキシ
基、シアノ基、ニトロ基、アセトキシ基、プロピオニル
オキシ基、メトキシカルボニル基、エトキシカルボニル
基、ベンゾイルオキシ基、フェノキシカルボニル基、ア
セチル基、プロピオニル基、ベンゾイル基、アクリロイ
ルオキシ基、ステアロイルオキシ基等のアルカノイル
基、またはＮ−フタルイミドメチル基等の置換基を、窒
素原子のα、β又はγ位の炭素に有するアルキル基を表
すが、窒素原子のα位の炭素にフェニル基の置換基を有
するアルキル基を除く。
R3は、水酸基、置換基を有していてもよいフェニル
基、Ｆ、Cl、Br等のハロゲン原子、メトキシ基、エトキ
シ基、ブトキシ基等のアルコキシ基、置換基を有してい
てもよいフェノキシ基、シアノ基、ニトロ基、アセトキ
シ基、プロピオニルオキシ基、メトキシカルボニル基、
エトキシカルボニル基、ベンゾイルオキシ基、フェノキ
シカルボニル基、アセチル基、プロピオニル基、ベンゾ
イル基、アクリロイルオキシ基、ステアロイルオキシ基
等のアルカノイル基、またはＮ−フタルイミドメチル基
等の置換基を、窒素原子のα、β又はγ位の炭素に有す
るアルキル基を表すが、窒素原子のα位の炭素にフェニ
ル基の置換基を有するアルキル基を除く。
R4,R5は、それぞれ水素原子、Ｆ、Cl,Br等のハロゲン
原子、メチル、エチル、ｎ−プロピル、イソプロピル、
ｎ−ブチル、ヘキシル等のアルキル基、メトキシ基、エ
トキシ基、プロポキシ基、イソプロポキシ基等のアルコ
キシ基、アルキル基、ハロゲン原子、ニトロ基、シアノ
基、アルコキシ基、アルコキシカルボニル基等の置換基
を有していてもよいフェノキシ基、シアノ基、ニトロ
基、アセトキシ基、メトキシカルボニル基、エトキシカ
ルボニル基、ベンゾイルオキシ基、フェノキシカルボニ
ル基、アセチル基、ベンゾイル基、ジメチルアミノカル
ボニル基及びモルホリノカルボニル基等からなる群より
選ばれた一種であり、R4とR5とは、一体となって、例え
ば、ナフタレン環やアントラセン環のような芳香環を形
成してもよい。
また、Ｘは、BF4,PF6,AsF6,SbF6,SbCl6,ClO4,FeO4等
の非求核性の対アニオン残基を表わす。
本発明のアニリニウム塩化合物は、使用用途によっ
て、化合物の使い分けを行うことができる。
例えば、アニリニウム塩化合物を重合開始剤として使
用し、重合体の合成や瞬間硬化用の硬化剤として使用す
る場合は、前記一般式（１）のR2が、窒素原子のα、β
又はγ位の炭素に置換基を有するアルキル基であり、R3
が、窒素原子のα、β又はγ位の炭素に置換基を有する
アルキル基であり、かつ置換基が、アルカノイル基やシ
アノ基のような電子吸引性基であることが望ましい。
一方、本発明のアニリニウム塩化合物をエポキシ化合
物等の硬化剤として使用する場合には、R1が、アルキル
基、窒素原子から数えてβ位の炭素が不飽和結合である
アルキル基、窒素原子のα位の炭素にエステル基、カル
ボニル基を有するアルキル基、芳香環に置換基を有して
もよいベンジル基、α−フェニルベンジル基、α−ナフ
チルメチル基又はβ−ナフチル基であり、R2が、アルキ
ル基又は窒素原子のα、β又はγ位の炭素に置換基を有
するアルキル基であり、R3は、窒素原子のα、β又はγ
位の炭素に置換基を有するアルキル基が好ましい。
（アニリニウム塩化合物の合成法）
本発明のアニリニウム塩化合物は、例えば、次の方法
で得ることができる。ベンジルブロマイド、ベンズヒド
リルブロマイド、ブロモ酢酸エチル、シンナミルブロマ
イド、クロチルブロマイド及びα又はβ−ブロモメチル
ナフタレン等の有機ハロゲン化合物、又はジメチル硫酸
やジエチル硫酸等のジアルキル硫酸、ｐ−トルエンスル
ホン酸メチルやベンゼンスルホン酸シンナミル、メタン
スルホン酸ベンジルなどのスルホン酸エステル化合物
と、Ｎ−（２−アセトキシエチル）−Ｎ−エチル−ｍ−
トルイジンやＮ−（２−ヒドロキシエチル）−Ｎ−（２
−シアノエチル）アニリンのようなN,N−ジ置換アニリ
ン誘導体とを、必要に応じて酢酸エチル、酢酸ブチル、
トルエン、アセトニトリル、メタノール、エタノール、
ジオキサン、エチルメチルケトン等の不活性溶媒存在
下、室温〜100℃で、数時間〜数日間反応させ、次い
で、得られた化合物を水もしくは水−メタノール等の水
−有機溶媒に溶解せしめ、六フッ化アンチモン酸カリウ
ム等の非求核性アニオンのアルカリ塩を加え激しく攪拌
し、析出した生成物を抽出等により、分離後、必要に応
じて精製し、乾燥して得ることができる。
一方、一般式（１）のR1が水素原子のアニリニウム塩
は、N,N−ジ置換アニリン誘導体と塩酸等の一価の酸と
を反応させ、次いで得られた化合物を水もしくは水−有
機溶媒に溶解せしめ、非求核性アニオンのアルカリ塩を
加え激しく攪拌し、析出した生成物を抽出等により、分
離後、必要に応じて精製し、乾燥して得ることができ
る。
（アニリニウム塩化合物の具体例）
本発明の代表的なアニリニウム塩化合物として、次の
ようなものが例示される。但し、式中のＸは、BF4,PF6,
AsF6,SbF6,SbCl6,ClO4,FeO4等の非求核性の対アニオン
残基を表わす。
（重合性化合物）
本発明に使用されるカチオン重合性化合物は、一般に
知られているカチオン重合性を有するモノマー、オリゴ
マ−やポリマーであれば何ら制限されることなく使用可
能であり、例えば、下記のようなものが例示される。
（ａ）ビニル化合物として、スチレン、α−メチルスチ
レン、ｐ−メトキシスチレン、ｐ−ｔ−ブトキシスチレ
ン等のスチレン化合物、メチルビニルエーテル、ｎ−ブ
チルビニルエーテル、エチルビニルエーテル、イソブチ
ルビニルエーテル、シクロヘキシルビニルエーテル、２
−クロロエチルビニルエーテル、２−フェノキシエチル
ビニルエーテル、２−ヒドロキシエチルビニルエーテ
ル、４−ヒドロキシブチルビニルエーテル、ステアリル
ビニルエーテル、２−アセトキシエチルビニルエーテル
等のアルキルビニルエーテル化合物、アリルビニルエー
テル、２−メタクリロイルオキシエチルビニルエーテ
ル、２−アクリロイルオキシエチルビニルエーテル等の
アルケニルビニルエーテル化合物、フェニルビニルエー
テル、ｐ−メトキシフェニルビニルエーテル等のアリー
ルビニルエーテル化合物、Ｎ−ビニルカルバゾール、Ｎ
−ビニルピロリドン等のカチオン重合性窒素含有化合
物、ブタンジオールジビニルエーテル、トリエチレング
リコールジビニルエーテル、シクロヘキサンジオールジ
ビニルエーテル、1,4−ベンゼンジメタノールジビニル
エーテル、ハイドロキノンジビニルエーテル、サゾルシ
ノールジビニルエーテル等の多官能ビニル化合物が挙げ
られる。
（ｂ）エポキシ化合物として、フェニルグリシジルエー
テル、ｐ−tert−ブチルフェニルグリシジルエーテル、
ブチルグリシジルエーテル、２−エチルヘキシルグリシ
ジルエーテル、アリルグリシジルエーテル、1,2−ブチ
レンオキサイド、1,3−ブタジエンモノオキサイド、1,2
−ドデシレンオキサイド、エピクロロヒドリン、1,2−
エポキシデカン、エチレンオキサイド、プロピレンオキ
サイド、スチレンオキサイド、シクロヘキセンオキサイ
ド、３−メタクリロイルオキシメチルシクロヘキセンオ
キサイド、３−アクリロイルオキシメチルシクロヘキセ
ンオキサイド、３−ビニルシクロヘキセンオキサイド等
の単官能モノマー、1,1,3−テトラデカジエンジオキサ
イド、リモネンジオキサイド、3,4−エポキシシクロヘ
キシルメチル−（3,4−エポキシシクロヘキシル）カル
ボキシレート、ジ（3,4−エポキシシクロヘキシル）ア
ジペート、ビスフェノールＡ型エポキシ樹脂、ビスフェ
ノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ
樹脂、ハロゲン化ビスフェノールＡ型エポキシ樹脂、ｏ
−,m−,p−クレゾールノボラック型エポキシ樹脂、ハロ
ゲン化ｏ−,m−,p−クレゾールノボラック型エポキシ樹
脂、フェノールノボラック型エポキシ樹脂、多価アルコ
ールのポリグリシジルエーテル等の多官能エポキシ化合
物が挙げられる。
（ｃ）ビシクロオルソエステル化合物として、１−フェ
ニル−４−エチル−2,6,7−トリオキサビシクロ〔2,2,
2〕オクタン、１−エチル−４−ヒドロキシメチル−2,
6,7−トリオキサビシクロ〔2,2,2〕オクタン等の化合物
が挙げられる。
（ｄ）スピロオルソカーボネート化合物として、1,5,7,
11−テトラオキサスピロ〔5,5〕ウンデカン、3,9−ジベ
ンジル−1,5,7,11−テトラオキサスピロ〔5,5〕ウンデ
カン、1,4,6−トリオキサスピロ〔4,4〕ノナン、２−メ
チル−1,4,6−トリオキサスピロ〔4,4〕ノナン、1,4,6
−トリオキサスピロ〔4,5〕デカン等の化合物が挙げら
れる。
なお、これらは、単独もしくは２種以上を併用して用
いても差し支えない。
（硬化剤）
本発明において、アニリニウム塩化合物を硬化剤とし
て使用する場合、アニリニウム塩化合物とカチオン重合
性化合物の配合割合は、カチオン重合性化合物100部に
対し、アニリニウム塩化合物0.01〜10部、好ましくは0.
1〜５部の割合で配合する。このアニリニウム塩化合物
が少ないと、カチオン重合性化合物の硬化性が低下し、
過剰であると硬化物の特性が低下する。
本発明のアニリニウム塩化合物を含有するカチオン重
合性化合物は、加熱により容易に硬化することができ
る。硬化温度は、10℃〜220℃、好ましくは、30℃〜200
℃、さらに好ましくは50℃〜180℃の範囲である。
本発明のアニリニウム塩化合物を含有するカチオン重
合性化合物は、α線、β線、γ線、中性子線、Ｘ線、加
速電子線等の電離性放射線によっても硬化することがで
きる。
（重合開始剤）
本発明のアニリニウム塩化合物を重合開始剤として使
用する場合において使用される溶媒は、トルエン、塩化
メチレン、クロロホルム等の通常カチオン重合で使用さ
れる溶媒が使用できる。また、酢酸エチル等のエステル
系の溶媒やメチルエチルケトン等のケトン系の溶媒も使
用でき、重合度も使用する溶媒によってコントロールす
ることができる。従って、アクリル酸エチルや1,4−ブ
タンジオールジメタクリレート等のアクリル酸エステル
モノマー中でも重合することができる。この点を利用す
ると、精製することなく硬化性のアクリル塗料を簡便に
調製することができる。
前記アニリニウム塩化合物とカチオン重合性モノマー
との使用比率は、所望する重合体の分子量により、任意
に設定することができる。
一方、重合をコントロールする目的で、ジオキサン等
の重合コントロール剤を添加し、重合速度、分子量およ
び分散度をコントロールすることもできる。
また、エタノールやエチレングリコール等の水酸基を
有する化合物を連鎖移動剤として使用することができ、
これにより分子量の調整等も可能となる。
更に、例えば、２−ヒドロキシエチルメタクリレート
のような官能基を有する化合物を連鎖移動剤として使用
すると、ポリマー中にメタクリル基等の官能基を導入す
ることができる。
本発明の重合開始剤として使用するアニリニウム塩化
合物は、活性に優れているため、重合を一旦終了した後
であっても、更にモノマーを加えることにより重合を再
開させることができ、この操作を数回繰り返して行って
も問題なく重合体が得られる。また、多少の水分を含ん
でいる場合であっても重合を得ることができる。従っ
て、重合溶媒系の重合体の濃度は、ある程度任意に設定
することが可能である。In order to achieve the above-mentioned object, the inventors of the present invention have made extensive studies, and by using a specific anilinium salt compound as a polymerization initiator, a cationically polymerizable compound can be easily prepared from around room temperature to 100 ° C. under mild conditions. Can be polymerized, and when used as a curing catalyst,
It has been found that a cured product which can be easily cured in a relatively low temperature range of 0 ° C. and has a high crosslink density and a high glass transition temperature and which has excellent physical properties is obtained. That is, the present invention is a cationic polymerization initiator characterized by containing an anilinium salt compound represented by the general formula (I) and at least one of the compounds. [In the formula, R 1 is a hydrogen atom, an alkyl group, an alkyl group in which the carbon at the β-position counted from the nitrogen atom is an unsaturated bond, an alkyl group having an ester group or a carbonyl group at the carbon at the α-position of the nitrogen atom, and an aromatic group. A benzyl group which may have a substituent on the ring, α
