JP2969384B2 - Method for producing trioxane - Google Patents
Method for producing trioxaneInfo
- Publication number
- JP2969384B2 JP2969384B2 JP3053710A JP5371091A JP2969384B2 JP 2969384 B2 JP2969384 B2 JP 2969384B2 JP 3053710 A JP3053710 A JP 3053710A JP 5371091 A JP5371091 A JP 5371091A JP 2969384 B2 JP2969384 B2 JP 2969384B2
- Authority
- JP
- Japan
- Prior art keywords
- cation exchange
- exchange resin
- trioxane
- formaldehyde
- weight
- 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 - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ホルムアルデヒドを陽
イオン交換樹脂と接触させてトリオキサンを製造する方
法に関するものである。さらに詳しくは、ホルムアルデ
ヒドを、スルホン酸基の他に少なくとも１個の電子吸引
性官能基をベンゼン環に有する陽イオン交換樹脂と接触
させてトリオキサンを製造する方法に関するものであ
る。The present invention relates to a method for producing trioxane by contacting formaldehyde with a cation exchange resin. More specifically, the present invention relates to a method for producing trioxane by contacting formaldehyde with a cation exchange resin having at least one electron-withdrawing functional group on a benzene ring in addition to a sulfonic acid group.
【０００２】[0002]
【従来の技術】トリオキサンは、ホルムアルデヒドの環
状三量体であり、主にポリオキシメチレン製造の原料と
して使用されている。トリオキサンの製造方法として
は、ホルムアルデヒドを酸触媒、例えば、硫酸、ベンゼ
ンスルホン酸、トルエンスルホン酸、シリカアルミナ、
ゼオライト、陽イオン交換樹脂等の存在下、加熱させて
トリオキサンを製造する方法が挙げられる。工業的なト
リオキサンの製造方法としては、硫酸を用いる方法が一
般的であるが、装置等の腐食、副生物が多い、パラホル
ムアルデヒドが生成しやすい等の問題がある。2. Description of the Related Art Trioxane is a cyclic trimer of formaldehyde, and is mainly used as a raw material for producing polyoxymethylene. As a method for producing trioxane, formaldehyde is used as an acid catalyst, for example, sulfuric acid, benzenesulfonic acid, toluenesulfonic acid, silica alumina,
A method of producing trioxane by heating in the presence of zeolite, a cation exchange resin, or the like can be given. An industrial method for producing trioxane is generally a method using sulfuric acid, but it has problems such as corrosion of equipment and the like, many by-products, and easy formation of paraformaldehyde.
【０００３】これらの問題を解決する方法として、陽イ
オン交換樹脂を用いる方法が提案されている。陽イオン
交換樹脂を用いてホルムアルデヒドからトリオキサンを
製造する方法としては、特公昭４０−１２７９４号公報
に装置の腐食問題を解決するための方法として、ゲル型
陽イオン交換樹脂（アンバーライト−ＩＲ−１２０）を
用いる方法が開示されている。また、特公昭６４−１１
０２５号公報にトリオキサンの選択率が良好な方法とし
て、巨大網目状陽イオン交換樹脂（ダイアイオンＰＫ２
０８）を用いる方法が開示されている。As a method for solving these problems, a method using a cation exchange resin has been proposed. As a method for producing trioxane from formaldehyde using a cation exchange resin, Japanese Patent Publication No. 40-12794 discloses a method for solving the corrosion problem of the apparatus, which is a gel type cation exchange resin (Amberlite-IR-120). ) Is disclosed. In addition, Japanese Patent Publication No. 64-11
No. 025, as a method having a good selectivity for trioxane, a giant mesh-like cation exchange resin (Diaion PK2
08) is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】陽イオン交換樹脂を用
いてトリオキサンを製造するに際して、トリオキサンを
効率良く製造するためには、高濃度のホルムアルデヒド
水溶液を陽イオン交換樹脂に接触させることが好まし
い。しかし、高濃度のホルムアルデヒド水溶液を陽イオ
ン交換樹脂に接触させて反応を継続すると、陽イオン交
