JP2001114748A - Method for producing resorcinol 2,4,6-trisulfonic acid - Google Patents
Method for producing resorcinol 2,4,6-trisulfonic acidInfo
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- JP2001114748A JP2001114748A JP28905599A JP28905599A JP2001114748A JP 2001114748 A JP2001114748 A JP 2001114748A JP 28905599 A JP28905599 A JP 28905599A JP 28905599 A JP28905599 A JP 28905599A JP 2001114748 A JP2001114748 A JP 2001114748A
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- JP
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- Prior art keywords
- resorcinol
- mol
- sulfuric acid
- trisulfonate
- fuming sulfuric
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は２，４，６−トリス
ルホン酸レゾルシンの製造方法に関する。２，４，６−
トリスルホン酸レゾルシンは有機化学品や高分子化合物
の中間体として用いられる。特にニトロ化においては高
い選択率で４，６−位のニトロ化を行うことができ、耐
熱性・強度・弾性率などの性質に優れたポリベンゾビス
オキサゾール（ＰＢＯ）樹脂の原料モノマーである４，
６−ジアミノレゾルシンの前駆体として利用される４，
６−ジニトロレゾルシンを高収率で得ることができる。The present invention relates to a method for producing resorcinol 2,4,6-trisulfonate. 2,4,6-
Resorcinol trisulfonate is used as an intermediate for organic chemicals and polymer compounds. In particular, in nitration, nitration at the 4,6-position can be performed with high selectivity, and is a raw material monomer of polybenzobisoxazole (PBO) resin excellent in properties such as heat resistance, strength, and elastic modulus. ,
4, used as a precursor of 6-diaminoresorcinol
6-Dinitroresorcin can be obtained in high yield.
【０００２】[0002]
【従来の技術】２，４，６−トリスルホン酸レゾルシン
はＢｅｒｉｃｈｉｔｅ．１０．１８２においてジスルホ
ン酸レゾルシンの結晶を発煙硫酸中２００℃で数時間加
熱することで製造できると記載されている。しかしジス
ルホン酸レゾルシンを製造した後、該化合物を単離して
次工程に使用することは、工程が煩雑となるうえ大幅な
収率の低下を招き、工業的に実施するには問題があっ
た。2. Description of the Prior Art Resorcinol 2,4,6-trisulfonate is disclosed in Berichite. 10.182 states that crystals of resorcinol disulfonate can be prepared by heating in fuming sulfuric acid at 200 ° C. for several hours. However, isolating the compound after the production of resorcinol disulfonate and using it in the next step complicates the process and causes a large decrease in yield, which is problematic in industrial practice.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は２，
４，６−トリスルホン酸レゾルシンを工業的に有利に製
造する方法を提供することにある。The object of the present invention is to
An object of the present invention is to provide a method for industrially advantageously producing resorcinol 4,6-trisulfonate.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題を
解決するため鋭意検討を行った結果、レゾルシンを原料
として直接２，４，６−トリスルホン酸レゾルシンが得
られる方法を見出し、本発明を完成するに到った。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a method for directly obtaining resorcinol 2,4,6-trisulfonate from resorcinol as a raw material. The invention has been completed.
【０００５】即ち、本発明は以下のものである。 （１）レゾルシンとスルホン化剤を接触させることによ
る２，４，６−トリスルホン酸レゾルシンの製造方法。 （２）スルホン化剤に発煙硫酸を用いることを特徴とす
る（１）記載の２，４，６−トリスルホン酸レゾルシン
の製造方法。 （３）用いる発煙硫酸がレゾルシンに対して３モル倍以
上の遊離のＳＯ3を含んでいることを特徴とする（２）
記載の２，４，６−トリスルホン酸レゾルシンの製造方
法。That is, the present invention is as follows. (1) A method for producing resorcinol 2,4,6-trisulfonate by bringing resorcinol into contact with a sulfonating agent. (2) The method for producing resorcinol 2,4,6-trisulfonate according to (1), wherein fuming sulfuric acid is used as the sulfonating agent. (3) The fuming sulfuric acid used is characterized in that it contains free SO 3 in an amount of 3 mol times or more of resorcinol (2).
A method for producing the resorcinol 2,4,6-trisulfonate described above.