-Phenylbenzyl group, α-naphthylmethyl group and β-
Represents one selected from the group consisting of naphthylmethyl groups,
R 2 represents an alkyl group or an alkyl group having a substituent on the carbon at the α, β or γ position of the nitrogen atom, and R 3 , an alkyl group having a substituent on the carbon at the α, β or γ position of the nitrogen atom. Represents R 4, R 5 represents any one of a hydrogen atom, a halogen atom, an alkoxy group, a nitro group, a cyano group or an alkanoyl group, and R 4 and R 5 together form an aromatic ring. Alternatively, X represents a non-nucleophilic counter anion residue] Hereinafter, the present invention will be described in detail. (Anilinium Salt Compound) The anilinium salt compound used in the present invention is represented by the above general formula (I). In the general formula (I), R 1 is a hydrogen atom, methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, t-butyl, n
-Pentyl, isopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-octyl,
From alkyl groups such as decyl, dodecyl and octadecyl, nitrogen atoms such as cinnamyl, crotyl, allyl, propargyl, 2-methyl-1-propenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl and 2-butynyl. An alkyl group in which the β-position carbon is an unsaturated bond, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-
Ethylhexyloxycarbonylmethyl, stearyloxycarbonylmethyl, α-methoxycarbonylbenzyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-cyclohexyloxycarbonylethyl, 1-dodecyloxycarbonylcarbonyl, 1-methoxycarbonylpropyl, 1 -Ethoxycarbonylpropyl, 1-octyloxycarbonylpropyl, phenoxycarbonylmethyl, 1-phenoxycarbonylethyl, 1-phenoxycarbonylpropyl, 2-acryloyloxyethoxycarbonylmethyl, acetylmethyl, phenacyl, α-benzoylbenzoyl, styrylcarbonylmethyl, Having an ester group or a carbonyl group at the α-carbon of the nitrogen atom such as 1-benzoylethyl, 1-benzoylpropyl, etc. Alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group and octadecyl group. , Halogen atom such as F, Cl, Br, methoxy group, ethoxy group, propoxy group, alkoxy group such as isopropoxy group, phenoxy group which may have a substituent, cyano group, nitro group, acetoxy group, methoxy group Carbonyl group, ethoxycarbonyl group, benzoyloxy group, phenoxycarbonyl group, acetyl group, alkanoyl group such as propionyloxy group, a benzyl group which may have a substituent such as a benzoyl group which may have a substituent, α-phenylbenzyl group, α-phenylbenzyl group, α-na Chirumechiru is one selected from the group the group consisting of β- naphthylmethyl group. R 2 is alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, octyl, decyl, dodecyl and octadecyl. Group or hydroxyl group,
A phenyl group which may have a substituent, a halogen atom such as F, Cl and Br, an alkoxy group such as a methoxy group, an ethoxy group and a butoxy group, a phenoxy group which may have a substituent, a cyano group, Alkanoyl groups such as nitro group, acetoxy group, propionyloxy group, methoxycarbonyl group, ethoxycarbonyl group, benzoyloxy group, phenoxycarbonyl group, acetyl group, propionyl group, benzoyl group, acryloyloxy group, stearoyloxy group, or N- It represents an alkyl group having a substituent such as a phthalimidomethyl group on the carbon at the α, β or γ position of the nitrogen atom, but excludes an alkyl group having a substituent of the phenyl group on the carbon at the α position of the nitrogen atom. R 3 may have a hydroxyl group, a phenyl group which may have a substituent, a halogen atom such as F, Cl and Br, an alkoxy group such as a methoxy group, an ethoxy group and a butoxy group, and an optionally substituted group. Phenoxy group, cyano group, nitro group, acetoxy group, propionyloxy group, methoxycarbonyl group,
Ethoxycarbonyl group, benzoyloxy group, phenoxycarbonyl group, acetyl group, propionyl group, benzoyl group, acryloyloxy group, alkanoyl group such as stearoyloxy group, or a substituent such as N-phthalimidomethyl group, a nitrogen atom α, It represents an alkyl group having a carbon atom at the β or γ position, but excludes an alkyl group having a substituent of a phenyl group at the carbon atom at the α position of a nitrogen atom. R 4 and R 5 are each a hydrogen atom, a halogen atom such as F, Cl or Br, methyl, ethyl, n-propyl, isopropyl,
Alkyl groups such as n-butyl and hexyl, alkoxy groups such as methoxy group, ethoxy group, propoxy group and isopropoxy group, substituents such as alkyl group, halogen atom, nitro group, cyano group, alkoxy group and alkoxycarbonyl group. From a phenoxy group which may have, a cyano group, a nitro group, an acetoxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzoyloxy group, a phenoxycarbonyl group, an acetyl group, a benzoyl group, a dimethylaminocarbonyl group and a morpholinocarbonyl group. It is a kind selected from the group consisting of R 4 and R 5, and may together form an aromatic ring such as a naphthalene ring or an anthracene ring. X represents a non-nucleophilic counter anion residue such as BF 4 , PF 6 , AsF 6 , SbF 6 , SbCl 6 , ClO 4 and FeO 4 . The anilinium salt compound of the present invention can be selectively used depending on the intended use. For example, when an anilinium salt compound is used as a polymerization initiator and is used as a curing agent for polymer synthesis or flash curing, R 2 in the general formula (1) is a nitrogen atom α or β.
Or an alkyl group having a substituent at the γ-position carbon, R 3
