JP4122085B2 - Method for producing sulfonium compound - Google Patents
Method for producing sulfonium compound Download PDFInfo
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- JP4122085B2 JP4122085B2 JP08018898A JP8018898A JP4122085B2 JP 4122085 B2 JP4122085 B2 JP 4122085B2 JP 08018898 A JP08018898 A JP 08018898A JP 8018898 A JP8018898 A JP 8018898A JP 4122085 B2 JP4122085 B2 JP 4122085B2
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- sulfonium compound
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Description
【０００１】
【産業上の利用分野】
本発明は、スルホニウム化合物の製造方法に関する。更に詳しくは、光および／または熱硬化性組成物の重合触媒として有用であり、特にエポキシ樹脂やスチレンなどのカチオン重合性ビニル化合物の重合開始剤として効果を有するスルホニウム化合物の製造方法に関する。
【０００２】
【従来の技術】
従来、スルホニウム化合物の製造方法としては、数多くの方法が提案されている。このうち、カチオン重合触媒として有用な特定のスルホニウム ポリフルオロ亜金属錯塩類を得るためには、対応するスルホニウム ハライドにＮaＳbＦ6，ＫＳbＦ6，ＮaＰＦ6，ＮaＡsＦ6等を作用させ、塩交換反応をさせることが公知である。例えば、特開平８−１８８５６９号によれば、有機溶媒と水を用いた強酸性中で反応が行われているものの、この方法では、イオン交換反応が完全に進行しないために、より純度の高い重合触媒を得ることができない。
【０００３】
【発明が解決しようとする課題】
本発明は、スルホニウム塩の効率的な合成の方法を検討した結果、原料であるスルホニウム ハライドとＮaＳbＦ6，ＫＳbＦ6などのポリフルオロ亜金属錯塩類との塩交換反応を、酢酸エチル−水の２相系で弱酸性で行うことにより、生成物の純度、収率が向上することを見出し、本発明に至ったものである。
【０００４】
【発明の構成】
本発明は、下記化４で表される重合触媒として有用なスルホニウム化合物を製造するにあたり、化３で表されるスルホニウム化合物を水と酢酸エチルの存在下、ｐＨ２〜５において反応させるものである。ここで、ｐＨ２〜５に保つ方法は任意である。例えば、酸性緩衝液の添加や、ｐＨメーターを監視しながら酸／塩基を添加していく方法などが例示される。これにより、化３から化４への塩交換が安定することを見出したものである。
【０００５】
ここにおいて、ｐＨ２〜５に保つ方法は任意であるが、このｐＨ範囲は酢酸−酢酸塩緩衝液または塩酸−酢酸塩緩衝液により簡易に作り出すことができるので、当該緩衝液の添加が推奨される。かつ、緩衝液は化学反応の前後において、ｐＨが変化することが少ないので、反応の当初に添加するだけですむという利点があるために好ましい。
【０００６】
【化３】
【化４】
（ただし、式中Ｒ1は、水素，ハロゲン，炭素数１〜４のアルキル基のいずれかを、Ｒ2は、炭素数１〜４のアルキル基またはベンジル基を、Ｒ3は、炭素数１〜４のアルキル基，ベンジル基，ハロゲノベンジル基，メチルベンジル基，ジメチルベンジル基，トリメチルベンジル基，メトキシベンジル基，ジクロルベンジル基，トリクロルベンジル基，ニトロベンジル基，ジニトロベンジル基，トリニトロベンジル基，α−ナフチルメチル基，β−ナフチルメチル基のいずれかを、Ｘは、ハロゲン原子、Ｍはアルカリ金属、ＹはＳbＦ6，ＰＦ6，ＡsＦ6，ＢＦ4のいずれかを示す。）
【０００９】
本発明によって製造されるスルホニウム化合物は、４−ヒドロキシフェニルベンジルメチルスルホニウム ヘキサフルオロアンチモネート、４−ヒドロキシフェニルベンジルメチルスルホニウム ヘキサフルオロホスフェート、４−ヒドロキシフェニルベンジルメチルスルホニウム ヘキサフルオロアルセネート、４−ヒドロキシフェニルベンジルメチルスルホニウム テトラフルオロボレート、４−ヒドロキシフェニル（ｏ−メチルベンジル）メチルスルホニウム ヘキサフルオロアンチモネート、４−ヒドロキシフェニル（ｏ−メチルベンジル）メチルスルホニウム ヘキサフルオロホスフェート、４−ヒドロキシフェニル（ｏ−メチルベンジル）メチルスルホニウム ヘキサフルオロアルセネート、４−ヒドロキシフェニル（ｏ−メチルベンジル）メチルスルホニウム テトラフルオロボレート、４−ヒドロキシフェニル（ｐ−ニトロベンジル）メチルスルホニウム ヘキサフルオロアンチモネート、４−ヒドロキシフェニル（ｐ−ニトロベンジル）メチルスルホニウム ヘキサフルオロアンチモネート、４−ヒドロキシフェニル（ｐ−ニトロベンジル）メチルスルホニウム ヘキサフルオロホスフェート、４−ヒドロキシフェニル（α−ナフチルメチル）メチルスルホニウム ヘキサフルオロアンチモネート、４−ヒドロキシフェニル（α−ナフチルメチル）メチルスルホニウム ヘキサフルオロホスフェート等が挙げられる。
【００１０】
【作用】
