JPH0742334B2 - Method for producing water-soluble polystyrene sulfonic acid - Google Patents
Method for producing water-soluble polystyrene sulfonic acidInfo
- Publication number
- JPH0742334B2 JPH0742334B2 JP1996087A JP1996087A JPH0742334B2 JP H0742334 B2 JPH0742334 B2 JP H0742334B2 JP 1996087 A JP1996087 A JP 1996087A JP 1996087 A JP1996087 A JP 1996087A JP H0742334 B2 JPH0742334 B2 JP H0742334B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfonic acid
- polystyrene
- water
- polystyrene sulfonic
- halogenated hydrocarbon
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、純度の高い水溶性ポリスチレンスルホン酸を
高収率で製造する方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a highly pure water-soluble polystyrene sulfonic acid in a high yield.
ポリスチレンをスルホン化して水溶性のポリスチレンス
ルホン化物を得る方法として、ハロゲン化炭化水素溶媒
中で、クロールスルホン酸、無水硫酸又は無水硫酸と無
機あるいは有機化合物の錯体などをスルホン化剤とし、
各種架橋防止剤を併用してスルホン化する方法が知られ
ている。As a method of sulfonation of polystyrene to obtain a water-soluble polystyrene sulfonate, in a halogenated hydrocarbon solvent, chlorsulfonic acid, sulfuric anhydride or a complex of anhydrous sulfuric acid and an inorganic or organic compound as a sulfonating agent,
A method of sulfonation using various crosslinking inhibitors in combination is known.
このような方法によりポリスチレンがスルホン化される
と、得られるポリスチレンスルホン酸は反応溶媒に不溶
となり、該反応生成物をそのまま静置させるとポリスチ
レンスルホン酸が沈澱分離してくる。従って、従来から
反応溶媒は濾過、蒸留等により反応生成物から分離され
ていたが、従来の方法では、 （ｉ）濾別された固体状のポリスチレンスルホン酸のハ
ンドリングが困難でポリスチレンスルホン酸の回収率が
低下する。When polystyrene is sulfonated by such a method, the obtained polystyrenesulfonic acid becomes insoluble in the reaction solvent, and the polystyrenesulfonic acid precipitates and separates when the reaction product is left as it is. Therefore, although the reaction solvent has been conventionally separated from the reaction product by filtration, distillation, etc., in the conventional method, (i) it is difficult to handle the filtered solid polystyrene sulfonic acid, and the polystyrene sulfonic acid is recovered. The rate drops.
（ii）濾別されたポリスチレンスルホン酸は、相当量の
溶媒を含むため、用途によってはさらに溶媒の分離手段
が必要となる。(Ii) The filtered polystyrene sulfonic acid contains a considerable amount of solvent, and therefore a means for separating the solvent is required depending on the application.
（iii）溶媒に未反応ポリスチエンやスルホン基導入率
の低いポリスチレンが残存し、溶媒を再使用する場合、
溶媒を精製する必要がある。(Iii) When unreacted polystyrene or polystyrene having a low sulfone group introduction rate remains in the solvent and the solvent is reused,
The solvent needs to be purified.
（iv）装置が大型化し、エネルギーコストが高い。など
の欠点があった。(Iv) The device becomes large and the energy cost is high. There were drawbacks such as.
従って、本発明は、有機溶媒含量の少ない水溶性ポリス
チレンスルホン酸を高収率で製造でき、かつ水不溶性の
不純物を含まぬ高純度の水溶性ポリスチレンスルホン酸
を製造できる方法を提供することを目的とする。Accordingly, the present invention aims to provide a method capable of producing a water-soluble polystyrene sulfonic acid having a low organic solvent content in a high yield, and producing a high-purity water-soluble polystyrene sulfonic acid containing no water-insoluble impurities. And
本発明は、ポリスチレンをハロゲン化炭化水素溶媒中で
スルホン化して得た反応生成物中のスルホン酸に対し
て、特定量の水を添加すると、反応生成物が水層とハロ
ゲン化炭化水素とに層分離し、水溶性のポリスチレンス
ルホン酸が水層に溶解し、一方、未反応ポリスチレンや
スルホン基導入率の低いポリスチレンがそのままハロゲ
ン化炭化水素層中に残存し、所望の水溶性ポリスチレン
スルホン酸を簡易に分離できるとの知見に基づいてなさ
れたのである。The present invention, when a specific amount of water is added to the sulfonic acid in the reaction product obtained by sulfonation of polystyrene in a halogenated hydrocarbon solvent, the reaction product becomes an aqueous layer and a halogenated hydrocarbon. The layers are separated, and the water-soluble polystyrene sulfonic acid is dissolved in the water layer, while unreacted polystyrene and polystyrene with a low sulfone group introduction rate remain in the halogenated hydrocarbon layer as they are, and the desired water-soluble polystyrene sulfonic acid is obtained. This was done based on the finding that they can be easily separated.