Is preferably an alkyl group having a substituent on the carbon at the α, β or γ position of the nitrogen atom, and the substituent is an electron-withdrawing group such as an alkanoyl group or a cyano group. On the other hand, when the anilinium salt compound of the present invention is used as a curing agent for epoxy compounds and the like, R 1 is an alkyl group, an alkyl group in which the β-position carbon atom counted from the nitrogen atom is an unsaturated bond, or a nitrogen atom an ester group at the α-position carbon, an alkyl group having a carbonyl group, a benzyl group which may have a substituent on the aromatic ring, an α-phenylbenzyl group, an α-naphthylmethyl group or a β-naphthyl group, R 2 Is an alkyl group or an alkyl group having a substituent on the carbon at the α, β or γ position of the nitrogen atom, and R 3 is α, β or γ of the nitrogen atom.
An alkyl group having a substituent on the carbon at the position is preferable. (Synthesis Method of Anilinium Salt Compound) The anilinium salt compound of the present invention can be obtained, for example, by the following method. Organic halogen compounds such as benzyl bromide, benzhydryl bromide, ethyl bromoacetate, cinnamyl bromide, crotyl bromide and α or β-bromomethylnaphthalene, or dialkyl sulfuric acid such as dimethylsulfate and diethylsulfate, methyl p-toluenesulfonate. And sulfonic acid ester compounds such as cinnamyl benzene sulfonate and benzyl methane sulfonate, and N- (2-acetoxyethyl) -N-ethyl-m-
Toluidine and N- (2-hydroxyethyl) -N- (2
N-N-disubstituted aniline derivative such as -cyanoethyl) aniline, if necessary, ethyl acetate, butyl acetate,
Toluene, acetonitrile, methanol, ethanol,
In the presence of an inert solvent such as dioxane or ethyl methyl ketone, the reaction is carried out at room temperature to 100 ° C. for several hours to several days, and then the obtained compound is dissolved in water or a water-organic solvent such as water-methanol, It can be obtained by adding an alkali salt of a non-nucleophilic anion such as potassium fluorinated antimonate, stirring vigorously, separating the precipitated product by extraction, etc., purifying if necessary, and drying. On the other hand, an anilinium salt of the general formula (1) in which R 1 is a hydrogen atom is obtained by reacting an N, N-disubstituted aniline derivative with a monovalent acid such as hydrochloric acid and then treating the resulting compound with water or water-organic It can be obtained by dissolving in a solvent, adding an alkali salt of a non-nucleophilic anion, stirring vigorously, separating the precipitated product by extraction, etc., purifying if necessary, and drying. (Specific Examples of Anilinium Salt Compound) The following compounds are exemplified as typical anilinium salt compounds of the present invention. However, X in the formula is BF 4 , PF 6 ,
It represents a non-nucleophilic counter anion residue such as AsF 6 , SbF 6 , SbCl 6 , ClO 4 , and FeO 4 . (Polymerizable Compound) The cationically polymerizable compound used in the present invention can be used without any limitation as long as it is a generally known monomer, oligomer or polymer having a cationically polymerizable property. The following is exemplified. (A) As vinyl compounds, styrene compounds such as styrene, α-methylstyrene, p-methoxystyrene, pt-butoxystyrene, methyl vinyl ether, n-butyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, 2
-Alkyl vinyl ether compounds such as chloroethyl vinyl ether, 2-phenoxyethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, 2-acetoxyethyl vinyl ether, allyl vinyl ether, 2-methacryloyloxyethyl vinyl ether, 2-acryloyl Alkenyl vinyl ether compounds such as oxyethyl vinyl ether, phenyl vinyl ether, aryl vinyl ether compounds such as p-methoxyphenyl vinyl ether, N-vinylcarbazole, N
-Cationically polymerizable nitrogen-containing compounds such as vinylpyrrolidone, butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, 1,4-benzenedimethanol divinyl ether, hydroquinone divinyl ether, sazolcinol divinyl ether, and other polyfunctional compounds Vinyl compounds may be mentioned. (B) As an epoxy compound, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether,
Butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2
-Dodecylene oxide, epichlorohydrin, 1,2-
Monofunctional monomers such as epoxydecane, ethylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethyl cyclohexene oxide, 3-acryloyloxymethyl cyclohexene oxide, and 3-vinylcyclohexene oxide, 1,1,3-tetradeca Dienedioxide, limonenedioxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxycyclohexyl) carboxylate, di (3,4-epoxycyclohexyl) adipate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, Bisphenol S type epoxy resin, halogenated bisphenol A type epoxy resin, o
-, M-, p- cresol novolac type epoxy resin, halogenated o-, m-, p- cresol novolac type epoxy resin, phenol novolac type epoxy resin, polyfunctional epoxy compounds such as polyglycidyl ether of polyhydric alcohol To be (C) 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2
2] octane, 1-ethyl-4-hydroxymethyl-2,
Examples thereof include compounds such as 6,7-trioxabicyclo [2,2,2] octane. (D) 1,5,7, as spiro-orthocarbonate compound
11-Tetraoxaspiro [5,5] undecane, 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5,5] undecane, 1,4,6-trioxaspiro [4,4] Nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane, 1,4,6
And compounds such as trioxaspiro [4,5] decane. In addition, these may be used alone or in combination of two or more kinds. (Curing Agent) In the present invention, when an anilinium salt compound is used as a curing agent, the compounding ratio of the anilinium salt compound and the cationically polymerizable compound is 0.01 to 10 parts of the anilinium salt compound, preferably 100 parts of the cationically polymerizable compound. is 0.