本発明の主旨である化３から化４へのスルホニウム化合物のイオン交換反応は、水と酢酸エチルの存在下で、ｐＨ２〜５に保つことが必須である。ここで、ｐＨを２〜５に保つ方法は任意である。例えば、酢酸などの弱酸を直接、反応系に添加する方法も例示できる。この他に、化学的に多用されている緩衝液の添加による方法も推奨できる。この代表的なものとして、酢酸−酢酸ナトリウム，塩酸−酢酸塩緩衝液といった緩衝剤の系が挙げられる。
【００１１】
このとき、反応に供するＭＹで表される塩の添加量は、化３で表されるスルホニウム化合物１モルに対して、０.８〜１.２モルが好ましい。反応媒体として使用する水の量は、攪拌可能以上であればよく、酢酸エチルは原料の化３で表されるスルホニウム化合物を溶解せしめる量であればよい。水と酢酸エチルの比は任意であるものの、水１容量に対して酢酸エチルが０．１〜２容量が好ましい。
【００１２】
このイオン交換反応に要する時間は１時間以内である。ただし、スルホニウム塩の特性によっては３時間程度を要するものもある。これによって、化４で表されるスルホニウム化合物が高収率で得られる。また、反応温度は４０℃以下、好ましくは２０℃以下である。４０℃を越えると化４で表されるスルホニウム化合物の熱劣化を生じるために好ましくない。
【００１３】
【実施例】
以下に本発明の実施例を示すが、本発明の範囲はこれに限定されるものではない。
実施例 １
四ツ口コルベンに攪拌機、温度計をそれぞれ設置する。なお、以下の実施例においても同様の装置を使用した。４−ヒドロキシフェニルベンジルメチルスルホニウムクロライド１０６.５ｇ（0.40ｍｏｌ）,酢酸エチル 400mL,水 1300mLを仕込み、この系に酢酸と水酸化ナトリウムを加えながらｐＨ測定を行い、所定の酢酸−酢酸ナトリウム系を構成するようなｐＨとした。次に、ＮaＳbＦ6 １０３.５ｇ（0.40ｍｏｌ）を投入し、１０℃で３０分間反応した。反応後、分液により酢酸エチル層を取り出し濃縮し、白色結晶を得た。得られた結晶はＮＭＲ分析、ＩＲ分析及び元素分析の結果、４−ヒドロキシフェニルベンジルメチルスルホニウム ヘキサフルオロアンチモネートであることを確認した。
【００１４】
なお、ｐＨ１〜３に保つときは、塩酸に酢酸ナトリウムを加えて調製した。無添加とは溶媒のみを添加した系をさす。また、純度を測るためにＤＳＣ（示差走査熱量計）の外挿温度とＨＰＬＣの測定を行った。結果をまとめて表１に示す。
【００１５】
【表１】
実施例 ２
４−ヒドロキシフェニル（Ｏ−メチルベンジル）メチルスルホニウム クロライド２２４．７ｇ（0.80ｍｏｌ）,酢酸エチル 400mL,水 1300mLを仕込み、実施例１に準じてｐＨ調整した。次にＮaＳbＦ6 ２０７．０ｇ（0.80ｍｏｌ）を投入し、実施例１と同様に処理して白色結晶を得た。得られた結晶はＮＭＲ分析、ＩＲ分析及び元素分析の結果、４−ヒドロキシフェニル（Ｏ−メチルベンジル）メチルスルホニウム ヘキサフルオロアンチモネートであることを確認した。実施例１と同様に行った結果をまとめて表２に示す。
【００１７】
【表２】
実施例 ３
４−ヒドロキシフェニル（α−ナフチルメチル）メチルスルホニウム クロライド１１７．８ｇ（0.37ｍｏｌ）,酢酸エチル 400mL,水 1300mLを仕込み、実施例１に準じてｐＨ調整した。次にＮaＳbＦ6 ９５．７ｇ（0.37ｍｏｌ）を投入し、実施例１と同様に処理して白色結晶を得た。得られた結晶はＮＭＲ分析、ＩＲ分析及び元素分析の結果、生成物が、４−ヒドロキシフェニル（α−ナフチルメチル）メチルスルホニウム ヘキサフルオロアンチモネートであることを確認した。実施例１と同様に行った結果をまとめて表３に示す。
【００１９】
【表３】
【発明の効果】
本発明の製造方法により、スルホニウム化合物の塩交換反応が安定し、容易に取り出すことができる。また、収率が向上し、純度も高いものが得られるので、陰イオン交換反応が定量的に進行していることが理解される。よって、本発明の方法は、特定のスルホニウム化合物の効率的な合成反応に寄与することができる。[0001]
[Industrial application fields]
The present invention relates to a method for producing a sulfonium compound. More specifically, the present invention relates to a method for producing a sulfonium compound that is useful as a polymerization catalyst for a light and / or thermosetting composition, and that is particularly effective as a polymerization initiator for a cationically polymerizable vinyl compound such as an epoxy resin or styrene.
[0002]
[Prior art]
