JPH11152264A - Production of aromatic sulfonyl isocyanate - Google Patents
Production of aromatic sulfonyl isocyanateInfo
- Publication number
- JPH11152264A JPH11152264A JP9335049A JP33504997A JPH11152264A JP H11152264 A JPH11152264 A JP H11152264A JP 9335049 A JP9335049 A JP 9335049A JP 33504997 A JP33504997 A JP 33504997A JP H11152264 A JPH11152264 A JP H11152264A
- Authority
- JP
- Japan
- Prior art keywords
- isocyanate
- general formula
- urea
- aromatic
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、芳香族スルホニルイソ
シアナートの製造方法に関するものである。本発明によ
って得られるイソシアナートは、化学工業、樹脂工業、
塗料工業、染料工業などの分野において、ポリウレタン
系材料、ポリ尿素系材料、感熱・感圧紙用顕色剤、ポリ
エステル系高分子の加水分解防止安定剤などの原料とし
て極めて重要である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aromatic sulfonyl isocyanate. Isocyanate obtained by the present invention, chemical industry, resin industry,
In the fields of the paint industry and the dye industry, it is extremely important as a raw material for polyurethane-based materials, polyurea-based materials, developers for heat- and pressure-sensitive paper, stabilizers for preventing hydrolysis of polyester-based polymers, and the like.
【０００２】[0002]
【従来の技術】芳香族スルホンアミドをホスゲン化して
芳香族スルホニルイソシアナートを得る場合、触媒が必
要である。触媒としては脂肪族イソシアナートが優れた
効果のあることが知られている。（米国特許第４３７９
７５９号、米国特許第３４８４４６６号）2. Description of the Related Art A catalyst is required when an aromatic sulfonyl isocyanate is obtained by phosgenating an aromatic sulfonamide. It is known that aliphatic isocyanates have excellent effects as catalysts. (U.S. Pat.
No. 759, U.S. Pat. No. 3,484,466)
【０００３】ホスゲン化反応に使用された触媒は、ホス
ゲン化の反応終了後、溶媒と共に留出させ、回収使用す
るのが有利であり、そのため反応の溶媒の沸点に近い沸
点を有する炭素数３〜８、好ましくは４〜７の脂肪族イ
ソシアナートが使用される。通常触媒の回収率は７０〜
９０％であり、不足分は補充しなければならない。しか
しながら、これらの触媒は一般には市販されていない。[0003] The catalyst used in the phosgenation reaction is advantageously distilled off together with the solvent after the completion of the phosgenation reaction and recovered for use. Therefore, the catalyst having 3 to 3 carbon atoms having a boiling point close to the boiling point of the solvent for the reaction. 8, preferably 4 to 7 aliphatic isocyanates are used. Normally, the recovery rate of the catalyst is 70 to
90%, the shortfall must be replenished. However, these catalysts are not generally commercially available.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、市販され
ていない触媒の代替となる化合物の探索を鋭意検討した
結果、容易に入手可能な脂肪族アミンと目的とするスル
ホニルイソシアナートの反応生成物であるＮ−アリール
スルホニル−Ｎ’−アルキルウレアが脂肪族イソシアナ
ートと同等の触媒効果のあることを見いだし、本発明を
完成した。即ち、本発明は、一般式［Ｉ］ Ｒ1 ＳＯ2 ＮＨ2 ［Ｉ］ （式中、Ｒ1 はアルキル基、ハロゲン原子もしくはニト
ロ基で置換されていてもよいフェニル基又はナフチル基
を示す。）で表される芳香族スルホンアミドとホスゲン
とを、一般式［II］ Ｒ1 ＳＯ2 ＮＨＣＯＮＨＲ2 ［II］ （式中、Ｒ1 は前記と同じ意味を示し、Ｒ2 はＣ３〜８
のアルキル基又はシクロアルキル基を示す。）で表され
るウレア化合物を使用して反応させることを特徴とする
一般式［III ］Ｒ1 ＳＯ2 ＮＣＯ（式中、Ｒ1 は前記と
同じ意味を示す。）で表される芳香族スルホニルイソシ
アナートの製造方法である。Means for Solving the Problems The present inventors have intensively studied the search for a compound that can be used as a substitute for a catalyst that is not commercially available, and as a result, have found that the reaction between an easily available aliphatic amine and a desired sulfonyl isocyanate is possible. The present inventors have found that the product, N-arylsulfonyl-N'-alkylurea, has the same catalytic effect as aliphatic isocyanate, and completed the present invention. That is, the present invention provides a compound represented by the general formula [I] R 1 SO 2 NH 2 [I] wherein R 1 represents a phenyl group or a naphthyl group which may be substituted with an alkyl group, a halogen atom or a nitro group. ) Is represented by the general formula [II] R 1 SO 2 NHCONHR 2 [II] (wherein R 1 has the same meaning as described above, and R 2 represents C3-8
Represents an alkyl group or a cycloalkyl group. Wherein R 1 is an aromatic sulfonyl represented by the general formula [III] R 1 SO 2 NCO, wherein R 1 has the same meaning as described above. This is a method for producing isocyanate.