It is mixed in a ratio of 1 to 5 parts. When the amount of this anilinium salt compound is small, the curability of the cationically polymerizable compound decreases,
If it is excessive, the properties of the cured product deteriorate. The cationically polymerizable compound containing the anilinium salt compound of the present invention can be easily cured by heating. Curing temperature is 10 ℃ ~ 220 ℃, preferably 30 ℃ ~ 200
C., more preferably in the range of 50 to 180.degree. The cationically polymerizable compound containing the anilinium salt compound of the present invention can also be cured by ionizing radiation such as α rays, β rays, γ rays, neutron rays, X rays, and accelerated electron rays. (Polymerization Initiator) As the solvent used when the anilinium salt compound of the present invention is used as a polymerization initiator, a solvent such as toluene, methylene chloride or chloroform which is usually used in cationic polymerization can be used. In addition, ester solvents such as ethyl acetate and ketone solvents such as methyl ethyl ketone can be used, and the degree of polymerization can be controlled by the solvent used. Therefore, it is possible to polymerize in acrylic acid ester monomers such as ethyl acrylate and 1,4-butanediol dimethacrylate. By utilizing this point, a curable acrylic paint can be easily prepared without purification. The use ratio of the anilinium salt compound and the cationically polymerizable monomer can be arbitrarily set depending on the desired molecular weight of the polymer. On the other hand, for the purpose of controlling the polymerization, a polymerization control agent such as dioxane may be added to control the polymerization rate, molecular weight and dispersity. Further, a compound having a hydroxyl group such as ethanol or ethylene glycol can be used as a chain transfer agent,
This makes it possible to adjust the molecular weight. Furthermore, for example, when a compound having a functional group such as 2-hydroxyethyl methacrylate is used as a chain transfer agent, a functional group such as a methacrylic group can be introduced into the polymer. Since the anilinium salt compound used as the polymerization initiator of the present invention has excellent activity, it is possible to restart the polymerization by adding a monomer even after the polymerization is once completed. A polymer can be obtained without problems even if it is repeated. Further, the polymerization can be obtained even when it contains some water. Therefore, the concentration of the polymer in the polymerization solvent system can be arbitrarily set to some extent.
（実施例）
以下、本発明を実施例、比較例により、更に具体的に
説明する。但し、化合物No.は、表中のNo.を示す。
A.アニリニウム塩化合物の合成
（１）合成例１
Ｎ−エチル−Ｎ−メチル−Ｎ−〔２−（２−カルボキシ
−３−メチル−シクロヘキシルカルボニルオキシ）エチ
ル〕−ｍ−メチルアニリニウムヘキサフルオロアンチモ
ネートの合成（化合物No.2）
Ｎ−エチル−Ｎ−〔２−（２−カルボキシ−３−メチ
ル−シクロヘキシルカルボニルオキシ）エチル〕−ｍ−
メチルアニリン34.75gとジメチル硫酸12.61gを酢酸ブチ
ル20mlに溶解させ、100℃で８時間反応させた。得られ
た液状物を蒸留水100gに溶解させ、六フッ化アンチモン
酸カリウム27.48gを加え、十分に攪拌したのち冷却し
た。この溶液に酢酸エチルを加え、分液、濃縮し、濃縮
物を40℃で乾燥した。収率:95％
（２）合成例２
Ｎ−エチル−Ｎ−エチル−Ｎ−〔２−（２−カルボキシ
−３−メチル−シクロヘキシルカルボニルオキシ）エチ
ル〕−ｍ−メチルアニリニウムヘキサフルオロアンチモ
ネートの合成（化合物No.3）
Ｎ−エチル−Ｎ−〔２−（２−カルボキシ−３−メチ
ル−シクロヘキシルカルボニルオキシ）エチル〕−ｍ−
メチルアニリン34.75gとジエチル硫酸15.42gを酢酸ブチ
ル20mlに溶解させ、100℃で８時間反応させた。得られ
た液状物を蒸留水100gに溶解させ、六フッ化アンチモン
酸カリウム27.48gを加え、十分に攪拌したのち冷却し
た。この溶液に酢酸エチルを加え、分液、濃縮し、濃縮
物を40℃で乾燥した。収率:96％
（合成例３）
Ｎ−エトキシカルボニルメチル−N,N−ジ（２−ヒドロ
キシエチル）−ｍ−メチルアニリウムヘキサフルオロア
ンチモネートの合成（化合物No.11）
プロモ酢酸エチル5.01gとN,N−ジ（２−ヒドロキシエ
チル）−ｍ−メチルアニリン5.86gとを混合し、50℃で2
4日間反応させた。得られた液状物をエーテルで洗浄
し、40℃で減圧乾燥し、前駆体であるＮ−エトキシカル
ボニルメチル−N,N−ジ（２−ヒドロキシエチル）−ｍ
−メチルアニリウムブロマイドを得た。収率:57％
Ｎ−エトキシカルボニルメチル−N,N−ジ（２−ヒド
ロキシエチル）−ｍ−メチルアニリウムブロマイド3.62
gを蒸留水5mlとメチルエチルケトン2gの混合溶液に溶解
させ、六フッ化アンチモン酸カリウム3.30gを加え、十
分に攪拌したのち冷却した。この液に蒸留水45mlを加
え、十分に攪拌し、二層分離した溶液を分液後、40℃で
減圧乾燥して目的を得た。収率:46％
（合成例４）
Ｎ−フェナシル−N,N−ジ（２−ヒドロキシエチル）−
ｍ−メチルアニリニウムヘキサフルオロアンチモネート
の合成（化合物No.13）
N,N−ジ（２−ヒドロキシエチル）−ｍ−メチルアニ
リン7.81g、及びフェナシルブロマイド7.96gを混合し
て、50℃にて30日間反応させ、得られた液状物をエーテ
ルで洗浄し、40℃で減圧乾燥し、前駆体であるＮ−フェ
ナシル−N,N−ジ（２−ヒドロキシエチル）−ｍ−メチ
ルアニリニウムブロマイドを得た。収率:96％
Ｎ−フェナシル−N,N−ジ（２−ヒドロキシエチル）
−ｍ−メチルアニリニウムブロマイド3.94gを蒸留水5ml
とメチルエチルケトン2gの混合溶液に溶解させ、六フッ
化アンチモン酸カリウム3.30gを加え、十分に攪拌した
のち冷却した。この液に蒸留水45mlを加え、十分に攪拌
し、二層分離した溶液を分液後、40℃で減圧乾燥した目
的物を得た。収率:66％
（合成例５）
Ｎ−ベンジル−Ｎ−（２−ヒドロキシエチル）−Ｎ−
（２−シアノエチル）−アニリニウムヘキサフルオロア
ンチモネートの合成（化合物No.17）
ベンジルブロマイド5.13gとＮ−（２−シアノエチ
ル）−Ｎ−（２−ヒドロキシエチル）アニリン5.71gを
混合し、50℃で３日間反応させた。得られた固形物をエ
ーテルで洗浄し、40℃で減圧乾燥し、前駆体のＮ−ベン
ジル−Ｎ−（２−シアノエチル）−Ｎ−（２−ヒドロキ
シエチル）アニリニウムブロマイドを得た。収率:98％
次いで、Ｎ−ベンジル−Ｎ−（２−シアノエチル）−
Ｎ−（２−ヒドロキシエチル）アニリニウムブロマイド
3.61gを蒸留水5gとメチルエチルケトン2gの混合溶液に
溶解させ、六フッ化アンチモン酸カリウム3.30gを加
え、十分に攪拌したのち冷却した。この液に蒸留水45g
を加え、よく攪拌し二層分離した溶液を分液後、40℃で
減圧乾燥して目的物を得た。収率:66％
（合成例６）
Ｎ−エチル−Ｎ−ベンジル−Ｎ−（３−ブトキシ−２−
ヒドロキシプロピル）アニリニウムヘキサイフルオロア
ンチモネートの合成（化合物No.21）
Ｎ−エチル−Ｎ−ベンジルアニリンのｐ−トルエンス
ルホン酸塩38.53gとブチルグリシリルエーテル13.02gと