【０００６】[0006]
【発明の実施の形態】本発明の実施においては２，４，
６−トリスルホン酸レゾルシンを製造し得るような公知
のスルホン化剤が使用できる。スルホン化剤としては、
例えば濃硫酸、発煙硫酸、三酸化イオウ等が挙げられ
る。反応は適当な溶媒を用いてもよいが溶媒を用いず過
剰の濃硫酸または発煙硫酸中で行うのが工業上有利であ
る。本発明において２，４，６−トリスルホン酸レゾル
シンの選択率は硫酸中のＳＯ3濃度に大きく依存し、硫
酸中のＳＯ3濃度が低下するほど２，４，６−トリスル
ホン酸レゾルシンの選択率は低下する。例えば９５％硫
酸（ＳＯ3濃度７７．６％）を用いても２，４，６−ト
リスルホン酸レゾルシンの製造は可能であるが、９５％
硫酸（ＳＯ3濃度７７．６％）を用いた時の２，４，６
−トリスルホン酸レゾルシンの選択率は１２〜１７モル
％程度であり、残りの８３〜８８モル％は４，６−ジス
ルホン酸レゾルシンであった。工業上満足し得るような
収率を得るためには反応終了時の硫酸中のＳＯ3濃度が
８１．６％以上、即ち硫酸濃度が１００％であるか過剰
の遊離ＳＯ3を含む状態が必要である。該状態を維持す
るには、反応初期のＳＯ3濃度８６．０％以上、即ちレ
ゾルシンに対して３モル倍以上の遊離ＳＯ3を含む発煙
硫酸を用いてスルホン化を行えばよい。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the practice of the present invention, 2, 4,
Known sulfonating agents capable of producing resorcinol 6-trisulfonate can be used. As the sulfonating agent,
For example, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide and the like can be mentioned. The reaction may be carried out using an appropriate solvent, but it is industrially advantageous to carry out the reaction in an excess of concentrated sulfuric acid or fuming sulfuric acid without using a solvent. Selectivity of 2,4,6-sulfonic acid resorcinol in the present invention depends largely on the SO 3 concentration in sulfuric acid, the selection of more 2,4,6-sulfonic acid resorcin is lowered SO 3 concentration in sulfuric acid The rate drops. For example, it is possible to produce resorcinol 2,4,6-trisulfonate by using 95% sulfuric acid (SO 3 concentration: 77.6%).
2,4,6 when sulfuric acid (SO 3 concentration 77.6%) is used
-The selectivity of resorcinol trisulfonate was about 12 to 17 mol%, and the remaining 83 to 88 mol% was resorcinol 4,6-disulfonate. SO 3 concentration in sulfuric acid at the end of the reaction in order to obtain a yield as can be industrially satisfied 81.6% or more, that the sulfuric acid concentration is required conditions including excess of free SO 3 or a 100% It is. In order to maintain this state, sulfonation may be performed using fuming sulfuric acid containing 86.0% or more of SO 3 concentration at the beginning of the reaction, that is, 3 mol or more of free SO 3 with respect to resorcinol.
【０００７】用いるスルホン化剤の量は上記のＳＯ3濃
度を満たすものであれば特に制限されるものではない
が、容積効率および効率的攪拌の点からレゾルシンに対
して５〜５０重量倍が好ましい。The amount of the sulfonating agent to be used is not particularly limited as long as it satisfies the above-mentioned SO 3 concentration, but is preferably 5 to 50 times the weight of resorcin from the viewpoint of volumetric efficiency and efficient stirring. .
【０００８】レゾルシンとスルホン化剤を接触させる方
法はスルホン化剤の中にレゾルシンを装入するか或いは
その逆の方法のいずれでも良い。The method of contacting resorcin with the sulfonating agent may be either charging resorcin into the sulfonating agent or vice versa.
【０００９】反応温度は2０〜１５０℃の範囲であれば
よい。スルホン化時の発熱のため２０℃未満に保って反
応を行うことは過大な冷却能力を必要とするため好まし
くなく、１５０℃を越えると望ましくない副反応を起こ
す傾向がある。[0009] The reaction temperature may be in the range of 20 to 150 ° C. It is not preferable to carry out the reaction at a temperature lower than 20 ° C. due to the heat generated during the sulfonation, since an excessive cooling capacity is required. When the temperature exceeds 150 ° C., an undesirable side reaction tends to occur.
【００１０】反応マスから２，４，６−トリスルホン酸
レゾルシンを単離する方法としては硫酸ナトリウムなど
の無機塩の水溶液に反応マスを滴下して塩析したのち、
濾過・乾燥することで得られる。As a method for isolating resorcinol 2,4,6-trisulfonate from the reaction mass, the reaction mass is dropped into an aqueous solution of an inorganic salt such as sodium sulfate and salted out.
It is obtained by filtration and drying.