Conventionally, many methods have been proposed as a method for producing a sulfonium compound. Among these, in order to obtain specific sulfonium polyfluorometal complex complexes useful as a cationic polymerization catalyst, NaSbF 6 , KSbF 6 , NaPF 6 , NaAsF 6, etc. are allowed to act on the corresponding sulfonium halide to cause a salt exchange reaction. It is known. For example, according to Japanese Patent Laid-Open No. 8-188869, although the reaction is carried out in a strong acid using an organic solvent and water, this method has higher purity because the ion exchange reaction does not proceed completely. A polymerization catalyst cannot be obtained.
[0003]
[Problems to be solved by the invention]
As a result of studying an efficient method for synthesizing a sulfonium salt, the present invention has conducted a salt exchange reaction between a raw material, sulfonium halide, and a polyfluorosubmetallic complex such as NaSbF 6 , KSbF 6, and the like. It has been found that the purity and yield of the product are improved by carrying out the process in a weakly acidic phase system, and the present invention has been achieved.
[0004]
[Structure of the invention]
In the present invention, in producing a sulfonium compound useful as a polymerization catalyst represented by the following chemical formula 4, the sulfonium compound represented by the chemical formula 3 is reacted at pH 2 to 5 in the presence of water and ethyl acetate. Here, the method of maintaining the pH at 2 to 5 is arbitrary. For example, an acid buffer solution or a method of adding an acid / base while monitoring a pH meter is exemplified. As a result, it has been found that salt exchange from chemical 3 to chemical 4 is stable.
[0005]
Here, the method of maintaining the pH at 2 to 5 is arbitrary, but since this pH range can be easily created with an acetic acid-acetate buffer solution or a hydrochloric acid-acetate buffer solution, the addition of the buffer solution is recommended. . In addition, the buffer solution is preferable because the pH hardly changes before and after the chemical reaction, so that it only needs to be added at the beginning of the reaction.
[0006]
[Chemical 3]
[Formula 4]
(In the formula, R 1 is any one of hydrogen, halogen, and an alkyl group having 1 to 4 carbon atoms, R 2 is an alkyl group having 1 to 4 carbon atoms or a benzyl group, and R 3 is one having 1 carbon atom.) Alkyl group of ˜4, benzyl group, halogenobenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, dichlorobenzyl group, trichlorobenzyl group, nitrobenzyl group, dinitrobenzyl group, trinitrobenzyl group , Α-naphthylmethyl group, β-naphthylmethyl group, X is a halogen atom, M is an alkali metal, and Y is SbF 6 , PF 6 , AsF 6 , or BF 4 .