換樹脂からスルホン酸基が脱離してイオン交換容量が低
下し、トリオキサンの合成活性が低下するという問題が
生じる。In the production of trioxane using a cation exchange resin, in order to produce trioxane efficiently, it is preferable to contact a high concentration aqueous formaldehyde solution with the cation exchange resin. However, if the reaction is continued by contacting a high-concentration aqueous formaldehyde solution with the cation exchange resin, the sulfonic acid group is eliminated from the cation exchange resin, reducing the ion exchange capacity and decreasing the trioxane synthesis activity. Occurs.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記の問題
を解決するために鋭意検討を行った結果、スルホン酸基
の他に少なくとも１個の電子吸引性官能基をベンゼン環
に有する陽イオン交換樹脂を用いることにより、スルホ
ン酸基の脱離が抑制されることを見出し、本発明を完成
した。すなわち、本発明は、ホルムアルデヒドを、スル
ホン酸基の他に少なくとも１個の電子吸引性官能基をベ
ンゼン環に有する陽イオン交換樹脂と接触させてトリオ
キサンを製造する方法に関するものである。The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a benzene ring having at least one electron-withdrawing functional group in addition to a sulfonic acid group. The present inventors have found that elimination of sulfonic acid groups is suppressed by using an ion exchange resin, and have completed the present invention. That is, the present invention relates to a method for producing trioxane by contacting formaldehyde with a cation exchange resin having at least one electron-withdrawing functional group on a benzene ring in addition to a sulfonic acid group.
【０００６】本発明において、トリオキサンの製造に使
用される陽イオン交換樹脂は、当該陽イオン交換樹脂に
含まれるベンゼン環にスルホン酸基の他に少なくとも１
個の電子吸引性官能基、例えば、−Ｃｌ、−Ｂｒ、−
Ｉ、−Ｆ、−ＣＯＯＨ、−ＳＯ3 Ｈ、−ＮＯ2 、−Ｃ
Ｎ、−ＰＯ3 Ｈ2 、−ＣＯＯＲ（ただし、Ｒは炭素数１
〜１８のアルキル、または炭素数６〜１８のアリールを
表す。）を有するものである。ホルムアルデヒドからト
リオキサンを製造するに当たり、当該陽イオン交換樹脂
からスルホン酸基の脱離が抑制される原因については不
明であるが、ベンゼン環に置換した電子吸引性官能基に
よりベンゼン環の電子状態が影響を受け、ホルムアルデ
ヒドによる親電子的反応を受けにくくなったためと推定
される。In the present invention, the cation exchange resin used for the production of trioxane has at least one sulfonic acid group in addition to a sulfonic acid group on the benzene ring contained in the cation exchange resin.
Electron-withdrawing functional groups, for example, -Cl, -Br,-
I, -F, -COOH, -SO 3 H, -NO 2, -C
N, -PO 3 H 2, -COOR ( wherein, R is 1 carbon atoms
Represents an alkyl having 18 to 18 carbon atoms, or an aryl having 6 to 18 carbon atoms. ). In producing trioxane from formaldehyde, the cause of the suppression of elimination of sulfonic acid groups from the cation exchange resin is unknown. It is presumed that it became less susceptible to electrophilic reactions due to formaldehyde.
【０００７】本発明で用いられる陽イオン交換樹脂は、
ポリビニル化合物、例えば、ジビニルベンゼン、メチル
ジビニルベンゼン、エチルジビニルベンゼン、またはこ
れらの化合物の混合物等により架橋されており、その架
橋度はポリビニル化合物の含有量で制御されているが、
一般的には２〜３０重量％のポリビニル化合物を含んで
いる。The cation exchange resin used in the present invention is:
Polyvinyl compounds, for example, divinylbenzene, methyldivinylbenzene, ethyldivinylbenzene, or cross-linked by a mixture of these compounds, the degree of cross-linking is controlled by the content of the polyvinyl compound,
Generally, it contains 2 to 30% by weight of a polyvinyl compound.