【００１１】[0011]
【実施例】以下、実施例をあげて本発明をさらに詳細に
説明するが、本発明はこれらの実施例に限定されるもの
ではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００１２】実施例１ ３０％発煙硫酸１００ｇ（ＳＯ3濃度８７．１％、遊離
ＳＯ3量３．７５モル倍／レゾルシン）を氷冷し、レゾ
ルシン１１．０ｇ（０．１モル）をゆっくり装入した後
に９０℃に昇温したところ反応マスは暗赤色の均一溶液
となった。液体クロマトグラフィー（以下、ＨＰＬＣと
略する）による分析ではレゾルシンおよび４，６−ジス
ルホン酸レゾルシンのピークは確認されず、２，４，６
−トリスルホン酸レゾルシンの生成率は９９．８モル％
であった。 ＨＰＬＣ分析条件 カラム：ＹＭＣ−３１２Ａ（ＯＤＳ） 移動相：アセトニトリル：水：ＰＩＣ＝１０００：２０
００：１０ ＰＩＣ＝テトラブチルアンモニウムヒドロキシド 流速 ：１ｍｌ／ｍｉｎ 検出波長：２５４ｎｍ 恒温層：４０℃Example 1 100 g of 30% fuming sulfuric acid (SO 3 concentration 87.1%, free SO 3 amount 3.75 mol times / resorcinol) was cooled on ice, and 11.0 g (0.1 mol) of resorcin was slowly charged. When the temperature was raised to 90 ° C. after the addition, the reaction mass became a dark red homogeneous solution. In the analysis by liquid chromatography (hereinafter abbreviated as HPLC), resorcinol and resorcinol 4,6-disulfonate were not confirmed, and 2,4,6
The rate of formation of resorcinol trisulfonate is 99.8 mol%
Met. HPLC analysis conditions Column: YMC-312A (ODS) Mobile phase: acetonitrile: water: PIC = 1000: 20
00:10 PIC = tetrabutylammonium hydroxide Flow rate: 1 ml / min Detection wavelength: 254 nm Thermostat: 40 ° C.
【００１３】実施例２ ２４％発煙硫酸１００ｇ（ＳＯ3濃度８６．０％、遊離
ＳＯ3量３モル倍／レゾルシン）を氷冷し、レゾルシン
１１．０ｇ（０．１モル）をゆっくり装入した後に５０
℃に昇温したところ反応マスは暗赤色の均一溶液となっ
た。ＨＰＬＣによる分析では４，６−ジスルホン酸レゾ
ルシンの生成率は０．６モル％であり、２，４，６−ト
リスルホン酸レゾルシンの生成率は９９．３モル％であ
った。Example 2 100 g of 24% fuming sulfuric acid (SO 3 concentration: 86.0%, free SO 3 amount: 3 mol times / resorcinol) was cooled on ice, and 11.0 g (0.1 mol) of resorcin was slowly charged. 50 later
When the temperature was raised to ℃, the reaction mass became a dark red homogeneous solution. According to the analysis by HPLC, the production rate of resorcinol 4,6-disulfonic acid was 0.6 mol%, and the production rate of resorcinol 2,4,6-trisulfonic acid was 99.3 mol%.
【００１４】実施例３ １６％発煙硫酸１００ｇ（ＳＯ3濃度８４．６％、遊離
ＳＯ3量２モル倍／レゾルシン）を氷冷し、レゾルシン
１１．０ｇ（０．１モル）をゆっくり装入した後に９０
℃に昇温したところ反応マスは若干固形物の残ったオレ
ンジ色の粘調スラリーとなった。ＨＰＬＣによる分析で
は４，６−ジスルホン酸レゾルシンの生成率は９．５モ
ル％、２，４，６−トリスルホン酸レゾルシンの生成率
は９０．２モル％であった。引き続き反応マスを１３０
℃に昇温したところ赤色の均一溶液となったが、３０分
反応させた後の４，６−ジスルホン酸レゾルシンの生成
率は１３モル％、２，４，６−トリスルホン酸レゾルシ
ンの生成率は８７モル％であった。[0014] Example 3 16% fuming sulfuric acid 100 g (SO 3 concentration 84.6% free SO 3 content 2 mol times / resorcinol) was ice-cooled, and slowly charging the resorcin 11.0 g (0.1 mol) 90 later
When the temperature was raised to ° C, the reaction mass became an orange viscous slurry with some solids remaining. According to the analysis by HPLC, the production rate of resorcinol 4,6-disulfonic acid was 9.5 mol%, and the production rate of resorcinol 2,4,6-trisulfonic acid was 90.2 mol%. Subsequently, the reaction mass was increased to 130
When the temperature was raised to 0 ° C., a red homogeneous solution was obtained, but the rate of formation of resorcinol 4,6-disulfonate after reacting for 30 minutes was 13 mol%, and the rate of formation of resorcinol 2,4,6-trisulfonate. Was 87 mol%.