[0009]
The sulfonium compound produced by the present invention includes 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate, 4-hydroxyphenylbenzylmethylsulfonium hexafluorophosphate, 4-hydroxyphenylbenzylmethylsulfonium hexafluoroarsenate, 4-hydroxyphenylbenzyl. Methylsulfonium tetrafluoroborate, 4-hydroxyphenyl (o-methylbenzyl) methylsulfonium hexafluoroantimonate, 4-hydroxyphenyl (o-methylbenzyl) methylsulfonium hexafluorophosphate, 4-hydroxyphenyl (o-methylbenzyl) methyl Sulfonium hexafluoroarsenate, 4-hydroxyphenyl (o-methylbenzyl) ) Methylsulfonium tetrafluoroborate, 4-hydroxyphenyl (p-nitrobenzyl) methylsulfonium hexafluoroantimonate, 4-hydroxyphenyl (p-nitrobenzyl) methylsulfonium hexafluoroantimonate, 4-hydroxyphenyl (p-nitrobenzyl) ) Methylsulfonium hexafluorophosphate, 4-hydroxyphenyl (α-naphthylmethyl) methylsulfonium hexafluoroantimonate, 4-hydroxyphenyl (α-naphthylmethyl) methylsulfonium hexafluorophosphate, and the like.
[0010]
[Action]
The ion exchange reaction of the sulfonium compound from Chemical Formula 3 to Chemical Formula 4, which is the gist of the present invention, must be maintained at pH 2 to 5 in the presence of water and ethyl acetate. Here, the method of maintaining the pH at 2 to 5 is arbitrary. For example, a method of adding a weak acid such as acetic acid directly to the reaction system can also be exemplified. In addition to this, a method by addition of a chemically frequently used buffer solution can be recommended. Typical examples thereof include buffer systems such as acetic acid-sodium acetate and hydrochloric acid-acetate buffer.
[0011]
At this time, the addition amount of the salt represented by MY to be subjected to the reaction is preferably 0.8 to 1.2 mol with respect to 1 mol of the sulfonium compound represented by Chemical Formula 3. The amount of water used as a reaction medium is not limited as long as it can be stirred, and ethyl acetate may be an amount capable of dissolving the sulfonium compound represented by Chemical Formula 3 as a raw material. Although the ratio of water and ethyl acetate is arbitrary, 0.1 to 2 volumes of ethyl acetate is preferable with respect to 1 volume of water.
[0012]
The time required for this ion exchange reaction is within one hour. However, depending on the characteristics of the sulfonium salt, some may require about 3 hours. Thereby, the sulfonium compound represented by Chemical formula 4 can be obtained in high yield. The reaction temperature is 40 ° C. or lower, preferably 20 ° C. or lower. Exceeding 40 ° C. is not preferable because the sulfonium compound represented by Chemical formula 4 is thermally deteriorated.
[0013]
【Example】
Examples of the present invention are shown below, but the scope of the present invention is not limited thereto.
Example 1
Install a stirrer and a thermometer in the four-necked Kolben. The same apparatus was used in the following examples. Charge 106.5 g (0.40 mol) of 4-hydroxyphenylbenzylmethylsulfonium chloride, 400 mL of ethyl acetate, and 1300 mL of water, and measure the pH while adding acetic acid and sodium hydroxide to this system to form a predetermined acetic acid-sodium acetate system It was set to such pH. Next, 103.5 g (0.40 mol) of NaSbF 6 was added and reacted at 10 ° C. for 30 minutes. After the reaction, the ethyl acetate layer was taken out by liquid separation and concentrated to obtain white crystals. As a result of NMR analysis, IR analysis, and elemental analysis, the obtained crystal was confirmed to be 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate.
[0014]
In addition, when maintaining pH 1-3, it prepared by adding sodium acetate to hydrochloric acid. “No addition” refers to a system to which only a solvent is added. Moreover, in order to measure purity, the extrapolated temperature of DSC (differential scanning calorimeter) and the measurement of HPLC were performed. The results are summarized in Table 1.