【０００５】[0005]
【発明の実施の形態】本発明で使用される芳香族スルホ
ンアミドとしては、例えばベンゼンスルホンアミド、ｏ
−トルエンスルホンアミド、ｐ−トルエンスルホンアミ
ド、ｐ−クロロベンゼンスルホンアミド、ｍ−ニトロベ
ンゼンスルホンアミド、ｐ−ニトロベンゼンスルホンア
ミド、ｐ−メトキシベンゼンスルホンアミド、ナフタレ
ンスルホンアミド、メチルナフタレンスルホンアミドな
どが挙げられる。DETAILED DESCRIPTION OF THE INVENTION The aromatic sulfonamide used in the present invention includes, for example, benzenesulfonamide, o
-Toluenesulfonamide, p-toluenesulfonamide, p-chlorobenzenesulfonamide, m-nitrobenzenesulfonamide, p-nitrobenzenesulfonamide, p-methoxybenzenesulfonamide, naphthalenesulfonamide, methylnaphthalenesulfonamide and the like.
【０００６】本発明で使用する一般式［II］で表される
ウレア化合物（以下ウレアという）は溶媒の存在下、目
的とする芳香族スルホニルイソシアナートに脂肪族アミ
ンを添加し、混合加熱するだけで容易に調整される。溶
媒は必須ではないが、ウレアは融点が高く粘度も高いの
で一般には溶媒を使用する。溶媒はホスゲン化の溶媒と
同一のものを使用し、調整されたウレアはそのまま、溶
液で使用するのが好都合である。脂肪族アミンは炭素数
３〜８の容易に入手できるアミンで、例えばｉ−プロピ
ルアミン、ブチルアミン、ｓｅｃ−ブチルアミン、ｔｅ
ｒｔ−ブチルアミン、ｌ−メチルブチルアミン、シクロ
ヘキシルアミンなどが挙げられる。The urea compound represented by the general formula [II] (hereinafter referred to as "urea") used in the present invention is obtained by simply adding an aliphatic amine to a target aromatic sulfonyl isocyanate in the presence of a solvent, and mixing and heating. Easily adjusted. A solvent is not essential, but a solvent is generally used because urea has a high melting point and a high viscosity. It is convenient to use the same solvent as the solvent for phosgenation, and to use the adjusted urea as it is in a solution. Aliphatic amines are readily available amines having 3 to 8 carbon atoms, such as i-propylamine, butylamine, sec-butylamine, te
Examples thereof include rt-butylamine, 1-methylbutylamine, and cyclohexylamine.
【０００７】本発明におけるウレアの使用量は、初回の
反応では原料の芳香族スルホンアミドに対して０．１５
〜０．３５当量が用いられる。ホスゲン化の反応では、
使用したウレアはホスゲンと速やかに反応し、目的とす
る芳香族スルホニルイソシアナートと脂肪族イソシアナ
ートを生成し、ウレア調整に用いた芳香族スルホニルイ
ソシアナートが回収される。また、生成した脂肪族イソ
シアナートは原料スルホンアミドのホスゲン化の触媒と
して働いた後、溶媒と共に回収できる。触媒の回収率は
通常６０〜９０％である。次回の反応では、回収した脂
肪族イソシアナートと追加するウレアの合計が、芳香族
スルホンアミドに対し０．１５〜０．３５当量となるよ
うに僅かのウレアの追加で済ますことができ、経済的に
も有利である。[0007] The amount of urea used in the present invention is 0.15 with respect to the starting material aromatic sulfonamide in the first reaction.