【００１５】実施例４ １００％硫酸１００ｇ（ＳＯ3濃度８１．６％）を氷冷
し、レゾルシン１１．０ｇ（０．１モル）をゆっくり装
入した後に９０℃に昇温したところ反応マスは薄桃色の
スラリーとなった。ＨＰＬＣによる分析では４，６−ジ
スルホン酸レゾルシンの生成率は９３モル％、２，４，
６−トリスルホン酸レゾルシンの生成率は６．５モル％
であった。引き続き反応マスを１３０℃に昇温したが結
晶の溶解は見られず、薄桃色のスラリーのままであっ
た。６０分反応させた後の４，６−ジスルホン酸レゾル
シンの生成率は７９モル％、２，４，６−トリスルホン
酸レゾルシンの生成率は２１モル％であった。Example 4 100 g of 100% sulfuric acid (81.6% SO 3 concentration) was cooled on ice, 11.0 g (0.1 mol) of resorcin was slowly charged, and the temperature was raised to 90 ° C. A pale pink slurry was obtained. According to the analysis by HPLC, the yield of resorcinol 4,6-disulfonate was 93 mol%, 2,4,4
The yield of 6-resulfin trisulfonate is 6.5 mol%
Met. Subsequently, the temperature of the reaction mass was raised to 130 ° C., but no dissolution of the crystals was observed, and the slurry remained a pale pink slurry. After reacting for 60 minutes, the yield of resorcinol 4,6-disulfonic acid was 79 mol%, and the yield of resorcinol 2,4,6-trisulfonic acid was 21 mol%.
【００１６】実施例５ ９５％硫酸１００ｇ（ＳＯ3濃度７７．６％）を氷冷
し、レゾルシン１１．０ｇ（０．１モル）をゆっくり装
入した後に５０℃に昇温したところ反応マスは白色のス
ラリーとなった。ＨＰＬＣによる分析では４，６−ジス
ルホン酸レゾルシンの生成率は８８モル％、２，４，６
−トリスルホン酸レゾルシンの生成率は１２モル％であ
った。Example 5 100 g of 95% sulfuric acid (SO 3 concentration: 77.6%) was cooled on ice, 11.0 g (0.1 mol) of resorcin was slowly charged, and the temperature was raised to 50 ° C. A white slurry resulted. According to the analysis by HPLC, the yield of resorcinol 4,6-disulfonate was 88 mol%, 2,4,6
-The yield of resorcinol trisulfonate was 12 mol%.
【００１７】実施例６ ９５％硫酸２００ｇ（ＳＯ3濃度７７．６％）を氷冷
し、レゾルシン１１．０ｇ（０．１モル）をゆっくり装
入した後に５０℃に昇温したところ反応マスは白色のス
ラリーとなった。ＨＰＬＣによる分析では４，６−ジス
ルホン酸レゾルシンの生成率は８３モル％、２，４，６
−トリスルホン酸レゾルシンの生成率は１７モル％であ
った。以下に２，４，６−トリスルホン酸レゾルシンを
用いて４，６−ジニトロレゾルシンを合成した参考例を
示す。Example 6 200 g of 95% sulfuric acid (SO 2 concentration: 77.6%) was cooled on ice, 11.0 g (0.1 mol) of resorcin was slowly charged, and the temperature was raised to 50 ° C. A white slurry resulted. According to analysis by HPLC, the yield of resorcinol 4,6-disulfonate was 83 mol%, 2,4,6
-The yield of resorcinol trisulfonate was 17 mol%. The following shows a reference example in which 4,6-dinitroresorcin was synthesized using resorcinol 2,4,6-trisulfonate.