[0015]
[Table 1]
Example 2
4-hydroxyphenyl (O-methylbenzyl) methylsulfonium chloride 224.7 g (0.80 mol), ethyl acetate 400 mL, water 1300 mL were charged, and the pH was adjusted according to Example 1. Next, 207.0 g (0.80 mol) of NaSbF 6 was added and treated in the same manner as in Example 1 to obtain white crystals. As a result of NMR analysis, IR analysis and elemental analysis, the obtained crystal was confirmed to be 4-hydroxyphenyl (O-methylbenzyl) methylsulfonium hexafluoroantimonate. The results obtained in the same manner as in Example 1 are summarized in Table 2.
[0017]
[Table 2]
Example 3
4-hydroxyphenyl (α-naphthylmethyl) methylsulfonium chloride (117.8 g, 0.37 mol), ethyl acetate (400 mL), and water (1300 mL) were charged, and the pH was adjusted according to Example 1. Next, 95.7 g (0.37 mol) of NaSbF 6 was added and treated in the same manner as in Example 1 to obtain white crystals. As a result of NMR analysis, IR analysis, and elemental analysis, the obtained crystal was confirmed to be 4-hydroxyphenyl (α-naphthylmethyl) methylsulfonium hexafluoroantimonate. The results obtained in the same manner as in Example 1 are summarized in Table 3.
[0019]
[Table 3]
【The invention's effect】
By the production method of the present invention, the salt exchange reaction of the sulfonium compound is stabilized and can be easily taken out. Moreover, since a yield improves and a thing with high purity is obtained, it is understood that the anion exchange reaction is progressing quantitatively. Therefore, the method of the present invention can contribute to an efficient synthesis reaction of a specific sulfonium compound.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08018898A JP4122085B2 (en) | 1998-03-11 | 1998-03-11 | Method for producing sulfonium compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08018898A JP4122085B2 (en) | 1998-03-11 | 1998-03-11 | Method for producing sulfonium compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11255739A JPH11255739A (en) | 1999-09-21 |
| JP4122085B2 true JP4122085B2 (en) | 2008-07-23 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08018898A Expired - Lifetime JP4122085B2 (en) | 1998-03-11 | 1998-03-11 | Method for producing sulfonium compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4122085B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217551A (en) * | 2003-01-14 | 2004-08-05 | Sanshin Chem Ind Co Ltd | Sulfonium compound |
| JPWO2007111074A1 (en) | 2006-03-24 | 2009-08-06 | コニカミノルタエムジー株式会社 | Transparent barrier sheet and method for producing transparent barrier sheet |
| JPWO2007111092A1 (en) | 2006-03-24 | 2009-08-06 | コニカミノルタエムジー株式会社 | Transparent barrier sheet and method for producing transparent barrier sheet |
| EP2000297A1 (en) | 2006-03-24 | 2008-12-10 | Konica Minolta Medical & Graphic, Inc. | Transparent barrier sheet and method for producing transparent barrier sheet |
| JPWO2007111098A1 (en) | 2006-03-24 | 2009-08-06 | コニカミノルタエムジー株式会社 | Transparent barrier sheet and method for producing the same |
| JP5190665B2 (en) * | 2007-06-15 | 2013-04-24 | デクセリアルズ株式会社 | Epoxy resin composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2797024B2 (en) * | 1989-10-13 | 1998-09-17 | 三新化学工業株式会社 | Sulfonium compound |
| JP2592686B2 (en) * | 1989-10-31 | 1997-03-19 | 三新化学工業株式会社 | Dibenzylsulfonium compound |
| JPH06345726A (en) * | 1993-06-15 | 1994-12-20 | Nippon Soda Co Ltd | Novel sulfonium salt compound and its use as initiator for polymerization |
| JPH08188569A (en) * | 1995-01-06 | 1996-07-23 | Sanshin Chem Ind Co Ltd | Production of sulfonium compound |
| JP3954701B2 (en) * | 1996-09-26 | 2007-08-08 | 日本曹達株式会社 | Sulfonium salt compound, cationic polymerization initiator, and curable composition |
-
1998
- 1998-03-11 JP JP08018898A patent/JP4122085B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH11255739A (en) | 1999-09-21 |
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