すなわち、本発明は、平均分子量が200〜50,000のポリ
スチレンをハロゲン化炭化水素溶媒中でスルホン化した
後、原料ポリスチレン１重量部当り、次の条件（Ｉ）及
び（II）： １Ｂ20 ………（Ｉ） （式中、Ａ及びＢは、それぞれ原料ポリスチレン１重量
部当りのハロゲン化炭化水素溶媒量（重量比）及び添加
水量（重量比）を示す。） を満す量の水をスルホン化反応生成物に添加し、ポリス
チレンスルホン酸を水に溶解してハロゲン化炭化水素溶
媒と分離することを、特徴とする水溶性ポリスチレンス
ルホン酸の製造方法を提供する。That is, in the present invention, after polystyrene having an average molecular weight of 200 to 50,000 is sulfonated in a halogenated hydrocarbon solvent, the following conditions (I) and (II): 1B20 ... I) (In the formula, A and B respectively represent the amount of halogenated hydrocarbon solvent (weight ratio) and the amount of added water (weight ratio) per 1 part by weight of the raw material polystyrene). The present invention provides a method for producing a water-soluble polystyrene sulfonic acid, characterized in that the polystyrene sulfonic acid is dissolved in water to separate it from the halogenated hydrocarbon solvent.
本発明において原料として用いるポリスチレンは平均分
子量200〜50,000の範囲のものである。すなわち、平均
分子量が50,000を越えると反応系の粘度が高くなり、ハ
ンドリングが困難となるからであり、一方、平均分子量
が200未満だと、未反応スチレンモノマーの存在により
重合反応が併発して水不溶性スルホン化物の量が増大す
るからである。The polystyrene used as a raw material in the present invention has an average molecular weight of 200 to 50,000. That is, if the average molecular weight exceeds 50,000, the viscosity of the reaction system becomes high and handling becomes difficult, while if the average molecular weight is less than 200, the polymerization reaction occurs concurrently due to the presence of unreacted styrene monomer, and water is generated. This is because the amount of insoluble sulfonate increases.
本発明では上記ポリスチレンをハロゲン化炭化水素溶媒
に溶解させた後、常法によりポリスチレンをスルホン化
する。In the present invention, the polystyrene is dissolved in a halogenated hydrocarbon solvent, and then the polystyrene is sulfonated by a conventional method.
ここで用いるハロゲン化炭化水素溶媒としては、炭素数
１〜２の脂肪族ハロゲン化炭化水素が好ましく、具体的
にはメチレンジクロリド、1,2−ジクロルエタン、塩化
エチル、四塩化炭素、1,1−ジクロルエタン、1,1,2,2−
テトラクロロエタン、クロロホルム、エチレンジブロミ
ドなどのスルホン化剤に不活性なものが例示される。そ
して、該ハロゲン化炭化水素溶媒100重量部当り、ポリ
スチレンを１〜100重量部、好ましくは20〜40重量部を
添加して溶解させるのがよい。The halogenated hydrocarbon solvent used here is preferably an aliphatic halogenated hydrocarbon having 1 to 2 carbon atoms, specifically, methylene dichloride, 1,2-dichloroethane, ethyl chloride, carbon tetrachloride, 1,1- Dichloroethane, 1,1,2,2-
Examples thereof include those inert to sulfonating agents such as tetrachloroethane, chloroform and ethylene dibromide. Then, 1 to 100 parts by weight, preferably 20 to 40 parts by weight of polystyrene is added and dissolved in 100 parts by weight of the halogenated hydrocarbon solvent.
上記スルホン化に際し、スルホン化剤としてSO3を用い
るのがよい。すなわち、液状SO3、ガス状SO3、例えば窒
素ガス等の不活性ガスや脱湿空気などで希釈したガス状
SO3（希釈ガスSO3）及びハロゲン化炭化水素（好ましく
は炭素数１又は２のもの）で溶解希釈した液状SO3（希
釈液状SO3）を使用する。ここで、希釈ガスSO3として
は、SO3濃度が１〜12容量％好ましくは３〜４容量％の
ものが用いられ、希釈液状SO3としてはSO3濃度が１〜50
wt％、好ましくは５〜10wt％のものが用いられる。In the sulfonation, it is preferable to use SO 3 as a sulfonating agent. That is, liquid SO 3 or gaseous SO 3 , for example, a gaseous form diluted with an inert gas such as nitrogen gas or dehumidified air.