【０００８】本発明において使用するホルムアルデヒド
は、ホルムアルデヒドの水溶液として用いられる。ホル
ムアルデヒド水溶液のホルムアルデヒド濃度は特に制限
はないが、効率的にトリオキサンを製造するためには高
濃度のホルムアルデヒド水溶液が好ましく、具体的には
５０重量％以上、さらに好ましくは６０重量％以上であ
る。[0008] The formaldehyde used in the present invention is used as an aqueous solution of formaldehyde. The formaldehyde concentration of the aqueous formaldehyde solution is not particularly limited, but a high-concentration aqueous formaldehyde solution is preferred for efficient production of trioxane, specifically 50% by weight or more, more preferably 60% by weight or more.
【０００９】本発明の実施において、反応温度はパラホ
ルムアルデヒドが沈殿析出しないような温度に設定する
ことが望ましく、好ましくは３０〜２００℃、さらに好
ましくは５０〜１５０℃である。また、パラホルムアル
デヒドの沈殿析出を防止する添加剤を加えて反応させる
こともできる。In the practice of the present invention, the reaction temperature is desirably set to a temperature at which paraformaldehyde does not precipitate, preferably 30 to 200 ° C., more preferably 50 to 150 ° C. Further, the reaction can be carried out by adding an additive for preventing precipitation of paraformaldehyde.
【００１０】反応は固定床、流動床、攪拌槽等で行うこ
とができる。接触時間は反応方式によって選定される
が、一般に０．０１〜１８０分、好ましくは０．１〜１
２０分の範囲である。The reaction can be carried out in a fixed bed, a fluidized bed, a stirred tank or the like. The contact time is selected depending on the reaction system, but is generally 0.01 to 180 minutes, preferably 0.1 to 1 minute.
The range is 20 minutes.
【００１１】[0011]
【実施例】次に、実施例を挙げて本発明をさらに詳細に
説明する。 実施例１ 電子吸引性官能基として、Ｃｌを含有する陽イオン交換
樹脂（組成Ｃ４７．８重量％、Ｈ３．６重量％、Ｏ２
０．２重量％、Ｓ１３．４重量％、Ｃｌ １５．０重量
％）を反応蒸留装置の中で７０重量％のホルムアルデヒ
ド水溶液に１１５℃の温度で３ヶ月間浸漬した後、取り
出してイオン交換容量を測定した。結果は、浸漬前が
１．４０ meq／ml、浸漬後は０．８６ meq／mlであっ
た。Next, the present invention will be described in more detail with reference to examples. Example 1 A cation exchange resin containing Cl as an electron-withdrawing functional group (composition C 47.8% by weight, H 3.6% by weight, O 2
0.2% by weight, S13.4% by weight, Cl 15.0% by weight) were immersed in a 70% by weight aqueous formaldehyde solution at a temperature of 115 ° C. for 3 months in a reactive distillation apparatus. Was measured. The results were 1.40 meq / ml before immersion and 0.86 meq / ml after immersion.
【００１２】比較例１ 比較として、電子吸引性官能基を含まない陽イオン交換
樹脂（組成Ｃ５９．４重量％、Ｈ４．９重量％、Ｏ２
１．４重量％、Ｓ１４．３重量％）を実施例１と同じ条
件でテストした。結果は、浸漬前に１．３９ meq／mlで
あったイオン交換容量が、浸漬後は０．３７ meq／mlま
で低下していた。Comparative Example 1 For comparison, a cation exchange resin containing no electron-withdrawing functional group (composition C: 59.4% by weight, H: 4.9% by weight, O2
1.4% by weight, S14.3% by weight) were tested under the same conditions as in Example 1. As a result, the ion exchange capacity was 1.39 meq / ml before immersion, but decreased to 0.37 meq / ml after immersion.