を混合し、120℃で12時間反応させた。得られた液状物
を蒸留水100gに溶解させ、六フッ化アンチモン酸カリウ
ム27.48gを加え、十分に攪拌したのち冷却した。この溶
液に酢酸エチルを加えて分液し、二層分離した溶液を分
離後、濃縮し、濃縮物を40℃で減圧乾燥した。収率:98
％
（合成例７）
Ｎ−シンナミル−Ｎ−（２−ヒドロキシエチル）−Ｎ−
（２−シアノエチル）アニリニウムヘキサフルオロアン
チモネートの合成（化合物No.24）
シンナミルブロマイド5.91gとＮ−（２−ヒドロキシ
エチル）−Ｎ−（２−シアノエチル）アニリン5.91gと
を混合し、室温で２日間反応させた。得られた固形物を
エーテルで洗浄し、40℃で減圧乾燥し、前駆体のＮ−シ
ンナミル−（２−ヒドロキシ）−Ｎ−（２−シアノエチ
ル）アニリニウムブロマイドを得た。収率:99％
Ｎ−シンナミル−Ｎ−（２−ヒドロキシ）−Ｎ−（２
−シアノエチル）アニリニウムブロマイド3.87gを蒸留
水5gとメチルエチルケトン2gの混合溶液に溶解させ、六
フッ化アンチモン酸カリウム3.30gを加え、十分に攪拌
したのち冷却した。この液に蒸留水45gを加え、よく攪
拌し、二層分離した溶液を分液後、40℃で減圧乾燥し
た。収率:76％
（合成例８）
Ｎ−（２−アセトキシエチル）−Ｎ−（２−シアノエチ
ル）−Ｎ−ベンズヒドリル−ｍ−メチルアニリニウムヘ
キサフルオロアンチモネートの合成（化合物No.29）
Ｎ−（２−アセトキシエチル）−Ｎ−（２−シアノエ
チル）−ｍ−トルイジン10.56gとベンズヒドリルブロマ
イド7.41gとを混合して、50℃で24時間反応させた。得
られた固形物をエーテルで洗浄し、40℃で減圧乾燥し、
前駆体のＮ−（２−アセトキシエチル）−Ｎ−（２−シ
アノエチル）−Ｎ−ベンズヒドリル−ｍ−メチルアニリ
ニウムブロマイドを得た。収率:98％
Ｎ−（２−アセトキシエチル）−Ｎ−（２−シアノエ
チル）−Ｎ−ベンズヒドリル−ｍ−メチルアニリニウム
ブロマイド4.93gを蒸留水5gとメチルエチルケトン2gの
混合溶液に溶解させ、六フッ化アンチモン酸カリウム3.
30gを加え、十分に攪拌したのち冷却した。この液に蒸
留水45gを加え、よく攪拌し、二層分離した溶液を分液
後、40℃で減圧乾燥した。収率:78％
上記合成例１〜８の化合物を含め、以下の硬化性テス
ト及び重合性テストに使用した化合物の構造式、及びIR
スペクトルデーターを下記の表−１〜表−８に纏めて示
した。
B. 〈硬化性テスト〉
（１）DSC測定
合成したアニリニウム塩化合物をプロピレンカーボネ
ートに溶解させ、ERL−4221（UCC社製脂環型エポキシ）
およびUVR−6410（UCC社製グリシジル型エポキシ）に純
分として2.5部になるように各エポキシ化合物に添加
し、配合物を調製した。この配合物についてDSC測定を
行い、発熱開始温度とピークのトップ温度を求めた。
なお、DSCの測定条件は下記の通りであり、その測定
結果を表−９〜表−13に纏めて示した。
DSC測定機器:DSC220C（セイコー電子工業社製）
雰囲気 :窒素ガス気流中 30ml/分
昇温速度 :10℃／分
サンプル量 :0.3〜0.8mg
（比較試料１）
対比として、Ｎ−メチル−Ｎ−エチル−Ｎ−ベンジル
アニリウムヘキサフロロアンチモネートを重合開始剤に
用い、実施例と同様にDSC測定を行った。
（比較試料２）
Ｎ−（α−フェネチル）−N,N−ジメチル−Ｎ−（２
−ヒドロキシエチル）アンモニウムヘキサフロロアンチ
モネートを開始剤に用い、実施例と同様にしてERL−422
1（UCC社製脂環型エポキシ）およびUVR−6410（UCC社製
グリシジル型エポキシ）エポキシ化合物に添加して配合
物を調製し、DSC測定を行い、発熱ピークのトップ温度
を求めた。これらの結果を表−10及び表−12に纏めて示
した。
（２）粘弾性測定
上記で調製した配合物を130℃で30分硬化させ、その
試験片を粘弾性測定を行った。得られたスペクトルの損
失弾性率のピークを試験片のガラス転移温度とした。そ
の測定結果を表−13に示した。
（比較試料３）
Ｎ−（α−フェネチル）−N,N−ジメチル−ｐ−プロ
モアニリニウムヘキサロロアンチモネートを開始剤に用
い、実施例と同様に配合物を調製し、粘弾性測定を行っ
た。
C. 〈重合性テスト〉
フラスコ中で各溶媒にモノマーを溶解（必要に応じて
連鎖移動剤も溶解させておく）させ、各温度に保ち、メ
チルエチルケトンに溶解させたアニリニウム塩化合物を
加え、所定時間攪拌した。この溶液を直接GPC測定し、
分子量を求めた。分子量は、ポリスチレンをスタンダー
ドとした場合の値を示し、その結果を表−14に示した。
ここで使用したモノマー、溶媒および連鎖移動剤は、
次のようなものである。
１）モノマ−
CHO :シクロヘキセンオキサイド
Ｍ−100:3−メタクリロイルオキシメチルシクロヘキ
センオキサイド
IBVI :イソブチルビニルエーテル
PGE :フェニルグリシジルエーテル
SO :スチレンオキサイド
２）溶媒
CF:クロロホルム
T :トルエン
EA:酢酸エチル
３）連鎖移動剤
HEMA:2−ヒドロキシエチルメタクリレート
（発明の効果）
以上説明したように、本発明は、一般式（Ｉ）で示さ
れる新規なアニリニウム塩化合物及び該化合物の少なく
とも１種を含有することを特徴とするカチオン重合開始
剤であり、本発明のアニリニウム塩化合物は、以下の特
徴を有する。
（１）その置換基の適当な選択により、重合体の合成や
瞬間硬化用の重合開始剤、及びエポキシ化合物等の硬化
剤として使い分けすることができる。
（２）本発明の化合物を重合開始剤として使用した場合
には、重合開始温度が常温から100℃付近の温和な条件
下でで簡便にビニルエーテルやエポキシ化合物等のカチ
オン重合性モノマーを容易に重合させることができる。
また、触媒活性に優れているため、系内からモノマー
が消失したのち、さらにモノマーを加えることにより再
び重合を開始させることができ、溶媒の選択及び水酸基
を有する化合物のような連鎖移動剤を使用すると分子量
の調製が可能である。
（３）本発明の化合物を硬化用触媒としても用いた場合
には、常温から170℃付近の比較的低い温度において容
易に硬化させることができ、開始反応の際に脱離する成
分によって重合停止が起こりにくいため、架橋密度やガ
ラス転移温度が高い、優れた物性を有する硬化物を得る
ことができる。(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the compound No. indicates the No. in the table. A. Synthesis of anilinium salt compound (1) Synthesis example 1 N-ethyl-N-methyl-N- [2- (2-carboxy-3-methyl-cyclohexylcarbonyloxy) ethyl] -m-methylanilinium hexafluoroantimomo Synthesis of nate (Compound No. 2) N-ethyl-N- [2- (2-carboxy-3-methyl-cyclohexylcarbonyloxy) ethyl] -m-
34.75 g of methylaniline and 12.61 g of dimethylsulfate were dissolved in 20 ml of butyl acetate and reacted at 100 ° C. for 8 hours. The obtained liquid material was dissolved in 100 g of distilled water, 27.48 g of potassium hexafluoroantimonate was added, and the mixture was sufficiently stirred and then cooled. Ethyl acetate was added to this solution, liquid separation and concentration were carried out, and the concentrate was dried at 40 ° C. Yield: 95% (2) Synthesis Example 2 N-ethyl-N-ethyl-N- [2- (2-carboxy-3-methyl-cyclohexylcarbonyloxy) ethyl] -m-methylanilinium hexafluoroantimonate Synthesis (Compound No. 3) N-ethyl-N- [2- (2-carboxy-3-methyl-cyclohexylcarbonyloxy) ethyl] -m-
34.75 g of methylaniline and 15.42 g of diethylsulfate were dissolved in 20 ml of butyl acetate and reacted at 100 ° C. for 8 hours. The obtained liquid material was dissolved in 100 g of distilled water, 27.48 g of potassium hexafluoroantimonate was added, and the mixture was sufficiently stirred and then cooled. Ethyl acetate was added to this solution, liquid separation and concentration were carried out, and the concentrate was dried at 40 ° C. Yield: 96% (Synthesis Example 3) Synthesis of N-ethoxycarbonylmethyl-N, N-di (2-hydroxyethyl) -m-methylanilium hexafluoroantimonate (Compound No. 11) Ethyl bromoacetate 5.01 g And N, N-di (2-hydroxyethyl) -m-methylaniline (5.86 g) were mixed, and the mixture was mixed at 50 ° C for 2
The reaction was carried out for 4 days. The obtained liquid material was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-ethoxycarbonylmethyl-N, N-di (2-hydroxyethyl) -m.