Liquid SO 3 (diluted liquid SO 3 ) dissolved and diluted with SO 3 (diluting gas SO 3 ) and a halogenated hydrocarbon (preferably having a carbon number of 1 or 2) is used. Examples of the dilution gas SO 3, SO 3 concentration 1 to 12% by volume preferably used those 3-4 volume%, the SO 3 concentration as a diluent liquid SO 3 1 to 50
wt%, preferably 5 to 10 wt% is used.
本発明では、上記スルホン化剤を、SO3がポリスチレン
の構成モノマー単位当り、0.7〜2.0（モル比）、好まし
くは1.0〜1.5になるような量で用いてスルホン化を行う
のがよい。In the present invention, the sulfonating agent is preferably used in an amount such that SO 3 is 0.7 to 2.0 (molar ratio), preferably 1.0 to 1.5 per monomer unit of polystyrene.
尚、スルホン化反応は任意の反応器を用いて行うことが
できるが、剪断力が0.05（N/cm2）以上の撹拌器を備え
たものを用いるのがよく、スルホン化反応を10〜80℃、
好ましくは20〜40℃で行うのがよく、原料溶液が反応器
に滞留する時間を１〜60分、好ましくは５〜40分とする
のが望ましい。The sulfonation reaction can be carried out using any reactor, but it is preferable to use a reactor equipped with an agitator having a shearing force of 0.05 (N / cm 2 ) or more, and the sulfonation reaction can be carried out at 10 to 80 ℃,
It is preferable to carry out at 20 to 40 ° C., and it is desirable that the time for which the raw material solution stays in the reactor is 1 to 60 minutes, preferably 5 to 40 minutes.
本発明では上記のようにして得たスルホン化反応生成物
に、上記式（Ｉ）及び（II）を満す量の水を添加して撹
拌する。In the present invention, the sulfonation reaction product obtained as described above is added with water in an amount satisfying the above formulas (I) and (II) and stirred.
ここで式（Ｉ）中、Ｂとしては５〜15が好ましく、式
（II）中、 は、40〜47が好ましい。In the formula (I), B is preferably 5 to 15, and in the formula (II), Is preferably 40 to 47.
本発明では、特に式（Ｉ）に示すように水の添加量Ｂが
１未満では乳化がはげしく水層と有機溶媒層との分離が
困難であり、一方、Ｂが20を越えると装置が大きくなっ
て効率的ではない。又、式（II）に示すように、値が35
〜50の範囲外となると水溶性ポリスチレンスルホン酸の
分離効率が低下する。In the present invention, particularly as shown in the formula (I), when the addition amount B of water is less than 1, emulsification is violent and it is difficult to separate the water layer and the organic solvent layer, while when B exceeds 20, the apparatus becomes large. Is not efficient. Also, as shown in formula (II), the value is 35
If it is out of the range of -50, the separation efficiency of the water-soluble polystyrene sulfonic acid decreases.
本発明で用いる水としては、温度が10〜80℃好ましくは
30〜40℃のものがよい。つまり、水の温度が10℃以下で
は固体状に分散しているポリスチレンスルホン酸が水に
溶解しにくく、一方、80℃以上ではポリスチレンスルホ
ン酸の色調が悪くなり、副反応物の生成等が起こりやす
くなるからである。The water used in the present invention preferably has a temperature of 10 to 80 ° C.
30-40 ° C is recommended. That is, when the temperature of water is 10 ° C or lower, the polystyrenesulfonic acid dispersed in a solid state is difficult to dissolve in water, while when the temperature is 80 ° C or higher, the color tone of the polystyrenesulfonic acid becomes poor, and the formation of by-products occurs. Because it will be easier.
本発明では、上記分離に際し、水を添加した反応混合物
の温度を20〜50℃好ましくは30〜40℃にコントロールし
つつ撹拌して、ポリスチレンスルホン酸を水層に溶解す
るのがよい。水に溶解したポリスチレンスルホン酸と溶
媒とは比重差で分離し、たとえば、静置分離により上層
のポリスチレンスルホン酸水溶液と下層の溶媒とに２層
分離し、常法によりポリスチレンスルホン酸水溶液のみ
を取り出す。In the present invention, in the separation, it is preferable that the temperature of the reaction mixture containing water is controlled at 20 to 50 ° C., preferably 30 to 40 ° C. while stirring to dissolve the polystyrene sulfonic acid in the aqueous layer. The polystyrene sulfonic acid dissolved in water and the solvent are separated by a specific gravity difference, for example, two layers are separated into an upper layer polystyrene sulfonic acid aqueous solution and a lower layer solvent by static separation, and only the polystyrene sulfonic acid aqueous solution is taken out by a conventional method. .