~ 0.35 equivalents are used. In the phosgenation reaction,
The urea used quickly reacts with phosgene to produce the desired aromatic sulfonyl isocyanate and aliphatic isocyanate, and the aromatic sulfonyl isocyanate used for urea preparation is recovered. Further, the produced aliphatic isocyanate can be recovered together with the solvent after acting as a catalyst for phosgenation of the raw material sulfonamide. The recovery of the catalyst is usually 60 to 90%. In the next reaction, it is possible to add only a small amount of urea so that the total of the recovered aliphatic isocyanate and the added urea becomes 0.15 to 0.35 equivalent to the aromatic sulfonamide, and it is economical. It is also advantageous.
【０００８】本発明のウレアの調整は、溶媒の存在下ま
たは非存在下に、目的とする芳香族スルホニルイソシア
ナートと所望の触媒を生成させる脂肪族アミンを反応さ
せて得られる。この時、反応が遅い場合や、ウレアの結
晶が析出する場合は、加熱して反応を完結させるか、ま
たはウレアの結晶を溶解させる。ウレアの調整に必要な
目的とする芳香族スルホニルイソシアナートの量は多い
方が良いが効率を考慮し、脂肪族アミンに対し１．２〜
２当量が好ましい。もち論、芳香族スルホンアミドと脂
肪族イソシアナートとを反応させてもウレアを調整する
ことは可能であるが、脂肪族イソシアナートを製造する
工程が必要であり、メリットがない。The urea of the present invention can be prepared by reacting a desired aromatic sulfonyl isocyanate with an aliphatic amine which forms a desired catalyst in the presence or absence of a solvent. At this time, when the reaction is slow or urea crystals are precipitated, the reaction is completed by heating or the urea crystals are dissolved. The amount of the objective aromatic sulfonyl isocyanate required for the preparation of urea is preferably higher, but in consideration of efficiency, the amount is preferably from 1.2 to
Two equivalents are preferred. Of course, urea can be adjusted by reacting an aromatic sulfonamide with an aliphatic isocyanate, but a step of producing an aliphatic isocyanate is required, and there is no merit.
【０００９】本発明で、ウレア調整とホスゲン化は必ず
しも同一の溶媒でなくてもよいが、同一の溶媒の方が、
溶媒の分留などの必要がなく有利である。共通して用い
られる溶媒としては、反応に不活性なものなら良く、例
えばヘキサン、ヘプタン、オクタン、シクロヘキサンな
どの脂肪族炭化水素、ベンゼン、トルエン、キシレン、
エチルベンゼン、イソプロピルベンゼンなどの芳香族炭
化水素、ジクロロメタン、四塩化炭素、１，２−ジクロ
ロエタン、１，１，１，−トリクロロエタンなどのハロ
ゲン化脂肪族炭化水素、クロロベンゼン、ｏ−ジクロロ
ベンゼン、などのハロゲン化芳香族炭化水素などが挙げ
られる。In the present invention, the preparation of urea and the phosgenation do not necessarily have to be the same solvent.
This is advantageous because there is no need to fractionate the solvent. Commonly used solvents may be any solvents that are inert to the reaction, for example, hexane, heptane, octane, aliphatic hydrocarbons such as cyclohexane, benzene, toluene, xylene,
Aromatic hydrocarbons such as ethylbenzene and isopropylbenzene, halogenated aliphatic hydrocarbons such as dichloromethane, carbon tetrachloride, 1,2-dichloroethane and 1,1,1, -trichloroethane, halogens such as chlorobenzene and o-dichlorobenzene Aromatic hydrocarbons and the like.
【００１０】前記の芳香族スルホンアミドを、前記の溶
媒中でホスゲンと反応させるには、芳香族スルホンアミ
ドと溶媒、または回収された触媒を含む溶媒、および前
記のウレアを混合・加熱し、ホスゲンを吹き込む方法が
一般的である。ホスゲンの使用量は芳香族スルホンアミ
ドに対して１．１〜２．０当量である。In order to react the above-mentioned aromatic sulfonamide with phosgene in the above-mentioned solvent, the aromatic sulfonamide and the solvent or the solvent containing the recovered catalyst and the above-mentioned urea are mixed and heated, and the phosgene is mixed. Is generally used. The amount of phosgene used is 1.1 to 2.0 equivalents to the aromatic sulfonamide.