【００１８】参考例１ ３０％発煙硫酸５０ｇにレゾルシン５．５ｇ（０．０５
モル）をゆっくり装入した後に９０℃に昇温したところ
反応マスは暗赤色の溶液となり、ＨＰＬＣによる分析で
２，４，６−トリスルホン酸レゾルシンの生成が確認さ
れた。スルホン化マスを氷冷し、６０％硝酸１０．５ｇ
（０．１モル）を滴下したところ激しい発熱があり、反
応マスは黄褐色のスラリーとなった。該ニトロ化マスを
氷１００ｇ中に装入、ろ過して副生した２，４，６−ト
リニトロレゾルシンを除去した後、ろ液を１００℃に加
熱して加水分解を行なったところ徐々に結晶の析出が見
られた。結晶をろ別して窒素下で風乾し、４，６−ジニ
トロレゾルシン８．０２g（収率８０．３％／レゾルシ
ン）を得た。Reference Example 1 5.5 g of resorcinol (0.05 g in 50 g of 30% fuming sulfuric acid)
(Mol) was slowly charged and the temperature was raised to 90 ° C., the reaction mass became a dark red solution, and the analysis by HPLC confirmed formation of resorcinol 2,4,6-trisulfonate. The sulfonated mass is ice-cooled and 10.5 g of 60% nitric acid
(0.1 mol) was dripped, and vigorous heat was generated, and the reaction mass became a yellow-brown slurry. The nitrated mass was placed in 100 g of ice, filtered to remove 2,4,6-trinitroresorcin by-produced, and the filtrate was heated to 100 ° C. and hydrolyzed. Was observed. The crystals were separated by filtration and air-dried under nitrogen to obtain 8.02 g of 4,6-dinitroresorcin (yield: 80.3% / resorcin).
【００１９】[0019]
【発明の効果】本発明に係る製造方法においては、直接
レゾルシンの２，４，６−位のスルホン化を行うことが
できる。更に、スルホン化剤に発煙硫酸を用いる事、発
煙硫酸の量がレゾルシンに対して３モル以上の遊離のＳ
Ｏ3を含有していることにより高選択率、高収率でレゾ
ルシンの２，４，６−位のスルホン化を行うことができ
る。即ち２，４，６−トリスルホン酸レゾルシンを工業
的に有利に製造することができる。According to the production method of the present invention, the resorcinol can be directly sulfonated at the 2,4,6-position. Further, fuming sulfuric acid is used as a sulfonating agent, and the amount of fuming sulfuric acid is 3 mol or more relative to resorcinol.
O 3 high selectivity by containing a can be performed 2,4,6-position of the sulfonation of resorcinol in high yield. That is, resorcinol 2,4,6-trisulfonate can be industrially advantageously produced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 楠本 昌彦 福岡県大牟田市浅牟田町30番地 三井化学 株式会社内 Ｆターム(参考） 4H006 AA02 AC61 BC31 BE03 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahiko Kusumoto 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. F-term (reference) 4H006 AA02 AC61 BC31 BE03
Claims (3)
とによる２，４，６−トリスルホン酸レゾルシンの製造
方法。1. A method for producing resorcinol 2,4,6-trisulfonic acid by contacting resorcinol with a sulfonating agent.
徴とする請求項１記載の２，４，６−トリスルホン酸レ
ゾルシンの製造方法。2. The method for producing resorcinol 2,4,6-trisulfonate according to claim 1, wherein fuming sulfuric acid is used as the sulfonating agent.
ル倍以上の遊離のＳＯ3を含んでいることを特徴とする
請求項２記載の２，４，６−トリスルホン酸レゾルシン
の製造方法。3. The method for producing resorcinol 2,4,6-trisulfonate according to claim 2, wherein the fuming sulfuric acid used contains 3 mol or more of free SO 3 relative to resorcinol.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28905599A JP2001114748A (en) | 1999-10-12 | 1999-10-12 | Method for producing resorcinol 2,4,6-trisulfonic acid |
| US09/556,814 US6359180B1 (en) | 1999-04-30 | 2000-04-21 | Production method of 4,6-diaminoresorcin |
| KR1020000021959A KR100361998B1 (en) | 1999-04-30 | 2000-04-25 | Production method of 4,6-diaminoresorcin |
| TW89108108A TWI240719B (en) | 1999-04-30 | 2000-04-28 | Production method of 4,6-diaminoresorcin |
| CNB00117956XA CN1165521C (en) | 1999-04-30 | 2000-04-30 | Process for preparing 4,6-diamino-m-benzenediol |
| DE60002254T DE60002254T2 (en) | 1999-04-30 | 2000-05-02 | Process for the preparation of 4,6-diaminoresorcinol |
| EP00303678A EP1048644B1 (en) | 1999-04-30 | 2000-05-02 | Process for the preparation of 4,6-diaminoresorcin |
| US10/058,415 US6974881B2 (en) | 1999-04-30 | 2002-01-30 | Production method of 4,6-diaminoresorcin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28905599A JP2001114748A (en) | 1999-10-12 | 1999-10-12 | Method for producing resorcinol 2,4,6-trisulfonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001114748A true JP2001114748A (en) | 2001-04-24 |
Family
ID=17738247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28905599A Pending JP2001114748A (en) | 1999-04-30 | 1999-10-12 | Method for producing resorcinol 2,4,6-trisulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001114748A (en) |
-
1999
- 1999-10-12 JP JP28905599A patent/JP2001114748A/en active Pending
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