尚、上層として得られたポリスチレンスルホン酸水溶液
をそのままアルカリで中和して水溶性ポリスチレンスル
ホン酸塩を得ることが出来る。ここで用いるアルカリと
しては苛性ソーダ、苛性カリ等のアルカリ金属の水酸化
物又は炭酸塩、又は水酸化マグネシウム、水酸化カルシ
ウム等のアルカリ土類金属の水酸化物又は炭酸塩、若し
くは水酸化アンモニウム、アルカノールアミン等があげ
られる。中和は常法により行うことができる。The aqueous solution of polystyrene sulfonic acid obtained as the upper layer can be neutralized as it is with an alkali to obtain a water-soluble polystyrene sulfonate. Examples of the alkali used here include hydroxides or carbonates of alkali metals such as caustic soda and potassium hydroxide, hydroxides or carbonates of alkaline earth metals such as magnesium hydroxide and calcium hydroxide, or ammonium hydroxide and alkanolamines. Etc. Neutralization can be performed by a conventional method.
本発明によれば、有機溶媒含量が少なくかつ純度の高い
水溶性ポリスチレンスルホン酸を高い収率で製造できる
うえ、従来の欠陥である使用した有機溶媒の精製工程が
不要となるので、本発明の製造方法は工業的に極めて有
利な方法である。According to the present invention, water-soluble polystyrene sulfonic acid having a low organic solvent content and high purity can be produced in a high yield, and the purification step of the used organic solvent, which is a conventional defect, is not required. The manufacturing method is an industrially extremely advantageous method.
従って、本方法により得られたポリスチレンスルホン酸
又はその塩は、紙の帯電防止剤、コンクリート減水剤、
分散剤などとして幅広く利用される。Therefore, polystyrene sulfonic acid or a salt thereof obtained by this method is an antistatic agent for paper, a concrete water reducing agent,
Widely used as a dispersant.
次に実施例により本発明を説明するが、本発明はこれに
限定されるものではない。Next, the present invention will be described with reference to examples, but the present invention is not limited thereto.
実施例 平均分子量4,000又は10,000のポリスチレン50gを1,2ジ
クロルエタン溶媒に溶解したものを原料とし、液状SO3
をスルホン化剤として撹拌機付きのスルホン化反応器
中、SO3モル比1.1反応温度30℃でスルホン化を行った。
スルホン化終了後、スルホン酸を含む溶媒に所定量の水
を添加し、30℃で撹拌後、静置分離を行ない上層よりス
ルホン酸水溶液を得た。Example 50g of polystyrene having an average molecular weight of 4,000 or 10,000 was dissolved in 1,2 dichloroethane solvent as a raw material, and liquid SO 3
Was used as a sulfonating agent in a sulfonation reactor equipped with a stirrer at a SO 3 molar ratio of 1.1 at a reaction temperature of 30 ° C.
After the completion of the sulfonation, a predetermined amount of water was added to the solvent containing sulfonic acid, and the mixture was stirred at 30 ° C., and then statically separated to obtain an aqueous sulfonic acid solution from the upper layer.
これに水酸化カルシウムの40％水分散液をpH2になる様
に加え30分撹拌後、苛性ソーダにてpH7〜7.5に調整し、
ポリスチレンスルホン酸のCa塩を得た。実験条件及び結
果をまとめて表−１に示す。尚、表−中Ａ及びＢは、そ
れぞれ原料ポリスチレン１重量部当りの1,2−ジクロル
エタン量と添加した水の量を示す。To this, add 40% aqueous dispersion of calcium hydroxide to pH 2 and stir for 30 minutes, then adjust to pH 7-7.5 with caustic soda,
A Ca salt of polystyrene sulfonic acid was obtained. The experimental conditions and results are summarized in Table-1. In the table, A and B respectively represent the amount of 1,2-dichloroethane and the amount of added water per 1 part by weight of the raw material polystyrene.