【００１３】実施例２ 実施例１で使用したテスト前後の陽イオン交換樹脂につ
いて、それぞれトリオキサンの合成テストを行った。テ
ストは２００mlのガラス製オートクレーブに６５重量％
のホルムアルデヒド水溶液を１５０ｇ、陽イオン交換樹
脂を１０ml仕込み、９４℃の温度で反応を行った。１時
間後のホルムアルデヒド水溶液中のトリオキサン濃度の
分析値を表１に示す。Example 2 Trioxane synthesis tests were performed on the cation exchange resins before and after the test used in Example 1, respectively. The test was 65% by weight in a 200 ml glass autoclave.
Of 150 g of an aqueous formaldehyde solution and 10 ml of a cation exchange resin were reacted at a temperature of 94 ° C. The analytical value of the concentration of trioxane in the aqueous formaldehyde solution after one hour is shown in Table 1.
【００１４】比較例２ 比較例１で使用した陽イオン交換樹脂（テスト前後のサ
ンプル）について、実施例２と同じ条件でトリオキサン
の合成テストを行った。結果を表１に示す。Comparative Example 2 The cation exchange resin (sample before and after the test) used in Comparative Example 1 was subjected to a synthesis test of trioxane under the same conditions as in Example 2. Table 1 shows the results.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【発明の効果】ホルムアルデヒドからトリオキサンを製
造するに際し、本発明の陽イオン交換樹脂を用いること
により、陽イオン交換樹脂からのスルホン酸基の脱離が
抑制されるためにイオン交換容量の低下が小さく、した
がって、トリオキサンの製造を安定に行うことができ
る。EFFECT OF THE INVENTION In producing trioxane from formaldehyde, the use of the cation exchange resin of the present invention suppresses elimination of sulfonic acid groups from the cation exchange resin, so that the decrease in ion exchange capacity is small. Therefore, the production of trioxane can be stably performed.
Claims (5)
に少なくとも１個の電子吸引性官能基をベンゼン環に有
する陽イオン交換樹脂と接触させることを特徴とするト
リオキサンの製造方法。1. A process for producing trioxane, comprising contacting formaldehyde with a cation exchange resin having at least one electron-withdrawing functional group on a benzene ring in addition to a sulfonic acid group.
−Ｉ、−Ｆ、−ＣＯＯＨ、−ＳＯ３Ｈ、−ＮＯ２、−Ｃ
Ｎ、−ＰＯ３Ｈ２、−ＣＯＯＲ（ただし、Ｒは炭素数１
〜１８のアルキル、または炭素数６〜１８のアリールを
表す。）である請求項１記載の方法。2. The method according to claim 1, wherein the electron-withdrawing functional group is -Cl, -Br,
-I, -F, -COOH, -SO 3 H, -NO 2, -C
N, -PO 3 H 2, -COOR ( wherein, R is 1 carbon atoms
Represents an alkyl having 18 to 18 carbon atoms, or an aryl having 6 to 18 carbon atoms. 2. The method of claim 1, wherein
ルムアルデヒド水溶液である請求項１または２記載の方3. The method according to claim 1, wherein the aqueous solution is a formaldehyde solution.
法。Law.
１ないし３のいずれかに記載の方法。4. The method according to any one of 1 to 3.
求項１ないし４のいずれかに記載の方法。A method according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3053710A JP2969384B2 (en) | 1991-02-27 | 1991-02-27 | Method for producing trioxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3053710A JP2969384B2 (en) | 1991-02-27 | 1991-02-27 | Method for producing trioxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04273868A JPH04273868A (en) | 1992-09-30 |
| JP2969384B2 true JP2969384B2 (en) | 1999-11-02 |
Family
ID=12950388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3053710A Expired - Lifetime JP2969384B2 (en) | 1991-02-27 | 1991-02-27 | Method for producing trioxane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2969384B2 (en) |
-
1991
- 1991-02-27 JP JP3053710A patent/JP2969384B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04273868A (en) | 1992-09-30 |
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