-Methylanillium bromide was obtained. Yield: 57% N-ethoxycarbonylmethyl-N, N-di (2-hydroxyethyl) -m-methylanilium bromide 3.62
g was dissolved in a mixed solution of 5 ml of distilled water and 2 g of methyl ethyl ketone, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was sufficiently stirred and cooled. Distilled water (45 ml) was added to this solution, and the mixture was sufficiently stirred, and the solution obtained by separating the two layers was separated and dried under reduced pressure at 40 ° C. to obtain the object. Yield: 46% (Synthesis example 4) N-phenacyl-N, N-di (2-hydroxyethyl)-
Synthesis of m-methylanilinium hexafluoroantimonate (Compound No. 13) N, N-di (2-hydroxyethyl) -m-methylaniline 7.81 g and phenacyl bromide 7.96 g were mixed and heated to 50 ° C. The resulting liquid was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-phenacyl-N, N-di (2-hydroxyethyl) -m-methylanilinium bromide. Got Yield: 96% N-phenacyl-N, N-di (2-hydroxyethyl)
-M-methylanilinium bromide 3.94g distilled water 5ml
It was dissolved in a mixed solution of 2 g of methyl ethyl ketone and 3.30 g of potassium hexafluoroantimonate, and the mixture was sufficiently stirred and cooled. Distilled water (45 ml) was added to this liquid, and the mixture was sufficiently stirred to separate the solution obtained by separating the two layers and then dried under reduced pressure at 40 ° C. to obtain the desired product. Yield: 66% (Synthesis example 5) N-benzyl-N- (2-hydroxyethyl) -N-
Synthesis of (2-cyanoethyl) -anilinium hexafluoroantimonate (Compound No. 17) 5.13 g of benzyl bromide and 5.71 g of N- (2-cyanoethyl) -N- (2-hydroxyethyl) aniline were mixed, and the mixture was heated to 50 ° C. And reacted for 3 days. The obtained solid was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-benzyl-N- (2-cyanoethyl) -N- (2-hydroxyethyl) anilinium bromide. Yield: 98% Next, N-benzyl-N- (2-cyanoethyl)-
N- (2-hydroxyethyl) anilinium bromide
3.61 g was dissolved in a mixed solution of 5 g of distilled water and 2 g of methyl ethyl ketone, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was sufficiently stirred and cooled. 45g of distilled water in this liquid
Was added, and the mixture was well stirred and the two layers were separated, and the solution was separated and dried under reduced pressure at 40 ° C. to obtain the desired product. Yield: 66% (Synthesis example 6) N-ethyl-N-benzyl-N- (3-butoxy-2-
Synthesis of (hydroxypropyl) anilinium hexaifluoroantimonate (Compound No. 21) 38.53 g of p-toluenesulfonic acid salt of N-ethyl-N-benzylaniline and 13.02 g of butyl glycyl ether were mixed, and at 120 ° C. The reaction was carried out for 12 hours. The obtained liquid material was dissolved in 100 g of distilled water, 27.48 g of potassium hexafluoroantimonate was added, and the mixture was sufficiently stirred and then cooled. Ethyl acetate was added to this solution for liquid separation, the two layers of the solution were separated and concentrated, and the concentrate was dried under reduced pressure at 40 ° C. Yield: 98
% (Synthesis example 7) N-cinnamyl-N- (2-hydroxyethyl) -N-
Synthesis of (2-cyanoethyl) anilinium hexafluoroantimonate (Compound No. 24) 5.91 g of cinnamyl bromide and 5.91 g of N- (2-hydroxyethyl) -N- (2-cyanoethyl) aniline were mixed at room temperature. And reacted for 2 days. The obtained solid was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor N-cinnamyl- (2-hydroxy) -N- (2-cyanoethyl) anilinium bromide. Yield: 99% N-cinnamyl-N- (2-hydroxy) -N- (2
3.87 g of -cyanoethyl) anilinium bromide was dissolved in a mixed solution of 5 g of distilled water and 2 g of methyl ethyl ketone, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was sufficiently stirred and cooled. Distilled water (45 g) was added to this liquid, and the mixture was stirred well, and the solution obtained by separating the two layers was separated and dried under reduced pressure at 40 ° C. Yield: 76% (Synthesis Example 8) Synthesis of N- (2-acetoxyethyl) -N- (2-cyanoethyl) -N-benzhydryl-m-methylanilinium hexafluoroantimonate (Compound No. 29) N- 10.56 g of (2-acetoxyethyl) -N- (2-cyanoethyl) -m-toluidine and 7.41 g of benzhydryl bromide were mixed and reacted at 50 ° C. for 24 hours. The obtained solid was washed with ether and dried under reduced pressure at 40 ° C,
A precursor N- (2-acetoxyethyl) -N- (2-cyanoethyl) -N-benzhydryl-m-methylanilinium bromide was obtained. Yield: 98% N- (2-acetoxyethyl) -N- (2-cyanoethyl) -N-benzhydryl-m-methylanilinium bromide (4.93 g) was dissolved in a mixed solution of distilled water (5 g) and methyl ethyl ketone (2 g), and mixed with hexafluoride. Potassium antimonate 3.