Claims (1)
をハロゲン化炭化水素溶媒中でスルホン化した後、原料
ポリスチレン１重量部当り、次の条件（Ｉ）及び（I
I）： １Ｂ20 ………（Ｉ） （式中、Ａ及びＢは、それぞれ原料ポリスチレン１重量
部当りのハロゲン化炭化水素溶媒量（重量比）及び添加
水量（重量比）を示す。） を満す量の水をスルホン化反応生成物に添加し、ポリス
チレンスルホン酸を水に溶解してハロゲン化炭化水素溶
媒と分離することを、特徴とする水溶性ポリスチレンス
ルホン酸の製造方法。1. A polystyrene having an average molecular weight of 200 to 50,000 is sulfonated in a halogenated hydrocarbon solvent, and the following conditions (I) and (I) are added per 1 part by weight of the raw material polystyrene.
I): 1B20 ......... (I) (In the formula, A and B respectively represent the amount of halogenated hydrocarbon solvent (weight ratio) and the amount of added water (weight ratio) per 1 part by weight of the raw material polystyrene). A method for producing a water-soluble polystyrene sulfonic acid, characterized in that the polystyrene sulfonic acid is dissolved in water to separate it from the halogenated hydrocarbon solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1996087A JPH0742334B2 (en) | 1987-01-30 | 1987-01-30 | Method for producing water-soluble polystyrene sulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1996087A JPH0742334B2 (en) | 1987-01-30 | 1987-01-30 | Method for producing water-soluble polystyrene sulfonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63189404A JPS63189404A (en) | 1988-08-05 |
| JPH0742334B2 true JPH0742334B2 (en) | 1995-05-10 |
Family
ID=12013763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1996087A Expired - Lifetime JPH0742334B2 (en) | 1987-01-30 | 1987-01-30 | Method for producing water-soluble polystyrene sulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742334B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641487B2 (en) * | 1989-05-11 | 1994-06-01 | 三洋化成工業株式会社 | Method for producing aqueous solution of sulfonated polymer |
| AU678732B2 (en) * | 1994-11-14 | 1997-06-05 | Lion Corporation | Coherent method for preparing water-soluble sulfonated polymer |
| CN109336445A (en) * | 2018-12-13 | 2019-02-15 | 山东万山化工有限公司 | Production device and production method for improving sulfonation reaction efficiency in the production of naphthalene-based water reducing agent |
| CN115180862B (en) * | 2022-08-09 | 2023-08-08 | 佛山建发东方雨虹建材科技有限公司 | Preparation method of high-quality lignosulfonate water reducer |
-
1987
- 1987-01-30 JP JP1996087A patent/JPH0742334B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63189404A (en) | 1988-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2008303401A (en) | Process for bromination of polystyrene resin | |
| US10669231B2 (en) | Method for producing 2-acrylamido-2-methylpropane sulphonic acid | |
| JP3166215B2 (en) | Method for producing 1,2-naphthoquinonediazide-5-sulfonyl chloride | |
| JPH0742334B2 (en) | Method for producing water-soluble polystyrene sulfonic acid | |
| EP0564081B1 (en) | Production of an organic salt of a rare earth metal | |
| CN1398852A (en) | Prepn of methallyl sulfonate | |
| US2821549A (en) | Production of nuclear sulfonated vinyl aromatic compounds | |
| JP3159753B2 (en) | Method for producing arylimidoalkane peracid | |
| CN103097349B (en) | The purification of fluorine-containing paraffin sulfonate | |
| JPH0742335B2 (en) | Method for producing alkaline earth metal salt of polystyrene sulfonate | |
| US4739117A (en) | Process for the isolation of diaryl guanidines | |
| JPS5823388B2 (en) | Process for producing 2-amino-1-naphthalenesulfonic acid | |
| JPH0782207A (en) | Production of fluorenone and oxidation catalyst used therein | |
| EP0029242B1 (en) | Process for producing a mixed halogen-containing polycarbonate resin | |
| JP2877154B2 (en) | Method for producing 2,2-dimethoxy-2-phenylacetophenone | |
| JPS63172703A (en) | Continuous sulfonation method for polystyrene | |
| JP3203298B2 (en) | Integrated production method of water-soluble sulfonated polymer | |
| JP2712694B2 (en) | Process for producing phenylchlorothioformates | |
| US4671903A (en) | Sulfonation method of polystyrene | |
| JPS63189407A (en) | Method for producing water-soluble polystyrene sulfonic acid | |
| JPH0582401B2 (en) | ||
| JP2001058968A (en) | Method for producing 1,3-di (2-p-hydroxyphenyl-2-propyl) benzene | |
| JP2808696B2 (en) | Method for producing thiophosgene | |
| JPS63189406A (en) | Method for producing water-soluble polystyrene sulfonic acid | |
| JPH0533695B2 (en) |