【００１１】ホスゲン化の反応温度は通常１００〜１７
０℃の範囲が好ましい。低い温度では、原料の芳香族ス
ルホンアミドが溶解しないため反応が遅く実際的でな
い。また、高い温度では副反応などによる収率の低下や
触媒回収率の低下を招く結果となる。The reaction temperature for the phosgenation is usually 100 to 17
A range of 0 ° C. is preferred. At low temperatures, the reaction is slow and impractical because the starting aromatic sulfonamide does not dissolve. In addition, a high temperature results in a decrease in yield due to side reactions and a decrease in catalyst recovery.
【００１２】本発明の通常の好ましい態様は、次のよう
になる。還流冷却器、温度計、ホスゲン吹き込み管およ
び撹拌機を備えた反応器中に原料の芳香族スルホンアミ
ド、反応溶媒または触媒と共に回収された溶媒、ウレア
を仕込む。次に所定の温度まで加熱しホスゲンを吹き込
む。ホスゲン化反応終了後、溶媒と触媒の脂肪族イソシ
アナートを留去した後、濃縮液を蒸留して目的とする芳
香族スルホニルイソシアナートを取り出す。A preferred embodiment of the present invention is as follows. A raw material aromatic sulfonamide, a solvent recovered together with a reaction solvent or a catalyst, and urea are charged into a reactor equipped with a reflux condenser, a thermometer, a phosgene blowing tube and a stirrer. Next, it is heated to a predetermined temperature and phosgene is blown therein. After completion of the phosgenation reaction, the solvent and the aliphatic isocyanate as a catalyst are distilled off, and then the concentrated liquid is distilled to take out the desired aromatic sulfonyl isocyanate.
【００１３】[0013]
【実施例】以下に本発明を実施例により、具体的に説明
する。 ［実施例１］撹拌機、温度計、滴下ロートを備えた１リ
ットルの反応フラスコにトルエン６００ｍｌとｐ−トル
エンスルホニルイソシアナート７４ｇ（０．３７５モ
ル）を入れ、７０℃に保持しながらｓｅｃ−ブチルアミ
ン１８．３ｇ（０．２５モル）を１時間を要して滴下
し、さらに１時間かき混ぜ、Ｎ−ｐ−トルエンスルホニ
ル−Ｎ′−ｓｅｃブチルウレア溶液６１３ｇ（０．２５
モル）を調整した。The present invention will be specifically described below with reference to examples. Example 1 600 ml of toluene and 74 g (0.375 mol) of p-toluenesulfonyl isocyanate were placed in a 1-liter reaction flask equipped with a stirrer, a thermometer, and a dropping funnel. 18.3 g (0.25 mol) was added dropwise over 1 hour, and the mixture was further stirred for 1 hour, and 613 g (0.25 mol) of an Np-toluenesulfonyl-N'-secbutylurea solution was added.
Mol).
【００１４】還流冷却器、温度計、ホスゲン吹き込み管
および撹拌機を備えた内容積１リットルの反応フラスコ
に、調整したウレア溶液３４３ｇ（０．１４モル）とト
ルエン１５０ｍｌおよび原料のｐ−トルエンスルホンア
ミド１２０ｇ（０．７モル）を仕込んだ。In a 1-liter reaction flask equipped with a reflux condenser, a thermometer, a phosgene blowing tube, and a stirrer, 343 g (0.14 mol) of the prepared urea solution, 150 ml of toluene, and p-toluenesulfonamide as a raw material were added. 120 g (0.7 mol) were charged.
【００１５】次に撹拌下、加熱昇温し、還流下（内温１
０６〜１１０℃）ホスゲン９７ｇ（０．９８モル）を吹
き込んだ。ホスゲン化反応終了後、ホスゲン化で生成し
た触媒のｓｅｃ−ブチルイソシアナートを溶媒のトルエ
ンと共に留出させた。留出量は４１５ｇであった。この
留出液は、ブチルアミンを用いたイソシアナートの分析
からｓｅｃ−ブチルイソシアナート１１．４ｇ（回収率
８２％）を含んでいた。溶媒を留去した残りの液を減圧
蒸留し純度９８．８％のｐ−トルエンスルホニルイソシ
アナート１５８．９ｇを得た。ウレアからの回収分を除
いた収率は９５．１％であった。 ［実施例２］実施例１のホスゲン化で用いたものと同様
の反応フラスコに、実施例１で回収した触媒を含むトル
エン４１５ｇ（触媒１１．４ｇ、０．１１５モル）と実
施例１で調整したウレア溶液８５．９ｇ（０．０３５モ
ル）および原料のｐ−トルエンスルホンアミド１２０ｇ
（０．７モル）を仕込み、実施例１と同様にホスゲン化
を行い触媒を回収した。（回収率８０％） 残りの液を減圧蒸留し純度９９．０％のｐ−トルエンス
ルホニルイソシアナート１９２．３ｇ（収率９４．０
％）を得た。Next, the mixture is heated with stirring and heated to reflux (with an internal temperature of 1).