30 g was added, and the mixture was sufficiently stirred and then cooled. Distilled water (45 g) was added to this liquid, and the mixture was stirred well, and the solution obtained by separating the two layers was separated and dried under reduced pressure at 40 ° C. Yield: 78% Structural formulas of compounds used in the following curability test and polymerization test, including the compounds of Synthesis Examples 1 to 8 and IR
Spectral data are summarized in Tables 1 to 8 below. B. <Curing test> (1) DSC measurement The synthesized anilinium salt compound was dissolved in propylene carbonate, and ERL-4221 (UCC alicyclic epoxy)
And UVR-6410 (glycidyl type epoxy manufactured by UCC Co., Ltd.) was added to each epoxy compound so as to have a pure content of 2.5 parts to prepare a formulation. A DSC measurement was performed on this blend to determine the exothermic onset temperature and peak top temperature. The measurement conditions of DSC are as follows, and the measurement results are summarized in Table-9 to Table-13. DSC measuring device: DSC220C (manufactured by Seiko Denshi Kogyo Co., Ltd.) Atmosphere: Nitrogen gas stream 30 ml / min Temperature rising rate: 10 ° C / min Sample amount: 0.3-0.8 mg (Comparative sample 1) As a comparison, N-methyl-N- Using ethyl-N-benzylanilium hexafluoroantimonate as a polymerization initiator, DSC measurement was carried out in the same manner as in Examples. (Comparative Sample 2) N- (α-phenethyl) -N, N-dimethyl-N- (2
-Hydroxyethyl) ammonium hexafluoroantimonate was used as the initiator and ERL-422 was prepared in the same manner as in the example.
1 (UCC alicyclic epoxy) and UVR-6410 (UCC glycidyl epoxy) were added to the epoxy compound to prepare a mixture, and DSC measurement was performed to determine the top temperature of the exothermic peak. These results are summarized in Table-10 and Table-12. (2) Viscoelasticity measurement The composition prepared above was cured at 130 ° C for 30 minutes, and the test piece was subjected to viscoelasticity measurement. The peak of loss elastic modulus of the obtained spectrum was defined as the glass transition temperature of the test piece. The measurement results are shown in Table-13. (Comparative Sample 3) Using N- (α-phenethyl) -N, N-dimethyl-p-promoanilinium hexaloroantimonate as an initiator, a formulation was prepared in the same manner as in Example, and viscoelasticity measurement was performed. It was C. <Polymerization test> Dissolve the monomer in each solvent in the flask (dissolve the chain transfer agent if necessary), keep it at each temperature, add the anilinium salt compound dissolved in methyl ethyl ketone, and add it for a predetermined time. It was stirred. This solution is directly measured by GPC,
The molecular weight was determined. The molecular weight shows the value when polystyrene is used as the standard, and the results are shown in Table-14. The monomers, solvents and chain transfer agents used here are
It looks like this: 1) Monomer CHO: Cyclohexene oxide M-100: 3-methacryloyloxymethyl cyclohexene oxide IBVI: Isobutyl vinyl ether PGE: Phenyl glycidyl ether SO: Styrene oxide 2) Solvent CF: Chloroform T: Toluene EA: Ethyl acetate 3) Chain transfer agent HEMA: 2-hydroxyethyl methacrylate (Effects of the Invention) As described above, the present invention is a cationic polymerization initiator characterized by containing a novel anilinium salt compound represented by the general formula (I) and at least one of the compounds, The anilinium salt compound of the present invention has the following features. (1) By appropriately selecting the substituent, it can be properly used as a polymerization initiator for polymer synthesis or instant curing, and a curing agent such as an epoxy compound. (2) When the compound of the present invention is used as a polymerization initiator, a cationically polymerizable monomer such as vinyl ether or an epoxy compound can be easily and easily polymerized under mild conditions where the polymerization initiation temperature is from room temperature to about 100 ° C. Can be made. In addition, since it has excellent catalytic activity, after the monomer disappears from the system, the polymerization can be restarted by adding another monomer, and the selection of a solvent and the use of a chain transfer agent such as a compound having a hydroxyl group are used. Then, the molecular weight can be adjusted. (3) When the compound of the present invention is also used as a curing catalyst, it can be easily cured at a relatively low temperature from room temperature to 170 ° C., and the polymerization is stopped by a component that is eliminated during the initiation reaction. Is less likely to occur, a cured product having a high crosslink density and a high glass transition temperature and excellent physical properties can be obtained.