(06-110 ° C) 97 g (0.98 mol) of phosgene was blown in. After completion of the phosgenation reaction, the catalyst sec-butyl isocyanate formed by the phosgenation was distilled off together with toluene as a solvent. The amount of distillation was 415 g. The distillate contained 11.4 g of sec-butyl isocyanate (82% recovery) from analysis of isocyanate using butylamine. The remaining liquid obtained by distilling off the solvent was distilled under reduced pressure to obtain 158.9 g of p-toluenesulfonyl isocyanate having a purity of 98.8%. The yield excluding the amount recovered from urea was 95.1%. [Example 2] In a reaction flask similar to that used in the phosgenation of Example 1, 415 g (11.4 g, 0.115 mol of catalyst) of toluene containing the catalyst recovered in Example 1 was adjusted. 85.9 g (0.035 mol) of the obtained urea solution and 120 g of p-toluenesulfonamide as a raw material
(0.7 mol), phosgenation was carried out in the same manner as in Example 1, and the catalyst was recovered. The remaining liquid was distilled under reduced pressure and 192.3 g of 99.0% pure p-toluenesulfonyl isocyanate was obtained (yield 94.0%).
%).
【００１６】[0016]
【発明の効果】本発明は、市販されていない脂肪族イソ
シアナート触媒の代替として、容易に入手可能な脂肪族
アミンを用いる、効率的な高品位の芳香族スルホニルイ
ソシアナートの製造方法である。The present invention is an efficient method for producing high-quality aromatic sulfonyl isocyanate using a readily available aliphatic amine as a substitute for a commercially available aliphatic isocyanate catalyst.
Claims (1)
ロ基で置換されていてもよいフェニル基又はナフチル基
を示す。）で表される芳香族スルホンアミドとホスゲン
とを、一般式［II］ Ｒ1 ＳＯ2 ＮＨＣＯＮＨＲ2 ［II］ （式中、Ｒ1 は前記と同じ意味を示し、Ｒ2 はＣ３〜８
のアルキル基又はシクロアルキル基を示す。）で表され
るウレア化合物を使用して反応させることを特徴とする
一般式［III ］Ｒ1 ＳＯ2 ＮＣＯ（式中、Ｒ1 は前記と
同じ意味を示す。）で表される芳香族スルホニルイソシ
アナートの製造方法。1. A general formula [I] R 1 SO 2 NH 2 [I] (wherein, R 1 represents a phenyl group or a naphthyl group which may be substituted with an alkyl group, a halogen atom or a nitro group). Is represented by the general formula [II] R 1 SO 2 NHCONHR 2 [II] (wherein R 1 has the same meaning as described above, and R 2 represents C3-8
Represents an alkyl group or a cycloalkyl group. Wherein R 1 is an aromatic sulfonyl represented by the general formula [III] R 1 SO 2 NCO, wherein R 1 has the same meaning as described above. Method for producing isocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33504997A JP3887808B2 (en) | 1997-11-19 | 1997-11-19 | Process for producing aromatic sulfonyl isocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33504997A JP3887808B2 (en) | 1997-11-19 | 1997-11-19 | Process for producing aromatic sulfonyl isocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11152264A true JPH11152264A (en) | 1999-06-08 |
| JP3887808B2 JP3887808B2 (en) | 2007-02-28 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33504997A Expired - Lifetime JP3887808B2 (en) | 1997-11-19 | 1997-11-19 | Process for producing aromatic sulfonyl isocyanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3887808B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007501690A (en) * | 2003-08-07 | 2007-02-01 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | New catalysts for selective isocyanate dimerization |
-
1997
- 1997-11-19 JP JP33504997A patent/JP3887808B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007501690A (en) * | 2003-08-07 | 2007-02-01 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | New catalysts for selective isocyanate dimerization |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3887808B2 (en) | 2007-02-28 |
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