本発明の新規アニリニウム塩化合物は、カチオン重合
開始剤として利用でき、本発明のアニリニウム塩化合物
を含有するカチオン重合性組成物は、新しい重合体の合
成や成型樹脂、注型樹脂、塗料、接着剤、インキ等の材
料として好適である。The novel anilinium salt compound of the present invention can be used as a cationic polymerization initiator, and a cationically polymerizable composition containing the anilinium salt compound of the present invention can be used for the synthesis of new polymers, molding resins, casting resins, paints, adhesives. Suitable as a material for ink, ink, etc.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０７Ｃ 219/06 Ｃ０７Ｃ 219/06 219/12 219/12 219/14 219/14 225/06 225/06 225/16 225/16 229/18 229/18 229/38 229/38 229/60 229/60 237/30 237/30 255/42 255/42 Ｃ０８Ｆ 4/00 Ｃ０８Ｆ 4/00 Ｃ０８Ｇ 59/68 Ｃ０８Ｇ 59/68 65/10 65/10 85/00 85/00 (31)優先権主張番号 特願平5−132896 (32)優先日 平成５年５月11日(1993．5．11) (33)優先権主張国 日本（ＪＰ） (31)優先権主張番号 特願平5−297374 (32)優先日 平成５年11月２日(1993．11．2) (33)優先権主張国 日本（ＪＰ） (31)優先権主張番号 特願平5−86980 (32)優先日 平成５年３月15日(1993．3．15) (33)優先権主張国 日本（ＪＰ） (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 211/00 C07C 215/00 C07C 217/00 C07C 219/00 C07C 225/00 C07C 229/00 C07C 237/00 C07C 255/00 C08F 4/00 C08G 59/00 C08G 65/00 C08G 85/00 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI C07C 219/06 C07C 219/06 219/12 219/12 219/14 219/14 225/06 225/06 225/16 225/16 229/18 229/18 229/38 229/38 229/60 229/60 237/30 237/30 255/42 255/42 C08F 4/00 C08F 4/00 C08G 59/68 C08G 59/68 65/10 65 / 10 85/00 85/00 (31) Priority claim number Japanese Patent Application No. 5-132896 (32) Priority date May 11, 1993 (May 11, 1993) (33) Country of priority claim Japan (JP ) (31) Priority claim number Japanese Patent Application No. 5-297374 (32) Priority date November 2, 1993 (November 2, 1993) (33) Priority claim country Japan (JP) (31) Priority claim Number Japanese Patent Application No. 5-86980 (32) Priority date March 15, 1993 (March 15, 1993) (33) Priority claiming country Japan (JP) (58) Fields investigated (Int.Cl. 7 , DB name) C07C 211/00 C07C 215/00 C07C 217/00 C07C 21 9/00 C07C 225/00 C07C 229/00 C07C 237/00 C07C 255/00 C08F 4/00 C08G 59/00 C08G 65/00 C08G 85/00 CA (STN) REGISTRY (STN)
Claims (3)
塩化合物 一般式（Ｉ） 〔式中、 R1が、水素原子、アルキル基を表す場合、R2は、窒素原
子のβ位に水酸基、シアノ基及びアシルオキシ基からな
る群から選ばれる一種の置換基を有するアルキル基を表
し、R3は、窒素原子のβ位にシアノ基及びアシルオキシ
基からなる選ばれる一種の置換基を置換基として有する
アルキル基を表し、 R1が、窒素原子のβ位の炭素が不飽和結合であるアルケ
ニル基またはアルキニル基；窒素原子のα位の炭素にエ
ステル又はカルボニル基を有するアルキル基；アルキル
基、ハロゲン原子、アルケニル基、及びアルコキシカル
ボニル基からなる群から選ばれる一種の置換基を芳香環
に有してもよいベンジル基；α−フェニルベンジル基；
α−ナフチルメチル基；またはβ−ナフチルメチル基を
表す場合、R2はアルキル基、又は窒素原子のβ位の炭素
に水酸基、シアノ基、アシルオキシ基、及びハロゲン原
子からなる群から選ばれる一種の置換基を有するアルキ
ル基を表し、R3は、窒素原子のβ位の炭素に水酸基、シ
アノ基、アシルオキシ基、及びハロゲン原子からなる群
から選ばれる一種の置換基を有するアルキル基を表し、 R4、R5は、それぞれ水素原子、ハロゲン原子、アルコキ
シ基、ニトロ基、シアノ基又はアルカノイル基の何れか
一種を表し、R4とR5とは、一体となって芳香環を形成し
てもよい。また、Ｘは、非求核性の対アニオン残基を表
す〕1. An anilinium salt compound represented by the following general formula (I): general formula (I) (In the formula, when R 1 represents a hydrogen atom or an alkyl group, R 2 represents an alkyl group having one substituent selected from the group consisting of a hydroxyl group, a cyano group and an acyloxy group at the β-position of the nitrogen atom. , R 3 represents an alkyl group having as a substituent one kind of substituent selected from a cyano group and an acyloxy group at the β-position of the nitrogen atom, and R 1 represents an unsaturated bond at the β-position carbon of the nitrogen atom. An alkenyl group or alkynyl group; an alkyl group having an ester or a carbonyl group at the carbon at the α-position of the nitrogen atom; an aromatic ring having one substituent selected from the group consisting of an alkyl group, a halogen atom, an alkenyl group, and an alkoxycarbonyl group A benzyl group which may have; α-phenylbenzyl group;
When representing an α-naphthylmethyl group; or a β-naphthylmethyl group, R 2 is an alkyl group, or a kind selected from the group consisting of a hydroxyl group on the β-position carbon of the nitrogen atom, a cyano group, an acyloxy group, and a halogen atom. Represents an alkyl group having a substituent, R 3 represents an alkyl group having one substituent selected from the group consisting of a hydroxyl group, a cyano group, an acyloxy group, and a halogen atom on the carbon at the β-position of the nitrogen atom, R 3 4 and R 5 each represent any one of a hydrogen atom, a halogen atom, an alkoxy group, a nitro group, a cyano group or an alkanoyl group, and R 4 and R 5 together form an aromatic ring. Good. X represents a non-nucleophilic counter anion residue]
少なくとも一種を含有することを特徴とするカチオン重
合開始剤2. A cationic polymerization initiator comprising at least one kind of the anilinium salt compound according to claim 1.
合物の少なくとも一種及びカチオン重合化合物を含有す
ることを特徴とするカチオン重合性組成物。3. A cationically polymerizable composition containing at least one of the anilinium salt compound according to claim 1 and a cationically polymerized compound.
Applications Claiming Priority (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35950392 | 1992-12-25 | ||
| JP4-359503 | 1992-12-25 | ||
| JP5-86980 | 1993-03-15 | ||
| JP8017193 | 1993-03-15 | ||
| JP8698093 | 1993-03-15 | ||
| JP5-80171 | 1993-03-15 | ||
| JP10024193 | 1993-04-02 | ||
| JP5-100241 | 1993-04-02 | ||
| JP13289693 | 1993-05-11 | ||
| JP5-132896 | 1993-05-11 | ||
| JP29737493 | 1993-11-02 | ||
| JP5-297374 | 1993-11-02 | ||
| PCT/JP1993/001876 WO1994014754A1 (en) | 1992-12-25 | 1993-12-24 | Novel anilinium salt compound and polymerization initiator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO1994014754A1 JPWO1994014754A1 (en) | 1995-02-02 |
| JP3517240B2 true JP3517240B2 (en) | 2004-04-12 |
Family
ID=27551478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51500994A Expired - Fee Related JP3517240B2 (en) | 1992-12-25 | 1993-12-24 | New anilinium salt compound and polymerization initiator |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3517240B2 (en) |
| WO (1) | WO1994014754A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10179832B2 (en) * | 2014-04-15 | 2019-01-15 | Henkel Ag & Co. Kgaa | Storage stable heat activated quaternary ammonium catalysts for epoxy cure |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12418027B2 (en) | 2021-02-16 | 2025-09-16 | Lyten, Inc. | Plasticizer-inclusive polymeric-inorganic hybrid layer for a lithium anode in a lithium-sulfur battery |
| US12476274B2 (en) | 2021-02-16 | 2025-11-18 | Lyten, Inc. | Polymeric-inorganic hybrid layer for a lithium anode |
| US12444749B2 (en) | 2021-07-23 | 2025-10-14 | Lyten, Inc. | Anode protective layer for lithium-sulfur cylindrical cells |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1512982A (en) * | 1974-05-02 | 1978-06-01 | Gen Electric | Salts |
| JPS6344655A (en) * | 1986-08-13 | 1988-02-25 | Fuji Photo Film Co Ltd | Color photographic developer composition and method for processing silver halide color photographic sensitive material |
| JPH0737426B2 (en) * | 1989-06-05 | 1995-04-26 | 日本ペイント株式会社 | New benzyl ammonium salt |
| US5126225A (en) * | 1991-07-18 | 1992-06-30 | Eastman Kodak Company | Toners and developers containing ether-containing quaternary ammonium salts as charge control agents |
-
1993
- 1993-12-24 JP JP51500994A patent/JP3517240B2/en not_active Expired - Fee Related
- 1993-12-24 WO PCT/JP1993/001876 patent/WO1994014754A1/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10179832B2 (en) * | 2014-04-15 | 2019-01-15 | Henkel Ag & Co. Kgaa | Storage stable heat activated quaternary ammonium catalysts for epoxy cure |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1994014754A1 (en) | 1994-07-07 |
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